A long-life electrochromic device with dual-ion synergistic operation and a preparation method thereof

Abstract

The application relates to a long-life electrochromic device with double-ion synergistic working and a preparation method thereof. The long-life electrochromic device with double-ion synergistic working comprises a first transparent electrode layer, an inorganic electrochromic layer, an electrolyte layer, a gel-based ion storage layer and a second transparent electrode layer which are sequentially stacked; the material of the electrolyte layer is at least one of aluminum salt, preferably aluminum silicate, aluminum phosphate, aluminum borate, aluminum perchlorate and aluminum chloride; and the gel-based ion storage layer is a gel-based solid-state electrolyte containing lithium salt.

Description

Technical Field

[0001] This invention relates to a long-life electrochromic device with dual-ion synergistic operation and its preparation method, belonging to the fields of chemical material synthesis and functional materials technology. Background Technology

[0002] Energy is a crucial foundation for maintaining a nation's sustained economic development and ensuring people's material well-being. Today, energy shortages and environmental pollution are increasingly severe, prompting scientists to develop new energy sources while simultaneously seeking methods to conserve energy and reduce consumption. Electrochromic devices and technologies are primarily applied in energy-efficient building glass, vehicle windows, anti-glare rearview mirrors, displays, electronic paper, and camouflage applications. Low-E glass is a type of low-emissivity glass that works by reflecting most infrared radiation, reducing heat entering the room. Insulating glass reduces heat exchange between the indoor and outdoor spaces. Both aim to reduce indoor cooling energy consumption. However, these two types of windows, and their combinations, only facilitate cooling, not temperature regulation. That is, in cold winters, heat still struggles to enter the room.

[0003] Traditional electrochromic devices mainly consist of five thin films: two transparent conductive layers, an ion storage layer, an electrochromic layer, and an ion conduction layer. The ion storage layer assists the electrochromic layer in achieving the electrochromic reaction by applying a low voltage to the first and second conductive layers. The ion conduction layer provides lithium ions and diffuses the thin film, ensuring ion conductivity under an electric field. Its structure and fabrication process are among the most important technologies for guaranteeing the electrochromic performance of the device.

[0004] All-solid-state electrochromic devices possess stable structures and excellent resistance to water, oxygen, and ultraviolet radiation, avoiding the drawbacks of liquid and quasi-solid-state devices. However, their slow response speed due to low ion migration rates limits their application areas. Furthermore, all-solid-state electrochromic devices are prone to uneven coloring after multiple cycles, making it difficult to design and fabricate large-size devices. Compared to single-ion devices, dual-ion devices exhibit significant advantages, including better tuning capabilities, faster response speeds, and improved cycle stability due to lower driving voltages. Therefore, designing devices with dual-ion or even multi-ion synergistic migration holds promise for solving these problems. Typically, the conducting ions in dual-ion regulated electrochromic devices are provided by a single compound; however, the different chemical potentials of the various ions during cycling cause changes in the ion ratio during migration. This unfavorable change shortens the device's cycle stability. Summary of the Invention

[0005] To address the technical problem that "existing dual-ion electrochromic devices are prone to recombination due to ion migration velocity during cycling, which leads to a decrease in the cycle stability of the device," this invention provides a long-life electrochromic device with dual-ion synergistic operation and its preparation method.

[0006] On one hand, the present invention provides a long-life electrochromic device with dual-ion synergistic operation and its preparation method, comprising a first transparent electrode layer, an inorganic electrochromic layer, an electrolyte layer, a gel-based ion storage layer and a second transparent electrode layer stacked sequentially; the electrolyte layer is made of aluminum salt, preferably at least one of aluminum silicate, aluminum phosphate, aluminum borate, aluminum perchlorate and aluminum chloride; the gel-based ion storage layer is a lithium salt-containing gel-based solid electrolyte.

[0007] This patent connects a dielectric layer containing one type of migrating ion and an ion storage layer in series, utilizing the cation "unlocking effect" to achieve dual-ion synergistic migration. This ion migration method can fix the migration ratio of the two ions, significantly improving the device's cycle stability. Therefore, this patent designs Al and Li in a series structure as synergistic migrating ions. Compared to traditional materials such as lithium aluminum silicate, this invention can controllably adjust the ratio of Al and Li, achieving an overall improvement in the response speed and adjustment capability of the electrochromic device.

[0008] Preferably, the inorganic electrochromic layer is made of at least one of WO3, MoO3 and TiO2; and the thickness of the inorganic electrochromic layer is 100–500 nm.

[0009] Preferably, the thickness of the electrolyte layer is 50–300 nm.

[0010] Preferably, the thickness of the gel-based ion storage layer is 20–80 μm; the lithium salt is at least one of lithium chloride, lithium perchlorate, lithium phosphate, lithium silicate, and LiPON.

[0011] Furthermore, preferably, the gel-based ion storage layer also contains a magnesium salt, which is selected from at least one of magnesium chloride, magnesium perchlorate, magnesium phosphate, and magnesium silicate; the molar ratio of the lithium salt to the magnesium salt is 1:(0.05-0.2). In addition, this patent adds an appropriate amount of Mg to the electrolyte. 2+ Studies have shown that Mg 2+ With Li + In gel electrolytes, diions readily form, which not only enhance the migration rate of lithium ions but also prevent lithium ions from recombinating with defects. Specifically, Mg... 2+ Coupled with long chains in the electrolyte layer, and fixed between the long chains, its radius and Li +They are close in size and possess higher ion polarization performance, enabling them to modulate the coordination environment of lithium ions in the electrolyte, thereby promoting the dissociation of lithium ions from anions and increasing the migration rate and efficiency of lithium ions. In Li / Mg co-doping, if Mg... 2+ If the proportion of ions is too low, it cannot sufficiently promote the growth of Li. + Rapid migration, if Mg 2+ If the proportion of ions is too high, it will affect the total amount of Li ions in the resin. Excessive Mg ions will occupy the positions of Li ions, and excessive Mg ions will also cause problems. 2+ It may also break free from the resin's binding and enter the electrochromic layer, affecting the overall performance of the device. Furthermore, Mg... 2+ Able to promote Li + Rapid dissociation and migration of anions and electrolyte chains, but Mg 2+ Because of its higher electronegativity, it is fixed in the electrolyte layer and therefore does not participate in Al. 3+ The migration.

[0012] Preferably, the materials of the first transparent electrode layer and the second transparent electrode layer are independently selected from at least one of transparent conductive oxide and metal nanowires; the sheet resistance of the first transparent electrode layer and the second transparent electrode layer is 10 to 40 Ω / cm. 2 Transmittance ≥75%.

[0013] On the other hand, the present invention provides a method for preparing the above-mentioned long-life electrochromic device with dual-ion synergistic operation, wherein the method for preparing the gel-based ion storage layer includes:

[0014] (1) Weigh the light-curing resin, solvent, stabilizer, organic precursor and cationic salt in a molar ratio of 1:(1~3):(0.05~0.2):(0.5~2):(1~3) and stir in the dark until completely dissolved to obtain mixed solution 1;

[0015] (2) Add magnesium salt and initiator to the mixed solution to obtain mixed solution 2, and the anion of magnesium salt is the same as that of lithium salt;

[0016] (3) The obtained mixed solution 2 was spin-coated and then photocured under ultraviolet light to obtain a gel-based ion storage layer.

[0017] Preferably, the photocurable resin is selected from at least one of TTA21, L-6206, L-6380H, and L-6605; and the solvent is at least one of PMA, NMP, MDBE, and EMC.

[0018] The stabilizer is a transition metal organometallic compound, preferably ferrocene and its derivatives, and more preferably ferrocene, manganese ferrocene, or vinyl ferrocene.

[0019] The organic precursor includes an acid ester compound, preferably at least one of ethoxylated trimethylolpropane triacrylate (ETPTA) and trimethylolpropane triacrylate.

[0020] The spin coating speed is 1000–3000 rpm, and the time is 10–60 seconds.

[0021] The photocuring process involves irradiating the light with a 100-300W ultraviolet lamp for 5 to 30 seconds.

[0022] Preferably, the mixed solution 2 further comprises at least one of a leveling agent, an adhesion promoter, and a defoamer;

[0023] The leveling agent is selected from at least one of BYK333, BYK358N, BYK306 and BYK378, and the amount added is 0.5% to 2% of the total mass of the precursor;

[0024] The adhesion promoter is selected from at least one of BYK4500, BYK4509, BYK4510, and BYK4511, and the amount added is 0.05 to 0.2% of the total mass of the precursor.

[0025] The defoamer is selected from at least one of BYK011, BYK012 and BYK014, and the amount added is 0.1 to 0.5% of the total mass of the precursor.

[0026] Preferably, an inorganic electrochromic layer is prepared on the surface of the first transparent electrode layer by magnetron sputtering, laser pulse deposition, molecular beam epitaxy, spin coating, spraying, or dip coating.

[0027] Beneficial effects:

[0028] 1. The present invention designs Al and Li in a series structure as co-migrating ions. Compared with traditional materials such as lithium aluminum silicate, the present invention can controllably adjust the ratio of Al and Li, thereby improving the overall response speed and adjustment capability of electrochromic devices.

[0029] 2. The material involved in this invention is abundant on Earth, thus significantly reducing costs compared to conventional ion-conducting layers such as lithium tantalate and lithium niobate. Furthermore, the preparation process is simple, and the organic-inorganic composite structure effectively avoids interface defects. Attached Figure Description

[0030] Figure 1 This is a schematic diagram of the structure of the long-life electrochromic device with dual-ion synergistic operation of the present invention. Detailed Implementation

[0031] The present invention will be further illustrated by the following embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the present invention.

[0032] This patent proposes that dual-ion synergistic conduction not only has excellent response speed but also better regulation capability and significantly improves the cycling stability of the device.

[0033] In this disclosure, a long-life electrochromic device with dual-ion synergy includes: a first transparent electrode layer, an electrochromic layer, an electrolyte layer, a gel-based ion storage layer, and a second transparent electrode layer sequentially stacked. The electrolyte layer can be made of at least one of aluminum silicate, aluminum phosphate, aluminum borate, aluminum perchlorate, and aluminum chloride. The thickness of the electrolyte layer is 50–300 nm. The gel-based ion storage layer is made of a lithium-containing gel-based solid electrolyte. The lithium salt is at least one of lithium chloride, lithium perchlorate, lithium phosphate, lithium silicate, and LiPON.

[0034] In this invention, an aluminum ion-based electrolyte layer and a lithium ion-based ion storage layer are connected in series. Theoretical calculations and experiments have shown that under the influence of an external electric field, the Li in the ion storage layer... + Enter Al x Si y O3 ions disrupt the electrostatic balance within the conductive layer, reducing the strength of Al-O bonds and causing Al... 3+ Aluminum ions readily detach from O 2- The control of oxygen ions enables migration, achieving dual-ion migration. This patent connects a dielectric layer containing one type of migrating ion and an ion storage layer in series, utilizing a cation "unlocking effect" to achieve synergistic dual-ion migration. This ion migration method can maintain a fixed ratio of the two ion migrations, significantly improving the device's cycle stability.

[0035] Compared to single-ion devices, dual-ion devices exhibit significant advantages, including better regulation, faster response, and improved cycling stability due to lower drive voltage. Typically, the conduction ions in dual-ion regulated electrochromic devices are provided by a single compound; however, the different chemical potentials of the different ions during cycling cause changes in the ion ratio during migration. This adverse change shortens the device's cycling stability.

[0036] In an optional embodiment, the electrochromic layer is made of at least one of WO3, MoO3 and TiO2, and has a thickness of 100–500 nm.

[0037] In an optional embodiment, the materials of the first and second transparent electrode layers are each independently selected from at least one of transparent conductive oxides and metal nanowires. The sheet resistance of the first and second transparent electrode layers is 10–40 Ω / cm. 2 Visible light transmittance ≥75%.

[0038] The following exemplarily illustrates a method for fabricating a long-life electrochromic device with dual-ion synergy.

[0039] In this invention, the DC magnetron sputtering system used for magnetron sputtering deposition may include a deposition chamber, a sample inlet chamber, several target heads, a substrate, a DC current source, and a series of mechanical pumps and vacuum pumps. The target heads are at a certain angle to the substrate and separated by a certain distance. The DC power supply is connected to the target heads. The substrate is ultrasonically cleaned with acetone, anhydrous ethanol, and deionized water for 20 minutes each, and then dried with compressed air. A portion of the conductive substrate is covered with high-temperature tape as an electrode and fixed to the substrate tray. The substrate is placed in the sample inlet chamber, and the mechanical pump is turned on to evacuate to below 5 Pa. Then, the baffle valve is opened, and the vacuum level (baseline vacuum) reaches 10. -4 Splash chambers with Pa and below.

[0040] The specific sputtering deposition process is as follows: High-purity argon and oxygen are introduced into the sputtering chamber, with the purity of the argon and oxygen being 99.99% or higher. The total pressure and oxygen partial pressure within the chamber are controlled within the ranges of 0.5–2.0 Pa and 0–50%, respectively, with the oxygen partial pressure preferably being 0–25%. The vertical distance between the target and the substrate is controlled to be 10–20 cm, and the initial substrate temperature is room temperature. The DC power supply is turned on, and the power is controlled to be 30–200 W. The pre-sputtering time is 5–30 min, the sputtering time is 10–60 min, and the substrate temperature is room temperature. After sputtering, the substrate is removed after the substrate temperature has cooled to room temperature.

[0041] An inorganic electrochromic layer is continuously deposited on the surface of a transparent conductive glass substrate. The layer is prepared by magnetron sputtering using tungsten, molybdenum, or titanium as the target material. The sputtering gas is argon and oxygen, with a total pressure of 0.5-2.0 Pa, an oxygen partial pressure of 0-50%, a target-substrate distance of 10-20 cm, and an initial substrate temperature of room temperature. The applied DC power to the target is 30-150 W or the power density is 0.6-3.0 W / cm². 2 Electrochromic thin films with a thickness of 100nm–500nm were deposited.

[0042] Aluminum silicate, aluminum phosphate, aluminum borate, aluminum perchlorate, and aluminum chloride are used as targets. Argon is used as the sputtering gas, with a total pressure of 0.5-2.0 Pa. The distance between the target and the substrate is 10-20 cm, and the initial substrate temperature is room temperature. The DC power applied to the target is 30-150 W or the power density is 0.6-3.0 W / cm². 2 Electrolyte layer films with a thickness of 50nm–300nm were deposited.

[0043] The gel-based ion storage layer uses UV-curable resin as the substrate and adds appropriate amounts of solvent, cationic salt, stabilizer, reducing agent, defoamer, leveling agent, adhesion promoter, and initiator. A stable solution is obtained after thorough stirring and dissolution. As an example of preparing a UV-curable electrolyte precursor solution, the process includes: 1) Weighing the UV-curable resin, solvent, ferrocene, ETPTA, and lithium ion salt (hereinafter referred to as lithium salt) in a ratio of 1:(1-3):(0.05-0.2):(0.5-2):(1-3) and stirring in the dark until completely dissolved to obtain mixed solution 1; 2) Adding an appropriate amount (1-10)% of magnesium ion salt, whose anion is the same as that of the lithium ion salt, to mixed solution 1, and then adding (0.1-0.5)% of initiator, and further stirring thoroughly to obtain mixed solution 2.

[0044] The mixed solution 2 was deposited on the surface of the electrochromic layer using a spin coating process, with the rotation speed controlled at 1000-3000 rpm and the thickness of the gel-based ion storage layer controlled at 20-80 μm.

[0045] After spin coating, the top electrode is applied. The prepared device is then uniformly irradiated under a 100W UV lamp for 15 seconds. After the device has cured, excess organic matter on the device surface is removed using an organic solvent. This completes the fabrication process of the dual-ion electrochromic device.

[0046] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the appropriate range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below.

[0047] Example 1

[0048] (1) Select a transparent conductive glass substrate and continuously deposit an inorganic electrochromic layer on its surface. Use tungsten metal as the target material by magnetron sputtering, with argon and oxygen as the sputtering gases, a total pressure of 1.0 Pa, an oxygen partial pressure of 15%, a distance of 15 cm between the target and the substrate, an initial substrate temperature of room temperature, and a DC power of 70 W applied to the target material to deposit an electrochromic layer film with a thickness of 400 nm.

[0049] (2) Aluminum silicate Al x Si yO3 was used as the target material, argon was used as the sputtering gas, the total pressure was 1.0 Pa, the distance between the target and the substrate was 15 cm, the initial substrate temperature was room temperature, the DC power applied to the target was 80 W, and an RF power supply was used to deposit an electrolyte layer film with a thickness of 150 nm.

[0050] (3) Prepare the photocurable electrolyte precursor solution. 1) Weigh the photocurable resin, solvent, ferrocene, ETPTA, and lithium perchlorate in a ratio of 1:2:0.1:1:2 and stir in the dark until completely dissolved to obtain mixed solution 1; 2) Add Mg... 2+ Li + Magnesium perchlorate in a molar ratio of 1:7, 0.2% (total mass) of initiator (made of azobisisobutyronitrile), and further stirred thoroughly to obtain mixed solution 2;

[0051] (4) The mixed solution 2 was coated onto the surface of the electrochromic layer using a spin-coating process, with a spin speed controlled at 2500 rpm, resulting in a film thickness of 60 μm. After spin-coating, the top electrode was covered. The prepared device was then uniformly irradiated under a 100W UV lamp for 15 s. After the device cured, excess organic matter on the device surface was removed using an organic solvent. This completed the fabrication process of the long-life electrochromic device with dual-ion synergy.

[0052] Example 2

[0053] The fabrication process of the long-life electrochromic device with dual-ion synergy in Example 2 is the same as that in Example 1, except that in step (1), tungsten metal is used as the target material by magnetron sputtering, the sputtering gas is argon and oxygen, the total pressure is 1.0 Pa, the oxygen partial pressure is 15%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the DC power applied to the target material is 70 W, and an electrochromic layer film with a thickness of 100 nm is deposited.

[0054] Example 3

[0055] The fabrication process of the long-life electrochromic device with dual-ion synergy in Example 3 is the same as that in Example 1, except that in step (1), tungsten metal is used as the target material by magnetron sputtering, the sputtering gas is argon and oxygen, the total pressure is 1.0 Pa, the oxygen partial pressure is 15%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the DC power applied to the target material is 70 W, and an electrochromic layer film with a thickness of 500 nm is deposited.

[0056] Example 4

[0057] The fabrication process of the long-life electrochromic device with dual-ion synergy in Example 4 is the same as that in Example 1, except that in step (2), aluminum silicate is used as the target material, argon is used as the sputtering gas, the total pressure is 1.0 Pa, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the DC power applied to the target material is 80 W, and an RF power supply is used to deposit an electrolyte layer film with a thickness of 50 nm.

[0058] Example 5

[0059] The fabrication process of the long-life electrochromic device with dual-ion synergy in Example 5 is the same as that in Example 1, except that in step (2), aluminum silicate is used as the target material, argon is used as the sputtering gas, the total pressure is 1.0 Pa, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the DC power applied to the target material is 80 W, and an RF power supply is used to deposit an electrolyte layer film with a thickness of 300 nm.

[0060] Example 6

[0061] The preparation process of the long-life electrochromic device with dual-ion synergy in Example 6 is the same as that in Example 1, except that in step (3), a photocurable electrolyte precursor solution is prepared. 1) Weigh the photocurable resin, solvent, ferrocene, ETPTA and lithium perchlorate in a ratio of 1:2:0.1:1:2; 2) Stir the above mixed solution in the dark until completely dissolved; add Mg 2+ Li + Magnesium perchlorate in a molar ratio of 1:5. 4) Add 0.2% (total mass) of initiator (azobisisobutyronitrile), and stir thoroughly.

[0062] Example 7

[0063] The preparation process of the long-life electrochromic device with dual-ion synergy in Example 7 is the same as that in Example 1, except that in step (3), a photocurable electrolyte precursor solution is prepared. 1) Weigh the photocurable resin, solvent, ferrocene, ETPTA and lithium perchlorate in a ratio of 1:2:0.1:1:2; 2) Stir the above mixed solution in the dark until completely dissolved; 3) Add Mg 2 + Li + The molar ratio of magnesium perchlorate is 1:20. 4) Add 0.2% (total mass) of initiator (azobisisobutyronitrile), and stir thoroughly to obtain mixed solution 2.

[0064] Example 8

[0065] The preparation process of the long-life electrochromic device with dual-ion synergy in Example 8 is the same as that in Example 1, except that in step (4), the above mixed solution 2 is deposited on the surface of the electrochromic layer by spin coating at a rotation speed of 3000 rpm and a film thickness of 20 μm.

[0066] Example 9

[0067] The preparation process of the long-life electrochromic device with dual-ion synergy in Example 9 is the same as that in Example 1, except that in step (4), the above mixed solution is deposited on the surface of the electrochromic layer by spin coating at a rotation speed of 1000 rpm and a film thickness of 80 μm.

[0068] Example 10

[0069] The fabrication process of the long-life electrochromic device with dual-ion synergy in Example 10 is the same as that in Example 1, except that in step (2), silicon and aluminum are used as targets, argon and oxygen are used as sputtering gases, the total pressure is 1.0 Pa, the distance between the target and the substrate is 15 cm, the initial substrate temperature is room temperature, the DC power supply power on the aluminum target is 80 W, and the RF power supply power on the silicon target is 100 W. The sputtering time is 1 h.

[0070] Example 11

[0071] The preparation process of the long-life electrochromic device with dual-ion synergy in Example 11 is the same as that in Example 1, except that in step (3), the third step is to prepare the photocurable electrolyte precursor solution. 1) Weigh the photocurable resin, solvent, ferrocene, ETPTA and lithium chloride in a ratio of 1:2:0.1:1:2 and stir in the dark until completely dissolved to obtain mixed solution 1; 2) Add Mg to mixed solution 1. 2+ Li + Magnesium perchlorate (total mass) in a molar ratio of 1:7 and 0.2% (total mass) of initiator (azobisisobutyronitrile) were added and stirred thoroughly to obtain mixed solution 2.

[0072] Example 12

[0073] The preparation process of the long-life electrochromic device with dual-ion synergy in Example 12 is the same as that in Example 1, except that in step (3), a photocurable electrolyte precursor solution is prepared. 1) Weigh the photocurable resin, solvent, ferrocene, ETPTA and lithium perchlorate in a ratio of 1:2:0.1:1:2 and stir in the dark until completely dissolved to obtain mixed solution 1; 2) Add 0.2% of initiator (total mass, azobisisobutyronitrile) to mixed solution 1 and stir thoroughly to obtain mixed solution 2.

[0074] Example 13

[0075] The preparation process of the long-life electrochromic device with dual-ion synergy in Example 13 is the same as that in Example 1, except that in step (3), a photocurable electrolyte precursor solution is prepared. 1) Weigh the photocurable resin, solvent, ferrocene, ETPTA and lithium perchlorate in a ratio of 1:2:0.1:1:2 and stir in the dark until completely dissolved to obtain mixed solution 1; 2) Add Mg to mixed solution 1. 2+ Li + Magnesium perchlorate in a molar ratio of 1:0.5 and initiator (azobisisobutyronitrile) of 0.2% (total mass) were added and stirred thoroughly to obtain mixed solution 2. In Li / Mg co-doping, if the proportion of Mg ions is too low, it will not sufficiently promote the rapid migration of Li+. If the proportion of Mg ions is too high, it will affect the total amount of Li ions in the resin. Excessive Mg ions will occupy the Li positions, and excessive Mg... 2+ It may also break free from the resin's binding and enter the electrochromic layer, affecting the overall performance of the device.

[0076] Example 14

[0077] The preparation process of the long-life electrochromic device with dual-ion synergy in Example 14 is the same as that in Example 1, except that in step (3), a photocurable electrolyte precursor solution is prepared. 1) Weigh the photocurable resin, solvent, ferrocene, ETPTA and lithium perchlorate in a ratio of 1:2:0.1:1:2 and stir in the dark until completely dissolved to obtain mixed solution 1; 2) Add Mg 2+ Li + Magnesium perchlorate in a molar ratio of 1:3, 0.2% (total mass) of initiator (azobisisobutyronitrile), and further stirred thoroughly to obtain mixed solution 2.

[0078] Example 15

[0079] The preparation process of the long-life electrochromic device with dual-ion synergy in Example 15 is the same as that in Example 1, except that in step (3), a photocurable electrolyte precursor solution is prepared. 1) Weigh the photocurable resin, solvent, ferrocene, ETPTA and lithium perchlorate in a ratio of 1:2:0.1:1:2 and stir in the dark until completely dissolved to obtain mixed solution 1; 2) Add Mg to mixed solution 1. 2+ Li + Magnesium perchlorate in a molar ratio of 1:12, 0.2% (total mass) of initiator (azobisisobutyronitrile), and further stirred thoroughly to obtain mixed solution 2.

[0080] Example 16

[0081] The preparation process of the long-life electrochromic device with dual-ion synergy in Example 16 is the same as that in Example 1, except that in step (3), a photocurable electrolyte precursor solution is prepared. 1) Weigh the photocurable resin, solvent, ferrocene, ETPTA and lithium perchlorate in a ratio of 1:2:0.1:1:2 and stir in the dark until completely dissolved to obtain mixed solution 1; 2) Add Mg to mixed solution 1. 2+ Li + Magnesium perchlorate in a molar ratio of 1:30, and 0.2% (total mass) of initiator (azobisisobutyronitrile) were added and stirred thoroughly to obtain mixed solution 2. In Li / Mg co-doping, if the proportion of Mg ions is too low, it cannot sufficiently promote the rapid migration of Li+; if the proportion of Mg ions is too high, it will affect the total amount of Li ions in the resin. Excessive Mg ions will occupy Li positions, and excessive Mg... 2+ It may also break free from the resin's binding and enter the electrochromic layer, affecting the overall performance of the device.

[0082] Table 1 shows the structure and composition of a long-life electrochromic device with dual-ion synergy:

[0083]

[0084]

[0085] Table 2 shows the performance of long-life electrochromic devices with dual-ion synergy:

[0086] Response speed Cycle life Adjustment ability Example 1 0.7s 100,000 times 55％ Example 2 0.7s 81,000 times 28％ Example 3 0.9s 72,000 times 51％ Example 4 0.8s 91,000 times 43％ Example 5 0.9s 92,000 times 53％ Example 6 3.2s 58,000 times 38％ Example 7 1.3s 82,000 times 42％ Example 8 2.1s 92,000 times 32％ Example 9 1.1s 82,000 times 46％ Example 10 0.7s 81,000 times 53％ Example 11 3.1s 52,000 times 42％ Example 12 5.1s 39,000 times 48％ Example 13 8.9s 11,000 times 25.6％ Example 14 5.1s 31,000 times 32.1％ Example 15 1.1s 89,000 times 47％ Example 16 12.9s 21,000 times 31.1％

[0087] The response speed of the dual-ion synergistic long-life electrochromic device can be 0.7–13 s. The cycle life of the dual-ion synergistic long-life electrochromic device is 11,000–100,000 cycles. The adjustment capability of the dual-ion synergistic long-life electrochromic device is 25–55%.

[0088] Cycle life test method: Apply cyclic voltage to the device, with a high potential of 1.5V and a low potential of -3V, for a voltage duration of 0.05s and a hold time of 30s, with 1min as one cycle;

[0089] Adjustment capability: The difference in transmittance of the spectrum at 670 nm when a high potential and a low potential are applied to the device;

[0090] Response speed: The time required for the device to fully color from the faded state during cycle life testing.

Claims

1. A long-life electrochromic device with dual-ion synergistic operation, characterized in that, It includes a first transparent electrode layer, an inorganic electrochromic layer, an electrolyte layer, a gel-based ion storage layer, and a second transparent electrode layer, which are stacked sequentially. The electrolyte layer is made of aluminum salt; The gel-based ion storage layer is a lithium-containing gel-based solid electrolyte; the gel-based ion storage layer also contains a magnesium salt, which is selected from at least one of magnesium chloride, magnesium perchlorate, magnesium phosphate, magnesium silicate, magnesium nitrate and magnesium sulfate; the molar ratio of the lithium salt to the magnesium salt is 1:(0.05~0.2).

2. The long-life electrochromic device with dual-ion synergistic operation according to claim 1, characterized in that, The electrolyte layer is made of at least one of aluminum silicate, aluminum phosphate, aluminum borate, aluminum perchlorate, and aluminum chloride.

3. The long-life electrochromic device with dual-ion synergistic operation according to claim 1, characterized in that, The inorganic electrochromic layer is made of at least one of WO3, MoO3 and TiO2; the thickness of the inorganic electrochromic layer is 100–500 nm.

4. The long-life electrochromic device with dual-ion synergistic operation according to claim 1, characterized in that, The thickness of the electrolyte layer is 50–300 nm.

5. The long-life electrochromic device with dual-ion synergistic operation according to claim 1, characterized in that, The thickness of the gel-based ion storage layer is 20–80 μm; the lithium salt is at least one of lithium chloride, lithium perchlorate, lithium phosphate, and lithium silicate.

6. The long-life electrochromic device with dual-ion synergistic operation according to claim 1, characterized in that, The materials of the first and second transparent electrode layers are independently selected from at least one of transparent conductive oxides and metal nanowires; the sheet resistance of the first and second transparent electrode layers is 10–40 Ω / cm. 2 Transmittance ≥75%.

7. A method for preparing a long-life electrochromic device with dual-ion synergistic operation as described in claim 1, characterized in that, The method for preparing the gel-based ion storage layer includes: (1) Weigh the light-curing resin, solvent, stabilizer, organic precursor and lithium salt in a molar ratio of 1:(1~3):(0.05~0.2):(0.5~2):(1~3) and stir in the dark until completely dissolved to obtain mixed solution 1; (2) Add magnesium salt and initiator to mixed solution 1 to obtain mixed solution 2, and the anion of magnesium salt is the same as that of lithium salt; (3) The resulting mixed solution 2 was spin-coated and then cured under ultraviolet light to obtain a gel-based ion storage layer.

8. The preparation method according to claim 7, characterized in that, The photocurable resin is selected from at least one of TTA21, L-6206, L-6380H, and L-6605. The solvent is at least one of PMA, NMP, MDBE and EMC; The stabilizer is a transition metal organometallic compound; The organic precursor includes acid ester compounds; The spin coating speed is 1000-3000 rpm, and the time is 10-60 seconds; The photocuring process involves irradiating the light with a 100-300W ultraviolet lamp for 5 to 30 seconds.

9. The preparation method according to claim 7, characterized in that, The mixed solution 2 also contains at least one of a leveling agent, an adhesion promoter, and a defoamer; The leveling agent is selected from at least one of BYK333, BYK358N, BYK306 and BYK378, and the amount added is 0.5% to 2% of the total mass of the precursor; The adhesion promoter is selected from at least one of BYK4500, BYK4509, BYK4510, and BYK4511, and the amount added is 0.05% to 0.2% of the total mass of the precursor. The defoamer is selected from at least one of BYK011, BYK012 and BYK014, and the amount added is 0.1 to 0.5% of the total mass of the precursor.

10. The preparation method according to claim 7, characterized in that, An inorganic electrochromic layer is prepared on the surface of the first transparent electrode layer by magnetron sputtering, laser pulse deposition, molecular beam epitaxy, spin coating, spraying, or dip coating.

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