Electrochromic device fitting method and electrochromic device

Abstract

The invention provides an electrochromic device fitting method and an electrochromic device, and relates to the technical field of electrochromic devices.The fitting method comprises the steps that auxiliary ultraviolet radiation is impressed on the surface of an ion storage layer of a first base material and the surface of an electrochromic layer of a second base material through a soft template, and micro circular truncated cone areas of complementary structures are formed; inclining the first base material and the second base material, carrying out gradient spin-coating on the alumina sol, and forming an alumina layer in the micro-truncated cone area; performing plasma activation treatment on the aluminum oxide layer, and performing surface amination modification; coating the electrolyte precursor on the first base material, and enabling the micro circular truncated cone areas of the first base material and the second base material to be staggered, complementary and corresponding and pressed and attached to form an electrolyte layer; according to the application, through the micro circular truncated cone array, precise complementary correspondence is realized during lamination, and the covalence effect of the aluminum oxide layer is matched, so that the interlayer binding force is improved, and the problem of delamination caused by the fact that dry lamination only depends on physical adsorption is solved.

Description

Technical Field

[0001] This invention relates to the field of color-changing device technology, and in particular to a bonding method for an electrochromic device and an electrochromic device. Background Technology

[0002] Electrochromism refers to the phenomenon where the optical properties of a material (reflectivity, transmittance, absorptivity, etc.) undergo stable and reversible color changes under the influence of an applied electric field, manifesting as reversible changes in color and transparency. Due to its unique advantage of reversible controllability of optical properties, it shows broad application prospects in fields such as smart doors and windows, flexible electronic devices, and vehicle portholes. Its performance is highly dependent on the tight bonding and efficient ion transport of functional layers such as the electrochromic layer, ion storage layer, and electrolyte layer; the quality of the bonding process directly determines the mechanical stability, electrochemical performance, and lifespan of the device.

[0003] Existing electrochromic devices mostly employ dry bonding processes. Dry bonding relies on solid electrolyte membranes or adhesives to achieve interlayer bonding. Although the operation process is simple, the interlayer bonding strength depends solely on the physical adsorption of the adhesive, making it prone to delamination under long-term use or external force. Furthermore, voids easily exist at the interface between the solid electrolyte membrane and the functional layer, severely hindering ion transport efficiency. Summary of the Invention

[0004] Based on this, the purpose of the present invention is to provide a bonding method for an electrochromic device and an electrochromic device, aiming to solve at least one technical problem in the background art.

[0005] This invention provides a method for bonding an electrochromic device, the bonding method comprising: Photosensitive resins are coated on the surface of the ion storage layer of the first substrate and the surface of the electrochromic layer of the second substrate, respectively, and a micro-frustum region with a complementary structure is formed by ultraviolet radiation assisted by soft template imprinting. The photosensitive resin in the micro-frustum region is selectively removed by photolithography and etching, and the first substrate and the second substrate are tilted. Alumina sol is then gradient-coated and dried to form an alumina layer in the micro-frustum region. The alumina layer is subjected to plasma activation treatment, and surface amylation modification is performed by immersion in a modified solution, followed by removal of the remaining photosensitive resin in the non-micro frustum region. An electrolyte precursor is coated onto a first substrate. The micro-frustum regions of the first and second substrates are misaligned and complementary, and then pressed together to form an electrolyte layer. The edge of the bonded device is encapsulated using UV-curable adhesive to obtain an electrochromic device.

[0006] According to one aspect of the above technical solution, the thickness of the photosensitive resin is 1μm~5μm, the pressure of the soft template imprinting is 0.05MPa~0.5MPa, the wavelength of the ultraviolet radiation is 360nm~370nm, and the duration of the ultraviolet radiation is 20s~40s.

[0007] According to one aspect of the above technical solution, the step of depositing an alumina layer specifically includes: The steps of selectively removing the photosensitive resin from the micro-frustum regions by photolithography and etching specifically include: Photoresist is spin-coated onto the surface of photosensitive resin, and the non-micro-tectonic area is exposed to ultraviolet light. The unexposed micro-tectonic area is then developed to remove the photoresist. The thickness of the photoresist is 1μm~2μm. A micro-truncated array was obtained by removing the photosensitive resin in the micro-truncated area using oxygen plasma. The oxygen plasma flow rate was 10 sccm to 30 sccm, the power was 70 W to 90 W, the pressure was 40 Pa to 60 Pa, the etching time was 3 min to 7 min, and the micro-truncated array was arranged in hexagons with a center distance of 10 μm to 30 μm, a height of 1 μm to 5 μm, a bottom diameter of 5 μm to 10 μm, a top diameter of 3 μm to 6 μm, and a tilt angle of 70° to 80°. Soak in acetone for 8 to 12 minutes to remove the photoresist from the non-micro-tectonic areas.

[0008] According to one aspect of the above technical solution, the step of tilting the first substrate and the second substrate, gradient spin-coating alumina sol, and forming an alumina layer in the micro-frustum region after drying specifically includes: Aluminum isopropoxide was dissolved in anhydrous ethanol to form a precursor. Nitric acid solution was added dropwise under ice bath conditions to obtain alumina sol. The concentration of the precursor was 0.05 mol / L to 0.2 mol / L, the volume concentration of the nitric acid solution was 0.5% to 2%, and the molar ratio of water to aluminum isopropoxide was (2 to 4): 1. The first substrate and the second substrate are tilted at 10°~15°, and alumina sol is dripped onto the surfaces of the first substrate and the second substrate respectively. The coating is then spin-coated at 700r / min~900r / min for 10s~20s, and then the speed is increased to 2000r / min~3000r / min for 15s~25s. Repeat spin coating until the thickness of the alumina layer is 5nm~10nm; Vacuum dry at 70℃~90℃ for 25min~35min.

[0009] According to one aspect of the above technical solution, the plasma activation treatment conditions include: an argon plasma flow rate of 10 sccm to 30 sccm, a power of 40 W to 60 W, a pressure of 5 Pa to 20 Pa, and a treatment time of 2 min to 7 min.

[0010] According to one aspect of the above technical solution, the step of surface amination modification by immersion in a modified solution, followed by removal of residual photosensitive resin in the non-micro frustum region, specifically includes: Prepare an ethanol solution of 3-aminopropyltriethoxysilane with a volume fraction of 0.5%~2%, and then add 0.05wt%~0.2wt% of Tween-80 to obtain a modified solution. The first substrate and the second substrate were immersed in the modification solution for 20 min to 40 min, cleaned with anhydrous ethanol and vacuum dried to obtain an alumina layer with surface aminated modification. The photosensitive resin in the non-micro frustum region is removed by oxygen plasma, wherein the flow rate of the oxygen plasma is 10 sccm~30 sccm, the power is 70W~90W, the pressure is 40Pa~60Pa, and the etching time is 2min~7min.

[0011] According to one aspect of the above technical solution, the ion storage layer is a nickel oxide layer, and the thickness of the ion storage layer is 200nm~300nm; The electrochromic layer is a PSTU-PEDOT:PSS layer, and the thickness of the electrochromic layer is 150nm~200nm.

[0012] According to one aspect of the above technical solution, the electrolyte precursor solution includes PEGDA, [EMIM][TFSI], LiTFSI, and 4-aminobenzaldehyde, with a molar ratio of PEGDA, [EMIM][TFSI], LiTFSI, and 4-aminobenzaldehyde of (3~5):(4~6):1:(0.1~1). The molecular weight of PEGDA is 600~800, the gelation rate of the electrolyte precursor solution is 0.05mL / s~0.2mL / s, and the coating thickness of the electrolyte precursor solution is 20μm~200μm.

[0013] According to one aspect of the above technical solution, the step of applying pressure for bonding specifically includes: Vacuum pressure holding for 20s to 40s at -0.1MPa to -0.08MPa; Apply a pressure of 0.2MPa to 0.5MPa and hold for 8 to 15 minutes. Let it stand at room temperature away from light for 18 to 36 hours.

[0014] Another aspect of the present invention provides an electrochromic device, which is formed by bonding the electrochromic device using the above-described electrochromic device bonding method.

[0015] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. The first and second substrates form a hexagonal array of micro-truncated cones on their surfaces. During bonding, these cones precisely complement each other, forming a regular interlocking structure that disperses interlayer stress, prevents localized delamination, and increases the contact surface area. Combined with the covalent Schiff base bond between the amino groups of the alumina layer and the aldehyde groups of the electrolyte, this solves the delamination problem that dry bonding relies solely on physical adsorption, improves interlayer bonding, reduces interfacial resistance, and accelerates ion transport across the interface. Furthermore, the uniformly distributed gaps formed by the complementary micro-truncated cones provide directional migration paths for ions, reducing random diffusion losses.

[0016] 2. The alumina layer is prepared by gradient spin coating. The nanopores in the amorphous structure allow small molecule ions to pass through while isolating electrons, thus avoiding direct short circuit between the ion storage layer and the electrochromic layer.

[0017] 3. Vacuum pressure bonding and edge sealing processes will reduce liquid residue and bubbles, avoid local optical unevenness, and solve the problems of bubbles and gaps in wet bonding. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of the electrochromic device in this invention; In the figure: first substrate 10, second substrate 20, ion storage layer 30, electrochromic layer 40, alumina layer 50, electrolyte layer 60.

[0019] The following detailed description, in conjunction with the accompanying drawings, will further illustrate the present invention. Detailed Implementation

[0020] To facilitate understanding of the present invention, a more complete description will be given below with reference to the accompanying drawings. Several embodiments of the invention are illustrated in the drawings. However, the invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

[0021] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0022] This invention provides a method for bonding an electrochromic device, the bonding method comprising: steps S10 to S14. Step S10: Photosensitive resin is coated on the surface of the ion storage layer of the first substrate and the surface of the electrochromic layer of the second substrate, respectively, and a micro-frustum region with complementary structure is formed by ultraviolet radiation assisted by soft template imprinting. Please see Figure 1 The diagram shows the structure of the electrochromic device. Photosensitive resin is drop-coated onto the ion storage layer 30 and the electrochromic layer 40, respectively. The spin-coating rate is 700 r / min to 900 r / min, and the spin-coating time is 8 s to 12 s. The thickness of the photosensitive resin is 1 μm to 5 μm, and the viscosity is 400 mPa·s to 600 mPa·s. The material is epoxy acrylate photosensitive resin. Then, the photosensitive resin is cured by imprinting with a soft template at a pressure of 0.05MPa~0.5MPa and irradiating with ultraviolet light at a wavelength of 360nm~370nm for 20s~40s, and then the soft template is peeled off.

[0023] In addition, the soft template is made of PDMS material. The PDMS prepolymer and curing agent (such as Sylgard184 curing agent) are mixed at a mass ratio of 10:1, vacuum degassed, and cast onto the silicon wafer master mold with a thickness of 2mm. It is then cured in a 60℃ oven for 4 hours.

[0024] It should be noted that photosensitive resin has good fluidity and UV curing properties, and can completely replicate the microstructure of the template through soft template imprinting. The convex and concave complementary micro-turbines formed after curing ensure the bonding accuracy and structural stability.

[0025] Furthermore, both the first substrate 10 and the second substrate 20 are ITO-PET flexible substrates with a thickness of 0.1 mm to 0.3 mm. The ion storage layer 30 is a nickel oxide layer with a thickness of 200 nm to 300 nm; the electrochromic layer 40 is a PSTU-PEDOT:PSS layer with a thickness of 150 nm to 200 nm.

[0026] Step S11: Selectively remove the photosensitive resin in the micro-frustum region by photolithography and etching, tilt the first substrate and the second substrate, and gradient spin-coat alumina sol. After drying, an alumina layer is formed in the micro-frustum region. Specifically, photoresist is spin-coated onto the surface of photosensitive resin, the non-micro-tectonic area is exposed to ultraviolet light, and the photoresist in the unexposed micro-tectonic area is removed by development. The thickness of the photoresist is 1μm~2μm. The photosensitive resin in the micro-truncate region was removed by oxygen plasma, wherein the flow rate of the oxygen plasma was 10 sccm~30 sccm, the power was 70W~90W, the pressure was 40Pa~60Pa, and the etching time was 50s~70s. Soak in acetone for 8 to 12 minutes to remove the photoresist from the non-micro-tectonic areas.

[0027] It should be noted that the oxygen plasma decomposes the photosensitive resin into volatile substances through an oxidation reaction, etching only the micro-frustum region without photoresist protection, and finally forming a regular array of micro-frustums on the first substrate 10 and the second substrate 20, providing a substrate for the structured deposition of the alumina layer 50.

[0028] Furthermore, the alumina layer 50 deposited in the micro-frustum region serves as an insulating layer, blocking electron leakage and preventing short circuits when the micro-frustum regions between the ion storage layer 20 and the electron color-changing layer 40 are bonded together, without affecting the ion mobility.

[0029] Specifically, aluminum isopropoxide is dissolved in anhydrous ethanol to form a precursor, and nitric acid solution is added dropwise under ice bath conditions to obtain alumina sol. The concentration of the precursor is 0.05 mol / L to 0.2 mol / L, the volume concentration of the nitric acid solution is 0.5% to 2%, and the molar ratio of water to aluminum isopropoxide is (2 to 4): 1. The first substrate 10 and the second substrate 20 are tilted at 10°~15°. Alumina sol is dripped onto the surfaces of the first substrate 10 and the second substrate 20 respectively. The coating is then spin-coated at 700r / min~900r / min for 10s~20s, and then the speed is increased to 2000r / min~3000r / min for 15s~25s. Repeat spin coating until the thickness of the alumina layer 50 is 5nm~10nm; Vacuum dry at 70℃~90℃ for 25min~35min.

[0030] The alumina layer 50 is ultrathin, much thinner than the critical blocking thickness for ion transport, allowing ions to easily pass through via tunneling or pores. Furthermore, the alumina layer 50 prepared by the sol-gel method is an amorphous and dense structure, but it contains nanoscale pores (pore size of 0.5nm~2nm), which allow lithium ions and hydrogen ions to pass through.

[0031] In addition, alumina sol has poor wettability on the surface of cured photosensitive resin and is prone to agglomeration into particles, making it impossible to form a continuous and uniform film. This is to facilitate the subsequent oxygen plasma stripping of the photosensitive resin, and the tearing will not affect the alumina layer 50 on the micro-tidal array.

[0032] Step S12: The alumina layer is subjected to plasma activation treatment and surface aminated modification by immersion in a modified solution, and then the remaining photosensitive resin in the non-micro frustum region is removed. Specifically, the plasma activation treatment conditions include: an argon plasma flow rate of 10 sccm to 30 sccm, a power of 40 W to 60 W, a pressure of 5 Pa to 20 Pa, and a treatment time of 2 min to 7 min, to increase the hydroxyl density and facilitate subsequent amination.

[0033] The step of surface amination modification by immersion in a modified solution, followed by removal of residual photosensitive resin from the non-micro frustum region, specifically includes: Prepare an ethanol solution of 3-aminopropyltriethoxysilane with a volume fraction of 0.5%~2%, and then add 0.05wt%~0.2wt% of Tween-80 to obtain a modified solution. The first substrate 10 and the second substrate 20 are immersed in the modification solution for 20 min to 40 min, cleaned with anhydrous ethanol and vacuum dried to obtain an alumina layer 50 with surface aminated modification. A micro-truncated array is obtained by removing the photosensitive resin in the non-micro-truncated regions using oxygen plasma. The oxygen plasma flow rate is 10 sccm to 30 sccm, the power is 70 W to 90 W, the pressure is 40 Pa to 60 Pa, the etching time is 3 min to 7 min, the micro-truncated array is hexagonal, the center distance is 10 μm to 30 μm, the height of the micro-truncated array is 1 μm to 5 μm, the bottom diameter is 5 μm to 10 μm, the top diameter is 3 μm to 6 μm, and the tilt angle is 70° to 80°.

[0034] In this process, the surface of the alumina layer 50 is treated with argon plasma to increase the hydroxyl density, and then forms a stable Si-O-Al covalent bond with the siloxane group of 3-aminopropyltriethoxysilane, while retaining sufficient ion transport sites.

[0035] Step S13: The electrolyte precursor is coated onto the first substrate. The micro-frustum regions of the first and second substrates are misaligned and complementary and then pressed together to form an electrolyte layer by CCD visual positioning. The electrolyte precursor solution includes PEGDA, [EMIM][TFSI], LiTFSI, and 4-aminobenzaldehyde. The molar ratio of PEGDA, [EMIM][TFSI], LiTFSI, and 4-aminobenzaldehyde is (3~5):(4~6):1:(0.1~1). The molecular weight of PEGDA is 600~800. The dispensing rate of the electrolyte precursor solution is 0.05mL / s~0.2mL / s. The coating thickness of the electrolyte precursor solution is 20μm~200μm, and the thickness of the electrolyte layer 60 is 5μm~20μm.

[0036] Specifically, PEGDA, [EMIM][TFSI], LiTFSI, and 4-aminobenzaldehyde are mixed and stirred at a stirring rate of 600 r / min for 1 h, followed by vacuum degassing for 20 min.

[0037] Furthermore, the step of applying pressure to achieve adhesion specifically includes: Vacuum pressure holding for 20s to 40s at -0.1MPa to -0.08MPa; Apply a pressure of 0.2MPa to 0.5MPa and hold for 8 to 15 minutes. Allow the alumina layer 50 to stand in the dark for 18-36 hours to form Schiff base bonds (-C=N-) with the electrolyte precursor, thereby improving adhesion, reducing interfacial resistance, guiding ion transport, and further enhancing ion mobility.

[0038] Step S14: Use UV-curable adhesive to encapsulate the edge of the bonded device to obtain an electrochromic device.

[0039] Specifically, the device edge is encapsulated with UV-curable adhesive (containing Schiff base groups), with an adhesive layer width of 2mm~3mm, and cured by irradiation with 365nm UV light for 180s~300s.

[0040] Accordingly, the present invention also provides an electrochromic device, which is formed by bonding the electrochromic device using the above-described electrochromic device bonding method.

[0041] The present invention is further illustrated below with specific embodiments: Example 1 Embodiment 1 of the present invention provides a bonding method for an electrochromic device, the bonding method comprising: steps S10-S14, Step S10: Photosensitive resin is coated on the surface of the ion storage layer of the first substrate and the surface of the electrochromic layer of the second substrate, respectively, and a micro-frustum region with complementary structure is formed by ultraviolet radiation assisted by soft template imprinting. Specifically, photosensitive resin was drop-coated onto the ion storage layer and the electrochromic layer respectively, with a spin coating rate of 800 r / min and a spin coating time of 10 s. The thickness of the photosensitive resin was 3 μm, the viscosity was 500 mPa•s, and the material was epoxy acrylate photosensitive resin. Then, the photosensitive resin is cured by imprinting with a soft template at a pressure of 0.1 MPa and ultraviolet irradiation at a wavelength of 365 nm for 30 seconds, and then the soft template is peeled off.

[0042] In addition, the soft template is made of PDMS material. The PDMS prepolymer and curing agent are mixed at a mass ratio of 10:1, vacuum degassed, and cast onto the silicon wafer master mold with a thickness of 2mm. It is then cured in a 60℃ oven for 4 hours.

[0043] Furthermore, both the first and second substrates are ITO-PET flexible substrates with a thickness of 0.2 mm. The ion storage layer is a nickel oxide layer with a thickness of 250 nm (prepared by magnetron sputtering, target material Ni, argon / oxygen flow ratio 8:2, power 100 W, deposition time 30 min); the electrochromic layer is a PSTU-PEDOT:PSS layer with a thickness of 180 nm (prepared by spin coating, PSTU-PEDOT:PSS dispersion concentration 5 wt%, spin coating speed 3500 rpm, time 40 s, annealing temperature 120 °C, time 1 h).

[0044] Step S11: Selectively remove the photosensitive resin in the micro-frustum region by photolithography and etching, tilt the first substrate and the second substrate, and gradient spin-coat alumina sol. After drying, an alumina layer is formed in the micro-frustum region. Specifically, photoresist is spin-coated onto the surface of photosensitive resin, the non-micro-tectonic area is exposed to ultraviolet light, and the photoresist in the unexposed micro-tectonic area is removed by development. The thickness of the photoresist is 1.5 μm. A micro-truncated array was obtained by removing the photosensitive resin in the micro-truncated area using oxygen plasma. The oxygen plasma had a flow rate of 20 sccm, a power of 80 W, a pressure of 50 Pa, and an etching time of 60 s. The micro-truncated array was arranged in hexagons with a center-to-center distance of 12 μm, a height of 3 μm, a bottom diameter of 10 μm, and a top diameter of 1.5 μm. Soak in acetone for 10 minutes to remove the photoresist from the non-micro-tectonic areas.

[0045] Specifically, aluminum isopropoxide is dissolved in anhydrous ethanol to form a precursor, and nitric acid solution is added dropwise under ice bath conditions to obtain alumina sol. The concentration of the precursor is 0.1 mol / L, the volume concentration of the nitric acid solution is 1%, and the molar ratio of water to aluminum isopropoxide is 3:1. The first substrate and the second substrate are tilted at 13°. Alumina sol is dripped onto the surfaces of the first substrate and the second substrate respectively. The coating is then spin-coated at 800 r / min for 15 s, and then the speed is increased to 2500 r / min for 20 s. Repeat spin coating until the aluminum oxide layer is 8 nm thick; Vacuum dry at 80℃ for 30 min.

[0046] Step S12: The alumina layer is subjected to plasma activation treatment and surface aminated modification by immersion in a modified solution, and then the remaining photosensitive resin in the non-micro frustum region is removed. Specifically, the plasma activation treatment conditions include: an argon plasma flow rate of 20 sccm, a power of 50 W, a pressure of 10 Pa, and a treatment time of 5 min.

[0047] The step of surface amination modification by immersion in a modified solution, followed by removal of residual photosensitive resin from the non-micro frustum region, specifically includes: Prepare an ethanol solution of 1% (v / v) 3-aminopropyltriethoxysilane, and then add 0.1 wt% Tween-80 to obtain the modified solution. The first substrate and the second substrate were immersed in the modification solution for 30 minutes, cleaned with anhydrous ethanol and vacuum dried to obtain an alumina layer with surface aminated modification. A micro-truncated array was obtained by removing the photosensitive resin in the non-micro-truncated regions using oxygen plasma. The oxygen plasma flow rate was 20 sccm, the power was 80 W, the pressure was 50 Pa, the etching time was 5 min, and the micro-truncated array was arranged in hexagons with a center-to-center distance of 12 μm, a height of 3 μm, a bottom diameter of 8 μm, a top diameter of 5.6 μm, and a tilt angle of 75°.

[0048] Step S13: The electrolyte precursor is coated onto the first substrate. The micro-frustum regions of the first and second substrates are misaligned and complementary and then pressed together to form an electrolyte layer by CCD visual positioning. The electrolyte precursor solution comprises PEGDA, [EMIM][TFSI], LiTFSI, and 4-aminobenzaldehyde, with a molar ratio of PEGDA, [EMIM][TFSI], LiTFSI, and 4-aminobenzaldehyde of 4:4:1:0.5. The molecular weight of PEGDA is 700. The dispensing rate of the electrolyte precursor solution is 0.1 mL / s. The coating thickness of the electrolyte precursor solution is 50 μm, and the thickness of the electrolyte layer is 10 μm.

[0049] Specifically, PEGDA, [EMIM][TFSI], LiTFSI, and 4-aminobenzaldehyde are mixed and stirred at a stirring rate of 600 r / min for 1 h, followed by vacuum degassing for 20 min.

[0050] Furthermore, the step of applying pressure to achieve adhesion specifically includes: Vacuum pressure held at -0.09 MPa for 30 seconds; Apply a pressure of 0.2 MPa and hold for 10 minutes; Let stand at room temperature away from light for 24 hours.

[0051] Step S14: Use UV-curable adhesive to encapsulate the edge of the bonded device to obtain an electrochromic device.

[0052] Specifically, the device edge is encapsulated with UV-curable adhesive (containing Schiff base groups), with an adhesive layer width of 2.5 mm, and cured by irradiation with 365 nm UV light for 240 seconds.

[0053] Example 2 The second embodiment of the present invention provides a method for bonding an electrochromic device. The difference between the electrochromic device bonding method in this comparative example and the electrochromic device bonding method in the first embodiment is as follows: The thickness of the alumina layer is 5 nm.

[0054] Example 3 The third embodiment of the present invention provides a method for bonding an electrochromic device. The difference between the electrochromic device bonding method in this comparative example and the electrochromic device bonding method in the first embodiment is as follows: The thickness of the alumina layer is 10 nm.

[0055] Example 4 The present invention provides a method for bonding an electrochromic device according to Embodiment 4. The difference between the electrochromic device bonding method in this comparative example and the electrochromic device bonding method in Embodiment 1 is as follows: The plasma activation treatment time is 2 minutes.

[0056] Example 5 The present invention provides a method for bonding an electrochromic device in Embodiment 5. The difference between the electrochromic device bonding method in this comparative example and the electrochromic device bonding method in Embodiment 1 is as follows: The plasma activation treatment time is 7 minutes.

[0057] Example 6 The present invention provides a method for bonding an electrochromic device according to Embodiment Six. The difference between the electrochromic device bonding method in this comparative example and the electrochromic device bonding method in Embodiment One is as follows: The molar ratio of PEGDA, [EMIM][TFSI], LiTFSI, and 4-aminobenzaldehyde is 4:5:1:0.1.

[0058] Example 7 The present invention provides a method for bonding an electrochromic device according to Embodiment 7. The difference between the electrochromic device bonding method in this comparative example and the electrochromic device bonding method in Embodiment 1 is as follows: The molar ratio of PEGDA, [EMIM][TFSI], LiTFSI, and 4-aminobenzaldehyde is 4:5:1:1.

[0059] Example 8 The present invention provides a method for bonding an electrochromic device according to Embodiment 8. The difference between the electrochromic device bonding method in this comparative example and the electrochromic device bonding method in Embodiment 1 is as follows: The volume fraction of the ethanol solution of 3-aminopropyltriethoxysilane is 0.5%.

[0060] Example 9 The present invention provides a method for bonding an electrochromic device according to Embodiment Nine. The difference between the electrochromic device bonding method in this comparative example and the electrochromic device bonding method in Embodiment One is as follows: The volume fraction of the ethanol solution of 3-aminopropyltriethoxysilane is 2%.

[0061] Example 10 The present invention provides a method for bonding an electrochromic device according to Embodiment 10. The difference between the electrochromic device bonding method in this comparative example and the electrochromic device bonding method in Embodiment 1 is as follows: The center distance of the micro-truncations is 13μm, the height of the micro-truncations is 3μm, the bottom diameter is 7μm, the top diameter is 5.8μm, and the tilt angle is 78.5°.

[0062] Example 11 The electrochromic device bonding method provided in Embodiment Eleven of the present invention differs from the electrochromic device bonding method in Embodiment One in that: The center distance of the micro-truncates is 11 μm, the height of the micro-truncates is 3.5 μm, the bottom diameter is 9 μm, the top diameter is 5.2 μm, and the tilt angle is 72°.

[0063] Comparative Example 1 The present invention provides a method for bonding an electrochromic device in Comparative Example 1. The difference between the electrochromic device bonding method in this comparative example and the electrochromic device bonding method in the first embodiment is as follows: In areas without micro-conical frustums, traditional planar pressing and bonding is used.

[0064] Comparative Example 2 Comparative Example 2 of this invention provides a method for bonding an electrochromic device. The difference between the electrochromic device bonding method in this comparative example and the electrochromic device bonding method in the first embodiment is as follows: The microcylindrical region has a diameter of 8 μm.

[0065] Comparative Example 3 The present invention provides a method for bonding an electrochromic device in Comparative Example 3. The difference between the electrochromic device bonding method in this comparative example and the electrochromic device bonding method in the first embodiment is as follows: It has only an alumina layer, without plasma activation treatment or amination modification.

[0066] Comparative Example 4 The present invention provides a method for bonding an electrochromic device in Comparative Example 4. The difference between the electrochromic device bonding method in this comparative example and the electrochromic device bonding method in the first embodiment is as follows: Alumina layer is spin-coated at a single rotation speed of 2500 r / min for 20 s.

[0067] Comparative Example 5 Comparative Example 5 of this invention provides a method for bonding an electrochromic device. The difference between the electrochromic device bonding method in this comparative example and the electrochromic device bonding method in the first embodiment is as follows: 4-Aminobenzaldehyde is not added to the electrolyte precursor.

[0068] Please refer to Table 1 below, which shows the parameters corresponding to the above embodiments and comparative examples of the present invention. The interlaminar shear strength test method is as follows: the bonded electrochromic device is cut into a rectangular sample of 10mm × 25mm, ensuring that the interlaminar bonding area is 10mm × 10mm (only the effective bonding area is retained). At room temperature, the shear rate is 1mm / min, and the loading direction is perpendicular to the interlaminar interface. The shear strength is calculated as: maximum load (N) / bonding area (m²). 2 ), and take the average value of 5 parallel samples.

[0069] Transmittance change test (UV-Vis spectrophotometry): Cut the electrochromic device into a 20mm×20mm transparent sample, ensuring no bubbles or scratches. Test wavelength 550nm (center wavelength of visible light). Test the transmittance of the device in the faded state (applied +1.5V voltage for 30s) and colored state (applied -1.0V voltage for 30s) respectively. Calculate the transmittance change = transmittance in the faded state - transmittance in the colored state. Take the average value of the test values ​​of 5 different regions.

[0070] Cyclic stability test: The light transmittance adjustment process of the electrochromic device in actual use is simulated by cyclically applying the fading state-coloring state voltage. When the light transmittance change amplitude decays to 80% of the initial value, the cycle is stopped, the number of cycles is recorded, and the average value of 3 parallel samples is taken.

[0071] Table 1:

[0072] This invention significantly improves interlayer shear strength, light transmittance variation, and cycle stability by achieving misaligned complementary correspondence during the bonding of micro-frustum arrays, combined with the covalent Schiff base bond between the amino groups of the alumina layer and the aldehyde groups of the electrolyte.

[0073] In the description of this specification, references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0074] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. An electrochromic device lamination method, characterized by, The fitting method comprises: coating a photosensitive resin on the ion storage layer surface of the first substrate and the electrochromic layer surface of the second substrate respectively, forming a micro-dome region with complementary structure by soft template imprinting assisted by ultraviolet radiation; selectively removing the photosensitive resin of the micro-dome region by photolithography and etching, and tilting the first substrate and the second substrate, gradient spin-coating aluminum oxide sol, and forming an aluminum oxide layer in the micro-dome region after drying; carrying out plasma activation treatment on the aluminum oxide layer, and carrying out surface aminization modification by soaking in a modification solution, and then removing the remaining photosensitive resin in the non-micro-dome region; coating an electrolyte precursor on the first substrate, and making the micro-dome regions of the first substrate and the second substrate complementary to each other by CCD visual positioning, and then press-fitting to form an electrolyte layer; edge packaging the device after fitting by using ultraviolet curing glue, and obtaining an electrochromic device.

2. The electrochromic device lamination method of claim 1, wherein, The thickness of the photosensitive resin is 1-5 μm, the pressure of the soft template imprinting is 0.05-0.5 MPa, the wavelength of the ultraviolet radiation is 360-370 nm, and the time of the ultraviolet radiation is 20-40 s.

3. The electrochromic device lamination method of claim 1, wherein The step of selectively removing the photosensitive resin of the micro-dome region by photolithography and etching specifically comprises: spin-coating a photoresist on the surface of the photosensitive resin, and carrying out ultraviolet exposure on the non-micro-dome region, and then developing to remove the photoresist of the micro-dome region which is not exposed to light, wherein the thickness of the photoresist is 1-2 μm; removing the photosensitive resin of the micro-dome region by oxygen plasma to obtain a micro-dome array, wherein the flow rate of the oxygen plasma is 10-30 sccm, the power is 70-90 W, the pressure is 40-60 Pa, the etching time is 3-7 min, the micro-dome array is hexagonally arranged, the center distance is 10-30 μm, the micro-dome height is 1-5 μm, the bottom diameter is 5-10 μm, the top diameter is 3-6 μm, and the inclination angle is 70-80°; immersing in acetone for 8-12 min to remove the photoresist in the non-micro-dome region.

4. The electrochromic device lamination method of claim 1, wherein The step of tilting the first substrate and the second substrate, gradient spin-coating aluminum oxide sol, and forming an aluminum oxide layer in the micro-dome region after drying specifically comprises: dissolving aluminum isopropoxide in anhydrous ethanol to form a precursor, and adding nitric acid solution dropwise under ice bath condition to obtain aluminum oxide sol, wherein the concentration of the precursor is 0.05-0.2 mol / L, the volume concentration of the nitric acid solution is 0.5%-2%, and the molar ratio of water to aluminum isopropoxide is (2-4):1; tilting the first substrate and the second substrate by 10-15°, and drop-coating the aluminum oxide sol on the surfaces of the first substrate and the second substrate respectively, spin-coating at 700-900 r / min for 10-20 s, and then increasing the rotation speed to 2000-3000 r / min for 15-25 s; repeating the spin-coating until the thickness of the aluminum oxide layer is 5-10 nm; vacuum drying at 70-90 °C for 25-35 min.

5. The electrochromic device lamination method of claim 1, wherein The plasma activation treatment conditions include: the flow rate of argon plasma is 10-30sccm, the power is 40-60W, the pressure is 5-20Pa, and the treatment time is 2-7min.

6. The electrochromic device lamination method of claim 1, wherein, The step of surface amination modification by soaking in the modification solution and removing the remaining photosensitive resin in the non-micro-dome area specifically comprises: An ethanol solution of 3-aminopropyltriethoxysilane with a volume fraction of 0.5-2% is prepared, and 0.05wt%-0.2wt% Tween-80 is added to obtain a modification solution; The first substrate and the second substrate are soaked in the modification solution for 20-40min, cleaned with anhydrous ethanol, and vacuum dried to obtain an alumina layer with surface amination modification; The photosensitive resin in the non-micro-dome area is removed by oxygen plasma, wherein the flow rate of oxygen plasma is 10-30sccm, the power is 70-90W, the pressure is 40-60Pa, and the etching time is 2-7min.

7. The electrochromic device lamination method of claim 6, wherein, The ion storage layer is a nickel oxide layer, and the thickness of the ion storage layer is 200-300nm. The electrochromic layer is a PSTU-PEDOT:PSS layer, and the thickness of the electrochromic layer is 150-200nm.

8. The electrochromic device lamination method of claim 1, wherein, The electrolyte precursor solution comprises PEGDA, [EMIM][TFSI], LiTFSI, and 4-aminobenzaldehyde, and the molar ratio of PEGDA, [EMIM][TFSI], LiTFSI, and 4-aminobenzaldehyde is (3-5):(4-6):1:(0.1-1), the molecular weight of PEGDA is 600-800, the glue output speed of the electrolyte precursor solution is 0.05-0.2mL / s, and the coating thickness of the electrolyte precursor solution is 20-200μm.

9. The electrochromic device lamination method of claim 1, wherein, The step of applying pressure for lamination specifically comprises: Vacuum pressure is maintained at -0.1MPa to -0.08MPa for 20-40s; A pressure of 0.2-0.5MPa is applied, and the pressure is maintained for 8-15min; The device is placed in the dark at room temperature for 18-36h.

10. An electrochromic device, characterized in that, The electrochromic device is laminated by the electrochromic device lamination method of any one of claims 1-9.

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