Electrochromic automobile rearview mirror packaging structure and preparation method thereof

Abstract

This invention belongs to the field of electrochromic materials technology, and relates to an electrochromic automotive rearview mirror encapsulation structure and its preparation method. The electrochromic automotive rearview mirror encapsulation structure includes a substrate, a transparent conductive layer, an amyloid protein composite electrochromic layer, a starch-based solid electrolyte layer, an ion storage layer, a protective transparent conductive layer, and a starch-based encapsulation layer, stacked sequentially. This invention introduces a multi-layered structure of an amyloid protein composite system, effectively improving the fatigue resistance and weather resistance of the electrochromic layer, enhancing the mechanical strength and corrosion resistance of the electrodes, optimizing electrolyte stability and sealing barrier properties, and simultaneously improving visual consistency.

Description

Technical Field

[0001] This invention belongs to the field of electrochromic materials technology, and relates to an electrochromic automotive rearview mirror encapsulation structure and its preparation method. Background Technology

[0002] Electrochromic rearview mirrors achieve dynamic anti-glare functionality by reversibly changing the optical properties of electrochromic materials under voltage, making them a key component for improving driving safety. Their core structure typically includes a substrate, a transparent conductive layer, an electrochromic layer, an electrolyte layer, an ion storage layer, and an encapsulation layer. The working principle is as follows: under voltage, ions migrate from the ion storage layer through the electrolyte to the electrochromic layer, triggering a redox reaction that alters the material's light absorption / reflection characteristics, thus achieving anti-glare adjustment.

[0003] With the development of automotive intelligence, higher requirements are being placed on the long-term reliability, extreme environment adaptability, and visual experience of rearview mirrors. Currently, the mainstream electrochromic rearview mirror technology in the industry is an "inorganic material + solid electrolyte" system. Its core layers consist of: a substrate, an ITO transparent conductive layer, a WO3 inorganic electrochromic layer, a Li⁺ solid gel electrolyte layer, a NiO ion storage layer, another ITO transparent conductive layer, and a silicone rubber encapsulation layer. Its working principle is as follows: WO3, as the cathodic color-changing material, undergoes a reduction reaction at +1.5V, changing from a transparent state to blue; under reverse voltage, Li⁺ is released, restoring the transparent state. In this system's process, the WO3 layer is prepared by magnetron sputtering, the electrolyte is a polyethylene oxide gel electrolyte, and encapsulation relies on silicone rubber edge sealing.

[0004] However, existing material systems still have the following drawbacks: 1. Poor stability of the electrochromic layer: Pure WO3 inorganic layer has a brittle structure, and grain boundary cracking easily occurs after repeated ion insertion / extraction. (The text abruptly ends here, likely due to an incomplete sentence or missing information.) 4 The transmittance adjustment range decreases by more than 30% after each use; it is also sensitive to humidity, and ion migration channels are easily blocked in high humidity environments; secondly, the electrode protection is insufficient: the surface hardness of the ITO layer is low, the number of abrasion cycles is less than 500, and it is easily corroded by rainwater and car wash liquid. Local open circuits appear after 24 hours of salt spray testing; thirdly, electrolyte and sealing defects: the gel electrolyte is greatly affected by temperature. At -20℃, the ionic conductivity drops to 1 / 5 of the room temperature, resulting in a delayed color change response; the silicone rubber sealing layer has high water vapor permeability, which can easily cause electrolyte aging with long-term use; fourthly, the visual effect is poor: the thickness deviation of the WO3 layer prepared by magnetron sputtering is greater than 8%, resulting in obvious color difference between the edge and the center; the surface roughness of the ITO layer is high, and light reflection interference produces "rainbow pattern" light spots.

[0005] Therefore, there is an urgent need to develop an electrochromic automotive rearview mirror material system that can improve the fatigue resistance and weather resistance of the electrochromic layer, enhance the mechanical strength and corrosion resistance of the electrodes, optimize electrolyte stability and sealing barrier properties, and improve visual consistency. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide an electrochromic automotive rearview mirror encapsulation structure and its preparation method. By introducing a multi-layer structure of amyloid protein composite system, the fatigue resistance and weather resistance of the electrochromic layer are effectively improved, the mechanical strength and corrosion resistance of the electrodes are enhanced, the electrolyte stability and sealing barrier properties are optimized, and visual consistency is improved.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides an electrochromic automotive rearview mirror encapsulation structure, the electrochromic automotive rearview mirror encapsulation structure comprising a substrate, a transparent conductive layer, an amyloid protein composite electrochromic layer, a starch-based solid electrolyte layer, an ion storage layer, a protective transparent conductive layer, and a starch-based encapsulation layer stacked sequentially.

[0009] The electrochromic automotive rearview mirror encapsulation structure provided by this invention utilizes the β-sheet structure of amyloid protein to form a three-dimensional nanonetwork as a composite framework, enhancing the fatigue resistance and flexibility of the electrochromic layer; the cross-linking design of the starch-based solid electrolyte achieves high ionic conductivity and weather resistance over a wide temperature range; the protective transparent conductive layer enhances the mechanical strength and corrosion resistance of the electrodes; the "maze effect" of the starch-based encapsulation layer significantly improves the water vapor / oxygen barrier performance; through the overall starch-based composite design, it balances performance and environmental cost advantages.

[0010] Preferably, the substrate is made of at least one of transparent glass, polycarbonate, polymethyl methacrylate, or polyethylene terephthalate.

[0011] Among them, the transparent glass is preferably borosilicate glass, which has the advantages of high temperature resistance and high mechanical strength; the surface-hardened polycarbonate or polymethyl methacrylate has the advantages of being lightweight and impact-resistant.

[0012] Preferably, the transparent conductive layer comprises an ITO layer.

[0013] Preferably, the ion storage layer comprises at least one of NiO, IrO2, V2O5 or TiO2, and is preferably a NiO or NiO-V2O5 composite material, which has an ion insertion / extraction capacity that matches the electrochromic layer, can achieve charge balance, and improve cycle stability.

[0014] Preferably, based on a total mass percentage of 100 wt%, the raw material composition of the amyloid protein composite electrochromic layer includes: 10-30 wt% amyloid protein, 0.05-0.4 wt% dispersant, and the balance being inorganic electrochromic nanoparticles.

[0015] The amyloid protein composite electrochromic layer provided by this invention utilizes the β-sheet structure of amyloid protein to form a three-dimensional nanonetwork that encapsulates inorganic electrochromic nanoparticles. The β-sheet network framework can buffer the stress of repeated expansion / contraction of nanoparticles and reduce cracking. At the same time, the hydroxyl groups of amyloid protein form hydrogen bonds with the inorganic electrochromic nanoparticles, which can improve the interfacial stability.

[0016] The amyloid protein composite electrochromic layer contains 10-30 wt% amyloid protein in its raw material composition. For example, it can be 10 wt%, 15 wt%, 20 wt%, 25 wt%, or 30 wt%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0017] The mass percentage of dispersant in the raw material composition of the amyloid protein composite electrochromic layer is 0.05-0.4 wt%, for example, it can be 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt% or 0.4 wt%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0018] Preferably, the dispersant comprises any one or a combination of at least two of polyethylene glycol, polyvinylpyrrolidone, or sodium dodecylbenzenesulfonate. Typical but non-limiting combinations include combinations of polyethylene glycol and polyvinylpyrrolidone, combinations of polyvinylpyrrolidone and sodium dodecylbenzenesulfonate, or combinations of polyethylene glycol, polyvinylpyrrolidone, and sodium dodecylbenzenesulfonate.

[0019] Preferably, the inorganic electrochromic nanoparticles include WO3 nanoparticles and / or Nb2O5 nanoparticles.

[0020] It should be noted that if the color change response speed needs to be prioritized in practical applications, WO3 nanoparticles are preferred; if cost or specific spectral adjustment requirements need to be considered, Nb2O5 nanoparticles or a mixture of WO3 nanoparticles and Nb2O5 nanoparticles are preferred.

[0021] Preferably, the thickness of the amyloid protein composite electrochromic layer is 100-200 nm, for example, it can be 100 nm, 120 nm, 150 nm, 180 nm or 200 nm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0022] Preferably, based on a total mass percentage of 100wt%, the raw material composition of the starch-based solid electrolyte layer includes: 80-90wt% amyloid protein, 0.4-0.6wt% glutaraldehyde crosslinking agent, and the balance being LiClO4 ion conductor.

[0023] The starch-based solid electrolyte layer provided by this invention has hydroxyl groups of amyloid protein coordinated with Li⁺, which can provide ion conduction channels; the cross-linked structure inhibits crystallization and ensures that high ionic conductivity is maintained at -40℃.

[0024] The starch-based solid electrolyte layer contains 80-90 wt% amyloid protein in its raw material composition. For example, it can be 80 wt%, 82 wt%, 85 wt%, 88 wt%, or 90 wt%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0025] The mass percentage of glutaraldehyde crosslinking agent in the raw material composition of the starch-based solid electrolyte layer is 0.4-0.6 wt%, for example, it can be 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.55 wt% or 0.6 wt%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0026] Preferably, the protective transparent conductive layer comprises a bottom layer and a top layer, wherein the bottom layer is an ITO layer and the top layer is an amyloid-graphene composite protective layer.

[0027] The protective transparent conductive layer provided by this invention uses amyloid protein as a binder phase to enhance the interfacial bonding between graphene and ITO; the graphene sheets improve mechanical strength, and the hydroxyl groups of the amyloid protein form a passivation film to resist corrosion.

[0028] Preferably, the thickness of the ITO layer is 140-160nm, for example, it can be 140nm, 145nm, 150nm, 155nm or 160nm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0029] Preferably, the thickness of the amyloid-graphene composite protective layer is 50-100 nm, for example, it can be 50 nm, 60 nm, 80 nm, 90 nm or 100 nm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0030] Preferably, based on a total mass percentage of 100 wt%, the amyloid-graphene composite protective layer contains 5-15 wt% graphene and the remainder is amyloid protein.

[0031] The graphene content in the amyloid-graphene composite protective layer is 5-15 wt%, for example, it can be 5 wt%, 8 wt%, 10 wt%, 12 wt% or 15 wt%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0032] Preferably, the starch-based encapsulation layer is an amyloid-montmorillonite composite sealant layer.

[0033] In the starch-based encapsulation layer provided by this invention, montmorillonite sheets are oriented within the starch matrix to form a "maze effect," significantly reducing water vapor / oxygen permeability; the flexibility of amyloid protein can also be adapted to curved surface encapsulation.

[0034] Preferably, based on a total mass percentage of 100 wt%, the raw material composition of the starch-based encapsulation layer includes: 20-40 wt% montmorillonite, with the remainder being amyloid protein.

[0035] The mass percentage of montmorillonite in the raw material composition of the starch-based encapsulation layer is 20-40 wt%, for example, it can be 20 wt%, 25 wt%, 30 wt%, 35 wt% or 40 wt%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0036] Secondly, the present invention provides a method for fabricating an electrochromic automotive rearview mirror encapsulation structure as described in the first aspect, the method comprising the following steps:

[0037] The electrochromic automotive rearview mirror encapsulation structure is obtained by sequentially depositing a transparent conductive layer by magnetron sputtering, a sol-gel method for depositing an amyloid protein composite electrochromic layer, a starch-based solid electrolyte layer by UV curing, an ion storage layer by magnetron sputtering, a protective transparent conductive layer by dip-coating-curing, and a starch-based encapsulation layer by adhesive coating on the surface of the substrate.

[0038] The method for preparing an electrochromic automotive rearview mirror encapsulation structure provided by this invention utilizes a sol-gel method for an amyloid protein composite electrochromic layer, an ultraviolet curing process for a starch-based solid electrolyte, and a dip-coating-curing process for a protective transparent conductive layer. By controlling reasonable process parameters, an electrochromic automotive rearview mirror encapsulation structure with good fatigue resistance and weather resistance, high mechanical strength and corrosion resistance of the electrodes, excellent electrolyte stability and sealing barrier properties, and good visual consistency can be obtained.

[0039] Preferably, the specific steps for depositing the amyloid protein composite electrochromic layer using the sol-gel method include: mixing amyloid protein with deionized water, then adding a prescribed amount of inorganic electrochromic nanoparticles and a dispersant for ultrasonic dispersion, adjusting the pH value of the mixture to obtain a sol precursor; coating the sol precursor onto a transparent conductive layer using a dip-coating method, and then sequentially performing gelation and heat treatment to form the amyloid protein composite electrochromic layer.

[0040] Preferably, the mixing temperature is 55-65℃, the rotation speed is 300-500 r / min, and the time is 30-60 min.

[0041] The mixing temperature is 55-65℃, for example, it can be 55℃, 58℃, 60℃, 62℃ or 65℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0042] The mixing speed is 300-500 r / min, for example, it can be 300 r / min, 350 r / min, 400 r / min, 450 r / min or 500 r / min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0043] The mixing time is 30-60 minutes, for example, it can be 30 minutes, 35 minutes, 40 minutes, 50 minutes or 60 minutes, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0044] Preferably, the ultrasonic dispersion power is 150-200W and the time is 60-90min.

[0045] The power of the ultrasonic dispersion is 150-200W, for example, it can be 150W, 160W, 180W, 190W or 200W, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0046] The ultrasonic dispersion time is 60-90 minutes, for example, it can be 60 minutes, 65 minutes, 70 minutes, 80 minutes or 90 minutes, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0047] Preferably, the specific steps for adjusting the pH value of the mixture include: adding anhydrous ethanol dropwise, then adjusting the pH value of the mixture to 3.5-4.5 with hydrochloric acid, and stirring at 25-30°C for 120-180 minutes.

[0048] The pH value of the mixture is adjusted to 3.5-4.5, for example, it can be 3.5, 4 or 4.5, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0049] The stirring temperature is 25-30℃, for example, it can be 25℃, 26℃, 28℃, 29℃ or 30℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0050] The stirring time is 120-180 min, for example, it can be 120 min, 140 min, 150 min, 160 min or 180 min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0051] Preferably, the volume ratio of anhydrous ethanol to deionized water is 1:(2-3), for example, it can be 1:2, 1:2.5 or 1:3, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0052] Preferably, the coating rate is 5-10 mm / s, the thickness of a single coating is 30-50 nm, and the coating is applied 1-3 times.

[0053] The coating rate is 5-10 mm / s, for example, it can be 5 mm / s, 6 mm / s, 8 mm / s, 9 mm / s or 10 mm / s, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0054] The thickness of a single coating is 30-50nm, for example, it can be 30nm, 35nm, 40nm, 45nm or 50nm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0055] The coating is applied 1-3 times, for example, once, twice or three times.

[0056] Preferably, in the coating process, the coating is pre-dried at 60-80°C for 10-15 minutes after each coating.

[0057] The pre-drying temperature is 60-80℃, for example, it can be 60℃, 65℃, 70℃, 75℃ or 80℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0058] The pre-drying time is 10-15 minutes, for example, it can be 10 minutes, 11 minutes, 12 minutes, 13 minutes or 15 minutes, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0059] Preferably, the gelation treatment is performed by standing at 40-50°C and 60-70% relative humidity for 6-8 hours.

[0060] The settling temperature is 40-50℃, for example, it can be 40℃, 42℃, 45℃, 48℃ or 50℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0061] The relative humidity for the resting period is 60-70%, for example, it can be 60%, 62%, 65%, 68% or 70%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0062] The settling time is 6-8 hours, for example, it can be 6 hours, 7 hours or 8 hours, but it is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0063] Preferably, the heat treatment is as follows: heating to 120-150℃ at a rate of 5-8℃ / min, holding at that temperature for 60-90min, and then heating to 200-250℃ at a rate of 3-5℃ / min, holding at that temperature for 120-150min.

[0064] The heating rate is 5-8℃ / min, for example, it can be 5℃ / min, 6℃ / min, 7℃ / min or 8℃ / min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0065] The endpoint of the temperature rise is 120-150℃, for example, it can be 120℃, 125℃, 130℃, 140℃ or 150℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0066] The heat preservation time is 60-90 minutes, for example, it can be 60 minutes, 65 minutes, 70 minutes, 80 minutes or 90 minutes, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0067] The heating rate is 3-5℃ / min, for example, it can be 3℃ / min, 4℃ / min or 5℃ / min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0068] The endpoint of the temperature rise is 200-250℃, for example, it can be 200℃, 210℃, 220℃, 230℃ or 250℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0069] The heat preservation time is 120-150 minutes, for example, it can be 120 minutes, 130 minutes, 140 minutes or 150 minutes, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0070] Preferably, the UV curing wavelength is 365-405 nm, and the irradiation power is 80-120 mW / cm². 2 The irradiation time is 30-60 seconds.

[0071] The curing wavelength for ultraviolet curing is 365-405nm, for example, it can be 365nm, 375nm, 385nm, 395nm or 405nm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0072] The UV curing irradiation power is 80-120 mW / cm². 2 For example, it could be 80mW / cm 2 90mW / cm 2 100mW / cm 2 110mW / cm 2 Or 120mW / cm 2 However, this does not limit the listed values; other unlisted values ​​within the range are also applicable.

[0073] The UV curing irradiation time is 30-60s, for example, it can be 30s, 35s, 40s, 50s or 60s, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0074] Preferably, the UV curing temperature is 25-35℃ and the relative humidity is ≤50%.

[0075] The UV curing temperature is 25-35℃, for example, it can be 25℃, 28℃, 30℃, 32℃ or 35℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0076] The relative humidity for UV curing is ≤50%, for example, it can be 50%, 40%, 30%, 20% or 10%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0077] Preferably, the specific steps of the dip-coating-curing method for depositing a protective transparent conductive layer include: mixing amyloid protein and graphene according to the formula amount, adding deionized water and stirring to form a dip coating solution; immersing the substrate after depositing the ion storage layer into the dip coating solution for dip coating, pulling it out and then performing pre-drying and curing in sequence; and depositing an ITO layer on the surface of the obtained amyloid protein-graphene composite protective layer by magnetron sputtering to form a protective transparent conductive layer.

[0078] Preferably, the stirring temperature is 45-55℃, the stirring speed is 200-300 r / min, and the stirring time is 40-60 min.

[0079] The stirring temperature is 45-55℃, for example, it can be 45℃, 48℃, 50℃, 52℃ or 55℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0080] The stirring speed is 200-300 r / min, for example, it can be 200 r / min, 220 r / min, 250 r / min, 280 r / min or 300 r / min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0081] The stirring time is 40-60 minutes, for example, it can be 40 minutes, 45 minutes, 50 minutes, 55 minutes or 60 minutes, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0082] Preferably, the dip coating temperature is 25-35℃ and the time is 10-20s.

[0083] The dip coating temperature is 25-35°C, for example, it can be 25°C, 28°C, 30°C, 32°C or 35°C, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0084] The dipping time is 10-20 seconds, for example, it can be 10 seconds, 12 seconds, 15 seconds, 18 seconds or 20 seconds, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0085] Preferably, the lifting rate is 3-8 mm / s, for example, it can be 3 mm / s, 4 mm / s, 5 mm / s, 6 mm / s or 8 mm / s, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0086] Preferably, the pre-drying temperature is 70-80℃ and the time is 20-30 minutes.

[0087] The pre-drying temperature is 70-80℃, for example, it can be 70℃, 72℃, 75℃, 78℃ or 80℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0088] The pre-drying time is 20-30 minutes, for example, it can be 20 minutes, 22 minutes, 25 minutes, 28 minutes or 30 minutes, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0089] If the protective transparent conductive layer is directly cured without pre-drying after dip coating, the free water in the dip coating solution will evaporate rapidly during high-temperature curing, forming defects such as pores and pinholes in the amyloid protein-graphene composite protective layer. On the one hand, this reduces the mechanical strength of the protective layer and the number of abrasion resistance cycles of the electrode. On the other hand, it damages the integrity of the passivation film, shortens the salt spray test tolerance time, and significantly reduces the corrosion resistance of the electrode. At the same time, pores increase light scattering, affecting the light transmittance and conductivity uniformity of the transparent conductive layer.

[0090] Preferably, the curing temperature is 110-130℃ and the time is 60-90 minutes.

[0091] The curing temperature is 110-130℃, for example, it can be 110℃, 115℃, 120℃, 125℃ or 130℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0092] The curing time is 60-90 minutes, for example, it can be 60 minutes, 65 minutes, 70 minutes, 80 minutes or 90 minutes, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0093] Preferably, the magnetron sputtering deposition has a power of 80-120W, a vacuum degree of 1-3Pa, and a deposition temperature of 100-150℃.

[0094] The power of the magnetron sputtering deposition is 80-120W, for example, it can be 80W, 90W, 100W, 110W or 120W, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0095] The vacuum level of the magnetron sputtering deposition is 1-3 Pa, for example, it can be 1 Pa, 2 Pa or 3 Pa, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0096] The deposition temperature of the magnetron sputtering deposition is 100-150℃, for example, it can be 100℃, 110℃, 120℃, 130℃ or 150℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0097] Preferably, the preparation steps of the starch-based encapsulation layer include: mixing amyloid protein, montmorillonite, and deionized water according to the formula to obtain an amyloid protein-montmorillonite composite sealant; applying the sealant along the edge of the substrate after depositing the protective transparent conductive layer using a dispensing method, and curing it to form a starch-based encapsulation layer.

[0098] The adhesive encapsulation method used in this invention can be adapted to the common curved surface structure of automotive rearview mirrors, which can avoid the mechanical stress generated during the lamination process that could cause the internal film layer to crack. At the same time, the adhesive layer can fill the tiny gaps between the substrate and the encapsulation cover, further improving the sealing barrier performance.

[0099] Preferably, the mixing temperature is 50-60℃, the rotation speed is 300-400 r / min, and the time is 60-90 min.

[0100] The mixing temperature is 50-60℃, for example, it can be 50℃, 52℃, 55℃, 58℃ or 60℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0101] The mixing speed is 300-400 r / min, for example, it can be 300 r / min, 320 r / min, 350 r / min, 380 r / min or 400 r / min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0102] The mixing time is 60-90 minutes, for example, it can be 60 minutes, 70 minutes, 80 minutes or 90 minutes, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0103] Preferably, the width of the coated adhesive layer is 2-5 mm and the thickness is 100-200 μm.

[0104] The width of the coated adhesive layer is 2-5mm, for example, it can be 2mm, 3mm, 4mm or 5mm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0105] The thickness of the coated adhesive layer is 100-200μm, for example, it can be 100μm, 120μm, 150μm, 180μm or 200μm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0106] Preferably, the curing temperature is 80-100℃ and the time is 120-180min.

[0107] The curing temperature is 80-100℃, for example, it can be 80℃, 85℃, 90℃, 95℃ or 100℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0108] The curing time is 120-180 minutes, for example, it can be 120 minutes, 140 minutes, 150 minutes or 180 minutes, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0109] It should be noted that if the substrate is a curved rearview mirror, after coating and before curing, immediately align and attach the matching encapsulation cover plate, apply a uniform pressure of 0.1-0.3MPa, and let it stand for 30-60 minutes in an environment of 25-35℃ and relative humidity ≤60% to allow the adhesive layer to initially cure.

[0110] The pressure is 0.1-0.3 MPa, for example, it can be 0.1 MPa, 0.2 MPa or 0.3 MPa, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0111] The settling temperature is 25-35℃, for example, it can be 25℃, 30℃ or 35℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0112] The relative humidity for resting is ≤60%, for example, it can be 60%, 40% or 20%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0113] The settling time is 30-60 minutes, for example, it can be 30 minutes, 50 minutes or 60 minutes, but it is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0114] Preferably, the thickness of the transparent conductive layer is 5-12cm, for example, it can be 5cm, 8cm or 12cm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0115] Preferably, the thickness of the ion storage layer is 6-15cm, for example, it can be 6cm, 10cm or 15cm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0116] The choice of film thickness affects particle energy and film thickness uniformity. Too small a spacing can easily lead to film defects, while too large a spacing will significantly reduce the deposition rate.

[0117] In the magnetron sputtering deposition process, if a metal / oxide target is used for DC magnetron sputtering, the sputtering power is 50-300W and the power density is 1-5W / cm³. 2 If an insulated target is used for radio frequency magnetron sputtering, the sputtering power is 100-500W. The sputtering power determines the plasma density and the sputtering yield of the target material. Excessive power can easily cause the target material to overheat and the film grains to become coarse.

[0118] During the magnetron sputtering deposition process, the working pressure of the argon atmosphere is 0.1-1 Pa; for reactive sputtering, an Ar / O2 mixed gas is used with a total pressure of 0.3-0.8 Pa and an O2 content of 1-10%. The working pressure can control the mean free path of the sputtered particles. Too high a pressure will reduce the particle energy, while too low a pressure will make the plasma discharge unstable.

[0119] During the magnetron sputtering deposition process, the substrate temperature for depositing the transparent conductive layer is between room temperature and 250°C. High temperature can improve the conductivity of the film layer, but excessively high temperature can easily cause substrate deformation. The substrate temperature for depositing the ion storage layer is between 100-3500°C, which can promote thin film crystallization and enhance ion storage performance.

[0120] During the magnetron sputtering deposition process, the sputtering time is adjusted according to the target film thickness. The pre-sputtering time for metal targets is 5-15 min, and the pre-sputtering time for ceramic targets is 10-30 min, used to remove the oxide layer on the target surface.

[0121] During the magnetron sputtering deposition process, the magnetic field strength on the target surface is 50-300 mT. A suitable magnetic field strength can constrain electron movement, increase plasma density, and enhance sputtering efficiency and film thickness uniformity.

[0122] The process parameters involved in the above magnetron sputtering are conventional parameters, and those skilled in the art can make adaptive selections according to the actual application scenario. This invention will not elaborate further.

[0123] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0124] Compared with the prior art, the present invention has the following beneficial effects:

[0125] The electrochromic automotive rearview mirror encapsulation structure provided by this invention utilizes the β-sheet structure of amyloid protein to form a three-dimensional nanonetwork as a composite framework, enhancing the fatigue resistance and flexibility of the electrochromic layer, with a performance degradation rate as low as below 10%. The cross-linking design of the starch-based solid electrolyte achieves high ionic conductivity and weather resistance at low temperatures, with an ionic conductivity exceeding 6.8% at -40℃, enabling it to adapt to high temperature, high humidity, and ultraviolet environments. The protective transparent conductive layer enhances the mechanical strength and corrosion resistance of the electrodes, increasing the electrode's abrasion resistance to over 950 cycles and salt spray test tolerance to over 650 hours. The "maze effect" of the starch-based encapsulation layer significantly improves water vapor / oxygen barrier performance, with a water vapor permeability as low as 1.5 g / (m²). 2 The film thickness deviation is below 3.2% (days) and the whole system starch-based composite design takes into account both performance and environmental cost advantages. Detailed Implementation

[0126] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0127] Example 1

[0128] This embodiment provides an electrochromic automotive rearview mirror encapsulation structure, which includes a borosilicate glass substrate, an ITO layer, an amyloid protein composite electrochromic layer, a starch-based solid electrolyte layer, a NiO ion storage layer, a protective transparent conductive layer, and an amyloid protein-montmorillonite composite sealant layer stacked sequentially.

[0129] Based on a total mass percentage of 100 wt%, the raw material composition of the amyloid protein composite electrochromic layer includes: 20 wt% amyloid protein, 0.2 wt% polyethylene glycol, and the balance being WO3 nanoparticles; the thickness of the amyloid protein composite electrochromic layer is 150 nm; based on a total mass percentage of 100 wt%, the raw material composition of the starch-based solid electrolyte layer includes: 85 wt% amyloid protein, 0.5 wt% glutaraldehyde crosslinking agent, and the balance being LiClO4 ion conductor; The protective transparent conductive layer comprises a bottom layer and a top layer. The bottom layer is an ITO layer with a thickness of 150 nm, and the top layer is an amyloid-graphene composite protective layer with a thickness of 80 nm. Based on a total mass percentage of 100 wt%, the amyloid-graphene composite protective layer contains 10 wt% graphene and the remainder is amyloid protein. Based on a total mass percentage of 100 wt%, the amyloid-montmorillonite composite sealant layer comprises 30 wt% montmorillonite and the remainder is amyloid protein.

[0130] The fabrication method of the electrochromic automotive rearview mirror encapsulation structure includes the following steps:

[0131] An ITO layer was deposited on the surface of a borosilicate glass substrate using magnetron sputtering, followed by the deposition of an amyloid-based electrochromic layer using a sol-gel method. The specific steps included: mixing amyloid-based protein with deionized water at 60°C, a rotation speed of 500 rpm, and a time of 50 min; then adding the prescribed amount of inorganic electrochromic nanoparticles and polyethylene glycol for ultrasonic dispersion at 180 W for 70 min; adding anhydrous ethanol dropwise at a volume ratio of 1:2.5 (ethanol to deionized water); adjusting the pH of the mixture to 4 with hydrochloric acid; and stirring at 28°C for 150 min. A sol precursor was obtained. The sol precursor was coated onto a transparent conductive layer using a dip-coating method at a rate of 8 mm / s, with a single coating thickness of 40 nm. Two coatings were applied, and each coating was pre-dried at 70 °C for 12 min after each coating. The layer was then allowed to stand at 45 °C and 65% relative humidity for 7 h. The temperature was then increased to 130 °C at a rate of 6 °C / min and held for 70 min, followed by an increase to 220 °C at a rate of 4 °C / min and a holding time of 140 min. Finally, a starch-based solid electrolyte layer was deposited using UV curing at a wavelength of 385 nm and an irradiation power of 100 mW / cm². 2 The irradiation time was 40 seconds, the UV curing temperature was 30°C, and the relative humidity was 30%. A NiO ion storage layer was deposited using magnetron sputtering, followed by a protective transparent conductive layer deposited using a dip-coating-curing method. The specific steps included: mixing amyloid protein and graphene according to the formula, adding deionized water, stirring at 50°C, rotating at 250 r / min for 50 minutes to form a dip-coating solution; immersing the substrate with the deposited ion storage layer into the dip-coating solution at 30°C for 15 seconds, then pulling it out at a rate of 5 mm / s, followed by pre-drying at 75°C for 25 minutes and curing at 120°C for 70 minutes to obtain the amyloid protein-graphite composite. The surface of the olefin composite protective layer is deposited with an ITO layer by magnetron sputtering at a power of 100W, a vacuum of 2Pa, and a deposition temperature of 120℃ to form a protective transparent conductive layer. Finally, a starch-based encapsulation layer is coated by adhesive method. The preparation steps include: mixing amyloid protein, montmorillonite, and deionized water according to the formula, at a temperature of 55℃, a rotation speed of 350r / min, and a time of 70min to obtain an amyloid protein-montmorillonite composite sealant; applying the sealant along the edge of the substrate after the deposition of the protective transparent conductive layer by dispensing method, with a coating width of 3mm and a thickness of 150μm; curing at 90℃ for 160min to obtain the electrochromic automotive rearview mirror encapsulation structure.

[0132] Example 2

[0133] This embodiment provides an electrochromic automotive rearview mirror encapsulation structure, which includes a borosilicate glass substrate, an ITO layer, an amyloid protein composite electrochromic layer, a starch-based solid electrolyte layer, a NiO ion storage layer, a protective transparent conductive layer, and an amyloid protein-montmorillonite composite sealant layer stacked sequentially.

[0134] Based on a total mass percentage of 100 wt%, the raw material composition of the amyloid protein composite electrochromic layer includes: 10 wt% amyloid protein, 0.05 wt% polyvinylpyrrolidone, and the balance being WO3 nanoparticles; the thickness of the amyloid protein composite electrochromic layer is 100 nm; based on a total mass percentage of 100 wt%, the raw material composition of the starch-based solid electrolyte layer includes: 80 wt% amyloid protein, 0.4 wt% glutaraldehyde crosslinking agent, and the balance being LiClO4 ion conductor; The protective transparent conductive layer comprises a bottom layer and a top layer. The bottom layer is an ITO layer with a thickness of 140 nm, and the top layer is an amyloid-graphene composite protective layer with a thickness of 50 nm. Based on a total mass percentage of 100 wt%, the amyloid-graphene composite protective layer contains 5 wt% graphene and the remainder is amyloid protein. Based on a total mass percentage of 100 wt%, the amyloid-montmorillonite composite sealant layer comprises 20 wt% montmorillonite and the remainder is amyloid protein.

[0135] The fabrication method of the electrochromic automotive rearview mirror encapsulation structure includes the following steps:

[0136] An ITO layer was deposited on the surface of a borosilicate glass substrate using magnetron sputtering, followed by the deposition of an amyloid-based electrochromic layer using a sol-gel method. The specific steps included: mixing amyloid-based protein with deionized water at 55°C, a rotation speed of 300 rpm, and a time of 60 min; then adding the prescribed amount of inorganic electrochromic nanoparticles and polyvinylpyrrolidone for ultrasonic dispersion at 150 W for 90 min; adding anhydrous ethanol dropwise at a volume ratio of 1:2 (ethanol to deionized water); adjusting the pH of the mixture to 3.5 with hydrochloric acid; and stirring at 25°C for 180 min. The sol precursor was obtained by dip coating. The sol precursor was then coated onto a transparent conductive layer using a dip-coating method at a rate of 5 mm / s, with a single coating thickness of 30 nm. Three coatings were applied, and each coating was pre-dried at 60 °C for 15 min after each coating. The layer was then allowed to stand at 40 °C and 60% relative humidity for 8 h. The temperature was then increased to 120 °C at a rate of 5 °C / min and held for 90 min, followed by an increase to 200 °C at a rate of 3 °C / min and a holding time of 150 min. Finally, a starch-based solid electrolyte layer was deposited using UV curing at a wavelength of 365 nm and an irradiation power of 80 mW / cm². 2The irradiation time was 60 seconds, the UV curing temperature was 25°C, and the relative humidity was 40%. A NiO ion storage layer was deposited using magnetron sputtering, followed by a protective transparent conductive layer deposited using a dip-coating-curing method. Specific steps included: mixing amyloid protein and graphene according to the formula, adding deionized water and stirring at 45°C, 200 r / min, for 60 minutes to form a dip-coating solution; immersing the substrate with the deposited ion storage layer into the dip-coating solution at 25°C for 20 seconds, then pulling it out at a rate of 3 mm / s, followed by pre-drying at 70°C for 30 minutes and curing at 110°C for 90 minutes to obtain the amyloid protein-graphene composite layer. The surface of the graphene composite protective layer is deposited with an ITO layer by magnetron sputtering at a power of 80W, a vacuum of 1Pa, and a deposition temperature of 100℃ to form a protective transparent conductive layer. Finally, a starch-based encapsulation layer is coated using an adhesive method. The preparation steps include: mixing amyloid protein, montmorillonite, and deionized water according to the formula, at a temperature of 50℃, a rotation speed of 300r / min, and a time of 90min to obtain an amyloid protein-montmorillonite composite sealant; applying the sealant along the edge of the substrate after the deposition of the protective transparent conductive layer using a dispensing method, with a coating width of 2mm and a thickness of 100μm; curing at 80℃ for 180min to obtain the electrochromic automotive rearview mirror encapsulation structure.

[0137] Example 3

[0138] This embodiment provides an electrochromic automotive rearview mirror encapsulation structure, which includes a polymethyl methacrylate substrate, an ITO layer, an amyloid protein composite electrochromic layer, a starch-based solid electrolyte layer, a NiO-V2O5 ion storage layer, a protective transparent conductive layer, and an amyloid protein-montmorillonite composite sealant layer stacked sequentially.

[0139] Based on a total mass percentage of 100 wt%, the raw material composition of the amyloid protein composite electrochromic layer includes: 30 wt% amyloid protein, 0.4 wt% sodium dodecylbenzenesulfonate, and the balance being WO3 nanoparticles; the thickness of the amyloid protein composite electrochromic layer is 200 nm; based on a total mass percentage of 100 wt%, the raw material composition of the starch-based solid electrolyte layer includes: 90 wt% amyloid protein, 0.6 wt% glutaraldehyde crosslinking agent, and the balance being LiClO4 ion conductor; The protective transparent conductive layer comprises a bottom layer and a top layer. The bottom layer is an ITO layer with a thickness of 160 nm, and the top layer is an amyloid-graphene composite protective layer with a thickness of 100 nm. Based on a total mass percentage of 100 wt%, the amyloid-graphene composite protective layer contains 15 wt% graphene and the remainder is amyloid protein. Based on a total mass percentage of 100 wt%, the amyloid-montmorillonite composite sealant layer comprises 40 wt% montmorillonite and the remainder is amyloid protein.

[0140] The fabrication method of the electrochromic automotive rearview mirror encapsulation structure includes the following steps:

[0141] An ITO layer was deposited on the surface of a polymethyl methacrylate substrate using magnetron sputtering, followed by the deposition of an amyloid-based electrochromic layer using a sol-gel method. The specific steps included: mixing amyloid protein with deionized water at 65°C, a rotation speed of 500 rpm, and a time of 30 min; then adding the prescribed amount of inorganic electrochromic nanoparticles and sodium dodecylbenzenesulfonate for ultrasonic dispersion at 200 W for 60 min; adding anhydrous ethanol dropwise at a volume ratio of 1:3 (ethanol to deionized water); adjusting the pH of the mixture to 4.5 with hydrochloric acid; and stirring at 30°C for 12 minutes. The sol precursor was obtained after 0 min. It was then coated onto a transparent conductive layer using a dip-coating method at a rate of 10 mm / s, with a single coating thickness of 50 nm. The coating was performed once, followed by pre-drying at 80 °C for 10 min after each coating. The layer was then allowed to stand at 50 °C and 70% relative humidity for 6 h. The temperature was then increased to 150 °C at a rate of 8 °C / min and held for 60 min, followed by an increase to 250 °C at a rate of 5 °C / min and a holding time of 120 min. Finally, a starch-based solid electrolyte layer was deposited using UV curing at a wavelength of 405 nm and an irradiation power of 120 mW / cm². 2The irradiation time was 30 seconds, the UV curing temperature was 35°C, and the relative humidity was 50%. A NiO-V₂O₅ ion storage layer was deposited using magnetron sputtering, followed by a protective transparent conductive layer deposited using a dip-coating-curing method. Specific steps included: mixing amyloid protein and graphene according to the formula, adding deionized water and stirring at 55°C, 300 rpm for 40 minutes to form a dip-coating solution; immersing the substrate with the deposited ion storage layer into the dip-coating solution at 35°C for 10 seconds, then pulling it out at a rate of 8 mm / s, followed by pre-drying at 80°C for 20 minutes and curing at 130°C for 60 minutes to obtain the amyloid protein-... The surface of the graphene composite protective layer is deposited with an ITO layer by magnetron sputtering at a power of 120W, a vacuum of 3Pa, and a deposition temperature of 150℃, forming a protective transparent conductive layer. Finally, a starch-based encapsulation layer is coated using an adhesive method. The preparation steps include: mixing amyloid protein, montmorillonite, and deionized water according to the formula, at a temperature of 60℃, a rotation speed of 400r / min, and a time of 60min to obtain an amyloid protein-montmorillonite composite sealant; applying the sealant along the edge of the substrate after the deposition of the protective transparent conductive layer using a dispensing method, with a coating width of 5mm and a thickness of 200μm; curing at 100℃ for 120min to obtain the electrochromic automotive rearview mirror encapsulation structure.

[0142] Example 4

[0143] This embodiment provides an electrochromic automotive rearview mirror encapsulation structure. The difference from Embodiment 1 is that, except for adjusting the mass percentage of amyloid protein in the amyloid protein composite electrochromic layer to 5wt%, everything else is the same as in Embodiment 1.

[0144] Example 5

[0145] This embodiment provides an electrochromic automotive rearview mirror encapsulation structure. The difference from Embodiment 1 is that, except for adjusting the mass percentage of amyloid protein in the amyloid protein composite electrochromic layer to 35wt%, everything else is the same as in Embodiment 1.

[0146] Example 6

[0147] This embodiment provides an electrochromic automotive rearview mirror packaging structure. The difference from Embodiment 1 is that, except for replacing the LiClO4 ion conductor of the starch-based solid electrolyte layer with LiTFSI, everything else is the same as in Embodiment 1.

[0148] Example 7

[0149] This embodiment provides an electrochromic automotive rearview mirror encapsulation structure. The difference from Embodiment 1 is that, except for replacing the montmorillonite in the amyloid-montmorillonite composite sealant layer with nano-SiO2, everything else is the same as in Embodiment 1.

[0150] Example 8

[0151] This embodiment provides an electrochromic car rearview mirror encapsulation structure. The preparation method of the electrochromic car rearview mirror encapsulation structure differs from that of Embodiment 1 in that, except for the step of adjusting the pH value of the mixture to 3 with hydrochloric acid in the specific step of depositing the amyloid protein composite electrochromic layer by the sol-gel method, the rest is the same as that of Embodiment 1.

[0152] Example 9

[0153] This embodiment provides an electrochromic car rearview mirror encapsulation structure. The preparation method of the electrochromic car rearview mirror encapsulation structure differs from that of Embodiment 1 in that, except for the step of adjusting the pH value of the mixture to 5 with hydrochloric acid in the specific step of depositing the amyloid protein composite electrochromic layer by the sol-gel method, the rest is the same as that of Embodiment 1.

[0154] Comparative Example 1

[0155] This comparative example provides an electrochromic automotive rearview mirror encapsulation structure. The difference between this example and Example 1 is that, except for replacing the amyloid protein in the amyloid protein composite electrochromic layer with chitosan by the same mass, everything else is the same as in Example 1.

[0156] Comparative Example 2

[0157] This comparative example provides an electrochromic automotive rearview mirror packaging structure. The difference between this example and Example 1 is that, except for the protective transparent conductive layer being adjusted to a single ITO layer, the rest is the same as Example 1.

[0158] Comparative Example 3

[0159] This comparative example provides an electrochromic automotive rearview mirror encapsulation structure, including a glass substrate, an ITO transparent conductive layer, a WO3 inorganic electrochromic layer, a Li⁺ solid gel electrolyte layer, a NiO ion storage layer, an ITO transparent conductive layer, and a silicone rubber encapsulation layer stacked together.

[0160] The electrochromic automotive rearview mirror packaging structures provided in Examples 1-9 and Comparative Examples 1-3 were subjected to fatigue resistance tests. The test conditions were: room temperature (23±2℃), RH (50±5)%, ±1.5V voltage switching for color change / fading (cycle period 3min) for 10,000 consecutive tests. The attenuation was ≤10%, with no film peeling or encapsulation cracking. The results are shown in Table 1.

[0161] Weather resistance test, the method and conditions are: high temperature and high humidity cycling. The UV accelerated aging process (340nm xenon arc lamp, 0.71W / (m²·nm), 60℃ / 50%RH) was performed for 1000h, and the following criteria were determined: transmittance change ≤5%, no defects in the encapsulation layer, yellowing index ≤3, and response time change ≤10%. The results are shown in Table 1.

[0162] Mechanical strength testing was conducted using the following method: 500g of #0000 steel wool was used for friction, and the number of friction cycles was recorded. The results are shown in Table 1.

[0163] Corrosion resistance test, method conditions are: 5% NaCl salt spray (35℃, sedimentation rate 1-2 mL / (80cm)). 2 The tolerance time was tested using the h) method. The results are shown in Table 1.

[0164] Electrolyte stability (low-temperature ionic conductivity) test, the method conditions are as follows: solid gel electrolyte film (50-100μm) is kept at -40℃ for 30min, and AC impedance method (10) is used. -2 -10 6 The ionic conductivity was measured and calculated using a 10 mV (Hz, 10 mV) method. The results are shown in Table 2.

[0165] The sealing barrier test was conducted under the following conditions: water vapor permeability of a 50mm diameter sample was measured using the electrolytic sensor method over 24 hours at 38℃ / 90%RH (unit: g / (m²)). 2 The results are shown in Table 2.

[0166] The film thickness deviation was detected using the following method and conditions: a step profiler (10 μN, 0.1 mm / s) was used to measure the thickness at 9 points, and the maximum thickness deviation was calculated and recorded. The results are shown in Table 2.

[0167] Table 1

[0168]

[0169] Table 2

[0170]

[0171] As can be seen from Tables 1 and 2, the electrochromic automotive rearview mirror packaging structure provided by the present invention has the characteristics of good fatigue resistance and weather resistance, high mechanical strength and corrosion resistance of electrodes, excellent electrolyte stability and sealing barrier properties, and good visual consistency.

[0172] A comparison of Examples 1 with Examples 4 and 5 reveals that insufficient amyloid protein content in the amyloid-based electrochromic layer leads to an incomplete three-dimensional nanonetwork framework, failing to adequately encapsulate the nanoparticles. On one hand, this fails to effectively buffer the stress from repeated expansion and contraction of the electrochromic particles, increasing the film's brittleness and causing a performance degradation rate exceeding 25% after cycling, resulting in a significant decrease in fatigue resistance. On the other hand, insufficient hydrogen bonding between amyloid protein and the electrochromic particles leads to poor interfacial stability, making the particles prone to aggregation under high humidity conditions. This obstructs ion migration channels, reduces the transmittance adjustment range, and weakens the adhesion between the film and the transparent conductive layer, making long-term use prone to peeling. Excessive dosage leads to a decrease in the proportion of electrochromic active ingredients in the composite electrochromic layer, a decline in optical modulation sensitivity, and a prolonged color-changing response time exceeding 1.5 seconds (compared to approximately 0.8 seconds in Example 1). Simultaneously, excessive amyloid protein easily aggregates within the membrane, resulting in a significant increase in membrane transmittance (transparent transmittance below 85%, compared to approximately 90% in Example 1). Furthermore, it is prone to thermo-oxidative aging under high-temperature conditions, causing the membrane to yellow, deteriorate optical uniformity, and affect visual consistency. A comparison between Example 1 and Example 6 shows that using LiTFSI instead of LiClO4 ion conductors in the starch-based solid electrolyte layer can improve ionic conductivity, but this increases cost. The compatibility with amyloid protein is slightly poor. As can be seen from the comparison between Example 1 and Example 7, the use of nano-SiO2 to replace montmorillonite in the amyloid protein-montmorillonite composite sealant layer can improve the barrier properties, but the "maze effect" is weaker than that of sheet montmorillonite, requiring a higher addition amount and easily leading to increased brittleness. As can be seen from the comparison between Example 1 and Examples 8 and 9, when the pH value is below 3.5, the β-sheet structure of amyloid protein will be destroyed by strong acid, the three-dimensional network will collapse, the electrochromic particles will be unevenly dispersed, and cracks will appear in the film layer. When the pH value is above 4.5, the stability of the sol precursor decreases, it is easy to gel prematurely, and uneven film thickness will occur during the coating process, with obvious color difference between the edge and the center, resulting in poor visual effect.

[0173] A comparison of Example 1 and Comparative Example 1 shows that the use of chitosan instead of amyloid in the amyloid composite electrochromic layer results in lower β-sheet structure order than amyloid, leading to poor overall performance. A comparison of Example 1 and Comparative Example 2 shows that the use of a single ITO layer in the protective transparent conductive layer reduces the mechanical strength and corrosion resistance of the electrode. A comparison of Example 1 and Comparative Example 3 shows that the electrochromic structures used in the prior art do not perform as well as the electrochromic structure of the amyloid composite system in this application.

[0174] In summary, the electrochromic automotive rearview mirror encapsulation structure provided by this invention utilizes the β-sheet structure of amyloid protein to form a three-dimensional nanonetwork as a composite framework, enhancing the fatigue resistance and flexibility of the electrochromic layer, with a performance degradation rate as low as below 10%. The cross-linking design of the starch-based solid electrolyte achieves high ionic conductivity and weather resistance at low temperatures, with an ionic conductivity exceeding 6.8% at -40℃, enabling it to adapt to high temperature, high humidity, and ultraviolet environments. The protective transparent conductive layer enhances the mechanical strength and corrosion resistance of the electrodes, increasing the electrode's abrasion resistance to over 950 cycles and its salt spray test tolerance to over 650 hours. The "maze effect" of the starch-based encapsulation layer significantly improves water vapor / oxygen barrier performance, with a water vapor permeability as low as 1.5 g / (m²). 2 The film thickness deviation is below 3.2% (days) and the whole system starch-based composite design takes into account both performance and environmental cost advantages.

[0175] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. An electrochromic automotive rearview mirror packaging structure, characterized in that, The electrochromic automotive rearview mirror encapsulation structure includes a substrate, a transparent conductive layer, an amyloid protein composite electrochromic layer, a starch-based solid electrolyte layer, an ion storage layer, a protective transparent conductive layer, and a starch-based encapsulation layer, which are stacked sequentially.

2. The electrochromic automotive rearview mirror packaging structure according to claim 1, characterized in that, Based on a total mass percentage of 100wt%, the raw material composition of the amyloid protein composite electrochromic layer includes: 10-30wt% amyloid protein, 0.05-0.4wt% dispersant, and the balance being inorganic electrochromic nanoparticles. Preferably, the inorganic electrochromic nanoparticles include WO3 nanoparticles and / or Nb2O5 nanoparticles; Preferably, the thickness of the amyloid protein composite electrochromic layer is 100-200 nm.

3. The electrochromic automotive rearview mirror packaging structure according to claim 1 or 2, characterized in that, Based on a total mass percentage of 100wt%, the raw material composition of the starch-based solid electrolyte layer includes: 80-90wt% amyloid protein, 0.4-0.6wt% glutaraldehyde crosslinking agent, and the balance being LiClO4 ion conductor.

4. The electrochromic automotive rearview mirror packaging structure according to any one of claims 1-3, characterized in that, The protective transparent conductive layer includes a bottom layer and a top layer, wherein the bottom layer is an ITO layer and the top layer is an amyloid-graphene composite protective layer. Preferably, the thickness of the ITO layer is 140-160 nm; Preferably, the thickness of the amyloid-graphene composite protective layer is 50-100 nm; Preferably, based on a total mass percentage of 100 wt%, the amyloid-graphene composite protective layer contains 5-15 wt% graphene and the remainder is amyloid protein.

5. The electrochromic automotive rearview mirror packaging structure according to any one of claims 1-4, characterized in that, The starch-based encapsulation layer is an amyloid protein-montmorillonite composite sealant layer; Preferably, based on a total mass percentage of 100 wt%, the raw material composition of the starch-based encapsulation layer includes: 20-40 wt% montmorillonite, with the remainder being amyloid protein.

6. A method for preparing an electrochromic automotive rearview mirror encapsulation structure as described in any one of claims 1-5, characterized in that, The preparation method includes the following steps: The electrochromic automotive rearview mirror encapsulation structure is obtained by sequentially depositing a transparent conductive layer by magnetron sputtering, a sol-gel method for depositing an amyloid protein composite electrochromic layer, a starch-based solid electrolyte layer by UV curing, an ion storage layer by magnetron sputtering, a protective transparent conductive layer by dip-coating-curing, and a starch-based encapsulation layer by adhesive coating on the surface of the substrate.

7. The preparation method according to claim 6, characterized in that, The specific steps for depositing the amyloid protein composite electrochromic layer using the sol-gel method include: mixing amyloid protein with deionized water, then adding a prescribed amount of inorganic electrochromic nanoparticles and a dispersant for ultrasonic dispersion, adjusting the pH of the mixture to obtain a sol precursor; coating the sol precursor onto a transparent conductive layer using a dip-coating method, and then sequentially performing gelation and heat treatment to form the amyloid protein composite electrochromic layer; Preferably, the specific steps for adjusting the pH value of the mixture include: adding anhydrous ethanol dropwise, then adjusting the pH value of the mixture to 3.5-4.5 with hydrochloric acid, and stirring at 25-30°C for 120-180 min; Preferably, the gelation treatment is performed by standing at 40-50°C and 60-70% relative humidity for 6-8 hours; Preferably, the heat treatment is as follows: heating to 120-150℃ at a rate of 5-8℃ / min, holding at that temperature for 60-90min, and then heating to 200-250℃ at a rate of 3-5℃ / min, holding at that temperature for 120-150min.

8. The preparation method according to claim 6 or 7, characterized in that, The UV curing wavelength is 365-405nm, and the irradiation power is 80-120mW / cm². 2 The irradiation time is 30-60 seconds; Preferably, the UV curing temperature is 25-35℃ and the relative humidity is ≤50%.

9. The preparation method according to any one of claims 6-8, characterized in that, The specific steps of the dip-coating-curing method for depositing a protective transparent conductive layer include: mixing amyloid protein and graphene according to the formula amount, adding deionized water and stirring to form a dip coating solution; immersing the substrate after depositing the ion storage layer into the dip coating solution for dip coating, pulling it out and then performing pre-drying and curing in sequence; and depositing an ITO layer on the surface of the obtained amyloid protein-graphene composite protective layer by magnetron sputtering to form a protective transparent conductive layer. Preferably, the dip-coating temperature is 25-35℃ and the time is 10-20s; Preferably, the pre-drying temperature is 70-80℃ and the time is 20-30 minutes; Preferably, the curing temperature is 110-130℃ and the time is 60-90 minutes; Preferably, the magnetron sputtering deposition has a power of 80-120W, a vacuum degree of 1-3Pa, and a deposition temperature of 100-150℃.

10. The preparation method according to any one of claims 6-9, characterized in that, The preparation steps of the starch-based encapsulation layer include: mixing amyloid protein, montmorillonite and deionized water according to the formula to obtain amyloid protein-montmorillonite composite sealant; applying the sealant along the edge of the substrate after the deposition of the protective transparent conductive layer using the dispensing method; and forming the starch-based encapsulation layer after curing. Preferably, the mixing temperature is 50-60℃, the rotation speed is 300-400 r / min, and the time is 60-90 min; Preferably, the width of the coated adhesive layer is 2-5 mm and the thickness is 100-200 μm; Preferably, the curing temperature is 80-100℃ and the time is 120-180 min.

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