Gel electrolyte and electrochromic element comprising same

Abstract

The present disclosure provides a gel-state electrolyte comprising: a solvent substrate; the spherical inorganic nanoparticles are dispersed in the solvent substrate, the spherical inorganic nanoparticles are bonded through an M-O-M structure, and M is Ti, Si, Al, Zr, V, Fe, Ni, Zn or a combination of the Ti, the Si, the Al, the Zr, the V, the Fe, the Ni and the Zn.

Description

Technical Field

[0001] The present invention relates to an electrochromic material, and in particular to a gel electrolyte and an electrochromic element containing the same. Background Art

[0002] Electrochromism is a phenomenon in which the optical properties of a material (reflectivity, transmittance, absorptivity, etc.) undergo stable and reversible color changes under the action of an external electric field, which manifests itself in appearance as reversible changes in color and transparency.

[0003] Currently, most of the components using electrochromic materials are sandwich-type layered structures including a glass or plastic substrate, a transparent conductive layer (indium tin oxide), an electrochromic layer, an electrolyte layer, and an ion storage layer. Among these membrane layers, the electrolyte layer used to provide ions to the electrochromic layer can usually be a liquid or solid electrolyte. Liquid electrolytes are usually more durable and easier to manufacture, but may have problems such as difficulty in packaging and electrolyte leakage. Although solid electrolytes do not have the problem of leakage, they have disadvantages such as poor ion conductivity and poor flexibility. Colloidal electrolytes are between solid and liquid states, each having some of the advantages of each.

[0004] In the past, most methods of making colloidal electrolytes were to make electrochromic molecules into polymer structures, or to mix polymer materials into electrochromic materials to form a viscous colloid. Although this method of making electrochromic elements has improved the shortcomings of liquid electrochromic elements such as leakage to a certain extent, it often affects the efficiency of the electrochromic itself, resulting in increased power loss or reduced response time.

[0005] In summary, it is necessary to provide further improvements on the existing processes of electrochromic elements to enhance the stability of the electrochromic elements without reducing the efficiency. Summary of the invention

[0006] The disclosed embodiment provides a gel electrolyte, including: a solvent base; and spherical inorganic nanoparticles dispersed in the solvent base, wherein the spherical inorganic nanoparticles are bonded to each other via a MOM structure, wherein M is a central atom.

[0007] The disclosed embodiment provides an electrochromic element, comprising: a first substrate, a surface of which has a first conductive layer; a second substrate, a surface of which has a second conductive layer, wherein the first conductive layer and the second conductive layer are relatively assembled; a gap glue, wherein the gap glue is bonded between the first conductive layer and the second conductive layer to form a receiving area between the first substrate, the second substrate and the gap glue; and an electrochromic composition filled into the receiving area, wherein the electrochromic composition comprises: a gel electrolyte; at least one cathode material; and at least one anode material; wherein at least one of the at least one cathode material and the at least one anode material is an electrochromic material. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] The embodiments of the present invention are best understood by the following detailed description in conjunction with the accompanying drawings. It should be noted that, in accordance with standard practice in the industry, the various components are not drawn to scale. In fact, the sizes of the various elements may be arbitrarily enlarged or reduced to clearly show the components of the embodiments of the present invention.

[0009] Figure 1 The preparation process of the gel electrolyte according to the embodiment of the present invention is briefly illustrated.

[0010] Figure 2A A side view of an electrochromic element using a liquid electrolyte according to an embodiment of the present invention is illustrated.

[0011] Figure 2B A side view of an electrochromic element using a gel electrolyte according to an embodiment of the present invention is shown.

[0012] Figure 3 Graphs 1 and 2 are the transmission spectra of devices A1 and B1 in the neutral state and the colored state in the embodiment of the present invention.

[0013] Figure 4 1 is the transmission spectra of the device A2 in the neutral state and the colored state before and after the thermal cycle in the embodiment of the present invention.

[0014] Figure 5 1 is the transmission spectra of the device B2 in the neutral state and the colored state before and after thermal cycling in an embodiment of the present invention.

[0015] Figure 6 1 is the transmission spectra of the device A3 in the neutral state and the colored state before and after the thermal cycle in the embodiment of the present invention.

[0016] Figure 7 1 is the transmission spectra of the device B3 in the neutral state and the colored state before and after thermal cycling in an embodiment of the present invention.

[0017] Figure 8 1 is the transmission spectra of the device A4 in the neutral state and the colored state before and after the thermal cycle in the embodiment of the present invention.

[0018] Fig. 9 1 is the transmission spectra of the device A5 in the neutral state and the colored state before and after the thermal cycle in the embodiment of the present invention.

[0019] Fig.10 1 is the transmission spectra of the device A6 in the neutral state and the colored state before and after the thermal cycle in the embodiment of the present invention. DETAILED DESCRIPTION

[0020] The following is a detailed description of each gel electrolyte disclosed herein and its application. It should be understood that the various embodiments provided below are merely illustrative descriptions and are not intended to limit the present disclosure. In addition, for simplicity, similar and / or corresponding element symbols may be used in different embodiments to indicate similar and / or corresponding elements. However, the use of these similar and / or corresponding element symbols is only for simplified description and does not represent that the different embodiments and / or structures discussed need to limit each other.

[0021] Gel electrolyte is an alternative solution to improve the problem of solution leakage and contamination caused by rupture of liquid electrochromic elements. In the past, most of the methods were to make electrochromic molecules into polymer structures, or to mix polymer materials into electrochromic materials to form a viscous colloid. Although the gel electrolyte formed in this way can improve the shortcomings of liquid electrochromic elements, since most of such gel electrolytes will naturally form a gel state at room temperature, such characteristics are often not conducive to their preparation on electrochromic elements. Based on the above, the storage stability of existing gel electrolytes is not completely satisfactory.

[0022] Therefore, the present disclosure provides a gel electrolyte and an electrochromic element containing the same. The gel electrolyte is formed by heating a dispersion mixed with an organic solvent substrate and inorganic nanoparticles. According to an embodiment of the present disclosure, the gel electrolyte further comprises an electrochromic material. According to an embodiment of the present disclosure, the inorganic nanoparticles are spherical and have a specific particle size. In this way, by using spherical inorganic nanoparticles with a specific particle size, the dispersion described in the present disclosure will not naturally form a gel state under a storage environment at room temperature (e.g., 4°C-40°C). Since the timing of the gel electrolyte described in the present disclosure to form a gel state is controllable (i.e., it will be converted into a gel state only by heating), compared with the prior art, the present disclosure provides a higher convenience in the preparation and application of the element.

[0023] Now, various aspects of the present disclosure will be described in more detail. In this regard, Figure 1 An exemplary embodiment of the method for preparing a gel electrolyte disclosed herein is briefly described. However, those skilled in the art will appreciate that other embodiments are also possible.

[0024] See also Figure 1 , the preparation process of the gel electrolyte of the embodiment of the present invention is described. First, the inorganic nanoparticles 101 are dispersed in the solvent base 102, and then the electrochromic material 103 is added. The mixed liquid of the inorganic nanoparticles 101, the solvent base 102 and the electrochromic material 103 is collectively referred to as the dispersion 104, and the dispersion 104 is heated to form a gel electrolyte 104'.

[0025] According to some embodiments of the present disclosure, the inorganic nanoparticles 101 are materials that can form a gel state by heating, such as SiO2, TiO2, Al2O3, ZrO2, V2O5, Fe3O4, NiO, ZnO, or a combination thereof. According to some embodiments of the present disclosure, the inorganic nanoparticles 101 are spherical inorganic nanoparticles with a size range of 10-40nm, such as 10-30nm, 15-30nm, 20-30nm. According to some embodiments of the present disclosure, the concentration of the inorganic nanoparticles 101 in the dispersion 104 is between 5% and 50wt%, such as 5%-40wt%, 10%-30wt%, 15%-20wt%. It should be noted that although the concentration of the inorganic nanoparticles 101 here may not be limited to the above range, in some embodiments, when the inorganic nanoparticles 101 are less than a certain level (e.g., <0.5wt%) in the dispersion 104, the dispersion 104 will not be able to become a gel state after heating.

[0026] According to some embodiments of the present disclosure, the solvent base 102 is an organic solvent, which is selected from solvents that can be used as electrolytes. Generally, it is a solvent with good electrochemical stability, high dielectric constant, low volatility and appropriate viscosity. According to some embodiments of the present disclosure, the solvent base 102 can be selected from cyclic carbonates, such as ethylene carbonate (EC), propylene carbonate (PC); chain carbonates, such as diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), or a combination thereof; other esters, such as butyrolactone, valerolactone, or a combination thereof. In some embodiments, the solvent base 102 can also be selected from solvents other than esters, such as sulfolane, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, other suitable electrolyte solvents or a combination thereof.

[0027] According to some embodiments of the present disclosure, the electrochromic material 103 may form a cathode electrochromic material or an anode electrochromic material in a gel state. In some embodiments, the cathode material may be selected from C1-C10 alkyl viologen, phenyl viologen, ester viologen, acyl viologen, carboxyl anthraquinone, C1-C8 alkyl anthraquinone, ester anthraquinone, acyl anthraquinone or a combination thereof. In some embodiments, the anode material may be selected from acyl triphenylamine, carbazole triphenylamine, C1-C10 alkyl phenazine, phenothiazine, ester phenothiazine, acyl phenothiazine, C1-C8 alkyl phenothiazine, alkoxyphenyl phenothiazine, phenoxazine, ester phenoxazine, acyl phenoxazine, C1-C10 alkyl phenoxazine, p-phenylenediamine, C1-C10 alkyl p-phenylenediamine, ester p-phenylenediamine, acyl p-phenylenediamine, thiophene, C1-C10 alkyl thiophene, ester thiophene, acyl thiophene, nitrile thiophene or a combination thereof. In some embodiments, the concentration of the electrochromic material 103 in the dispersion 104 is 0.005M-1M, such as 0.02M-0.8M, 0.03M-0.6M, 0.04M-0.4M, 0.05M-0.2M.

[0028] It is worth noting that in some embodiments of the present disclosure, the dispersion 104 remains liquid even when left at room temperature for a long time (eg, >75 hrs, >100 hrs) before being heated.

[0029] According to some embodiments of the present disclosure, the mixed solution of the dispersion 104 and the electrochromic material 103 is heated at 80° C.-85° C. for 1-2 hours, for example, at 100° C.-105° C. for 0.5-1 hour.

[0030] According to some embodiments of the present disclosure, the formed gel electrolyte has a solid content of about 0.5-40 wt %, for example, 0.5-35 wt %, 0.5-30 wt %.

[0031] According to some embodiments of the present disclosure, the inorganic nanoparticles 101 dispersed in the solution are bonded to each other through a MOM structure after heating. In some embodiments, depending on the inorganic nanoparticle material used (e.g., the exemplary materials SiO2, TiO2, Al2O3, etc. as described above), M can be Si, Ti, Al, Zr, V, Fe, Ni, Zn, or a combination thereof. In the embodiment where the inorganic nanoparticles 101 used are SiO2 and the dispersion 104 is acidic, the surface of the inorganic nanoparticles 101 has Si-OH groups on the surface under an acidic environment, such as Figure 1 A partial enlargement of the surface of inorganic nanoparticle 101 Figure 1As shown in A. After simple heating, the Si-OH groups on the surface of the inorganic nanoparticles 101 are dehydrated to form a stable Si-O-Si chemical bond, so that the inorganic nanoparticles 101 are stacked on each other to form a network structure, as shown in FIG. Figure 1 A partial enlargement of the surface of inorganic nanoparticle 101 Figure 1 B, thereby converting the dispersion 104 from a liquid state to a gel electrolyte 104'. In the embodiment where the solvent base 102 is butyrolactone, butyrolactone can undergo a reversible ring-opening reaction via hydrolysis, and the charge carried after the ring-opening can subsequently interact with the charge of the inorganic nanoparticles 101 to facilitate the stacking of the inorganic nanoparticles 101. It should be understood that although Figure 1 SiO2 particles are used as an example for illustration, but the present invention can use any particles that can form MOM bonds through dehydration or other condensation reactions.

[0032] Next, refer to Figure 2A In some embodiments of the present invention, an electrochromic element is manufactured by using an electrochromic composition similar to the above-mentioned gel electrolyte. According to some embodiments of the present disclosure, a pair of electrodes of the electrochromic element 20 includes a first transparent conductive layer 202a, which is located on the surface of the first transparent substrate 201a, and a second transparent conductive layer 202b, which is located on the surface of the second transparent substrate 201b, wherein the first transparent conductive layer 202a and the second transparent conductive layer 202b are relatively assembled, and a gap glue 203 is bonded between the first transparent conductive layer 202a and the second transparent conductive layer 202b to bond the pair of electrodes, and a closed space is formed between the pair of electrodes and the gap glue 203. Next, the liquid electrochromic composition 204 is poured into the space between the first transparent conductive layer 202a and the second transparent conductive layer 202b and the gap glue 203 through the holes reserved in the gap glue 203 to seal the holes. Then, the liquid electrochromic composition 204 is simply heated to transform into a gel electrochromic composition 204'. Figure 2B As shown, in this way, the electrochromic element 20 is completed.

[0033] According to some embodiments of the present disclosure, the electrochromic composition 204 includes: inorganic nanoparticles 101 and solvent substrate 102 as in the aforementioned exemplary embodiments, as well as one or more cathode materials and one or more anode materials. According to some embodiments of the present disclosure, the cathode material may be selected from C1-C10 alkyl viologen, phenyl viologen, ester viologen, acyl viologen, carboxyl anthraquinone, C1-C8 alkyl anthraquinone, ester anthraquinone, acyl anthraquinone or a combination thereof. According to some embodiments of the present disclosure, the concentration range of the cathode material in the electrochromic composition is 0.001M-1M, for example, 0.02M-0.5M. In the exemplary embodiments provided herein, the concentration range of the cathode material is 0.01M-1M, for example, 0.02M-0.5M. According to some embodiments of the present disclosure, the anode material can be selected from acyl triphenylamine, carbazole triphenylamine, C1-C10 alkyl phenazine, phenothiazine, ester phenothiazine, acyl phenothiazine, C1-C8 alkyl phenothiazine, alkoxyphenyl phenothiazine, phenoxazine, ester phenoxazine, acyl phenoxazine, C1-C10 alkyl phenoxazine, p-phenylenediamine, C1-C10 alkyl p-phenylenediamine, ester p-phenylenediamine, acyl p-phenylenediamine, thiophene, C1-C10 alkyl thiophene, ester thiophene, acyl thiophene, nitrile thiophene or a combination thereof. According to some embodiments of the present disclosure, the concentration of the anode material in the electrochromic composition ranges from 0.01M to 1M, such as 0.02M to 0.5M.

[0034] According to some embodiments of the present disclosure, the first transparent substrate 201a and the second transparent substrate 201b may be made of glass or plastic (e.g., polycarbonate), and the first transparent conductive layer 202a and the second transparent conductive layer 202b may include, for example, indium tin oxide (ITO), antimony- or fluorine-doped tin oxide (FTO), antimony- or aluminum-doped zinc oxide, tin oxide. The gap glue 203 may be made by mixing a gap filler and a thermosetting or photochemically curable adhesive. The adhesive may be, for example, epoxy resin and acrylate resin. The gap filler may be, for example, plastic, glass beads, or some sand powder. The thickness of the gap glue 203 (i.e., the distance between the first transparent conductive layer 202a and the second transparent conductive layer 202b) is between 1 μm and 300 μm, such as 3 μm-290 μm, 5 μm-280 μm, 10 μm-270 μm, 15 μm-260 μm, 20 μm-250 μm, 25 μm-240 μm, 30 μm-230 μm, 50 μm-200 μm, 60 μm-180 μm, 70 μm-160 μm, 80 μm-140 μm, 90 μm-120 μm, 95 μm-115 μm, or 100 μm-110 μm. If the distance between the transparent conductive layers is too small, leakage and uneven color change may occur. If the distance between the transparent conductive layers is too large, the reaction speed may be slow. When the electrochromic element is not powered, the electrochromic composition is originally in a neutral state of being transparent. By applying a positive voltage to the electrochromic element, its color will gradually turn darker. Once the power is turned off, the electrochromic composition will return to its original transparent state in a short time (e.g., less than 10 seconds). The electrochromic element disclosed herein can be used in various fields, such as car windows, rearview mirrors, skylights, and large-size smart window applications in buildings.

[0035] In the present disclosure, a certain concentration (e.g., 10-30wt%) of spherical inorganic nanoparticles is dispersed in a solvent base. When necessary, the M-OH groups on the surface of the inorganic nanoparticles can be dehydrated by simple heating (e.g., heating to 80°C-120°C), and the inorganic nanoparticles form a network structure through the MOM structure, so that the original solution is transformed from a liquid state to a gel state. Since the present disclosure uses smaller spherical inorganic nanoparticles, compared with the prior art that uses larger flaky inorganic nanoparticles, the dispersion of the inorganic nanoparticles and the solvent base in the embodiments of the present disclosure can be in a liquid state for a long time at room temperature (e.g., 20°C-40°C) without naturally forming a gel state. Therefore, the solution can be heated and transformed into a gel state when necessary, which improves the storage stability and the convenience of component preparation.

[0036] Furthermore, the present invention discloses using a gel-state substance as the electrolyte of an electrochromic element, and mixing appropriate cathode materials and anode materials therein to form an electrochromic composition. With a certain concentration of inorganic nanoparticles, the shielding property of the electrochromic composition and the reliability of operation at high temperatures (e.g., 100°C-120°C) can be further improved.

[0037] In order to make the above and other purposes, features, and advantages of the present disclosure more obvious and understandable, several embodiments are given below in conjunction with the accompanying diagrams for more detailed description. However, it should be noted that the conditions used in the embodiments given below are only for illustrative purposes and are not intended to limit the scope of the rights claimed by the present disclosure:

[0038] [Preparation of gel electrolyte]

[0039] Example 1

[0040] 10g of spherical SiO2 nanoparticles with a size between 15-25nm and 1mL of electrochromic material alkylphenazine were placed in a reaction bottle. 90g of butyrolactone was added as a solvent to the reaction bottle to form 80mL of dispersion, so that the concentration of spherical SiO2 nanoparticles in the dispersion was 10wt%, and the concentration of electrochromic material alkylphenazine in the dispersion was 0.05M. The dispersion in the reaction bottle was heated to 80°C for 600 seconds, during which the dispersion gradually changed from liquid to gel.

[0041] [Comparison of Dispersion Storage Properties]

[0042] The dispersion before heating in the above step and Comparative Example 1 were placed at room temperature for testing. The remaining conditions of Comparative Example 1 and Example 1 were the same (solvent base type, electrochromic material type and concentration, etc.), except that Comparative Example 1 used flaky SiO2 nanoparticles with a size range of 20-80nm. The conditions and comparison results of Comparative Example 1 and Example 1 are shown in Table 1 below.

[0043] Table 1

[0044]

[0045]

[0046] From the results in Table 1, since the nanoparticles used in Example 1 are spherical SiO2 nanoparticles with a size range of 10-30 nm, compared with Comparative Example 1 which uses flaky SiO2 nanoparticles with a size range of 20-80 nm, the dispersion of Example 1 before heating remains in a liquid state even at room temperature even if it is left for a long time (>100 hrs).

[0047] [Conditions for forming a gel state]

[0048] The steps of Example 1 were carried out with various electrochromic material types and concentrations, inorganic nanoparticle concentrations, and solvent base types and concentrations in Table 2 to form Examples 2-4 and Comparative Examples 2-4. The various conditions used in Examples 2-4 and Comparative Examples 2-4 are shown in Table 2.

[0049] Table 2

[0050]

[0051] In Example 2 / Comparative Example 2, when the concentration of inorganic nanoparticles is sufficiently large (30wt%), when the material used is the electrochromic material alkylphenazine, the dispersion can form a gel state after heating for several hours; however, when the material used is the organic salt tetrabutylammonium bromide, the dispersion still cannot form a gel state after being heated for a long time (>24hrs).

[0052] In Example 3 / Comparative Example 3, it can be seen that when the concentration (weight percentage concentration (wt%)) of the inorganic nanoparticles is lower than a certain level (<0.5wt%), a gel state cannot be formed after being heated for a long time (>24 hrs).

[0053] In Example 4 / Comparative Example 4, it can be seen that when the solvent used is acetic acid instead of a suitable electrolyte solvent, the dispersion still cannot form a gel state after being heated for a long time (>24 hrs).

[0054] [Solvent base that can form a gel state]

[0055] Please refer to Table 3 below, which illustrates other examples capable of forming a gel state, Example 5 and Example 6. According to Example 5 and Example 6, the solvent base may use a second methylacetamide and acetone.

[0056] Table 3

[0057]

[0058] [Types of inorganic nanoparticles that can form a gel state]

[0059] Table 4 illustrates several embodiments of the present invention that can form a gel state. When the concentration of inorganic nanoparticles is 20 wt %, the types of inorganic nanoparticles that can be used to form a gel state include SiO2, Al2O3, and TiO2.

[0060] Table 4

[0061]

[0062] [Manufacturing of electrochromic elements]

[0063] The following is a detailed description of the manufacturing of the electrochromic element in the embodiment of this case.

[0064] Example 10

[0065] 7g of SiO2 spherical inorganic nanoparticles, 2mL of anode material alkyl viologen solution, and 3mL of cathode material acyl triphenylamine solution are dissolved in butyrolactone to form an electrochromic composition solution, wherein the concentration of SiO2 spherical inorganic nanoparticles in the electrochromic composition solution is 20wt%, the concentration of anode material alkyl viologen in the electrochromic composition solution is 0.05M, and the concentration of cathode material acyl triphenylamine in the electrochromic composition solution is 0.05M. Cut two pieces of ITO conductive glass of appropriate size, use gap glue (epoxy resin) to separate the glass spacer into a space of 100um to define the spacing between the ITO conductive glasses, fill the space between the ITO conductive glasses with the prepared electrochromic composition solution, and after sealing, heat the electrochromic composition solution to 100°C for 600 seconds. The electrochromic device prepared in this way is called device A1.

[0066] Example 11, Example 12, Example 13, Example 14, Example 15

[0067] Please refer to Table 5 below. Example 11, Example 12, Example 13, Example 14, and Example 15 are manufactured in a manner similar to Example 10, except that Example 11 uses alkyl phenazine and acyl triphenylamine as cathode materials in the electrochromic composition at the same time, wherein the concentration of alkyl phenazine in the electrochromic composition solution is 0.05M, and the concentration of acyl triphenylamine in the electrochromic composition solution is 0.02M; Example 12 uses phenothiazine as the cathode material in the electrochromic composition, wherein the concentration of phenothiazine in the electrochromic composition solution is 0.05M. The electrochromic devices prepared under the conditions of Example 11 and Example 12 are respectively referred to as Device A2 and Device A3; Example 13 uses ester anthraquinone as the anode material in the electrochromic composition, wherein the concentration of ester anthraquinone in the electrochromic composition solution is 0.05M, and tetrathiafulvalene is used as the cathode material in the electrochromic composition, wherein the concentration of tetrathiafulvalene in the electrochromic composition solution is 0.05M, and ethyl methyl carbonate is used as the solvent base; Example 14 uses ester anthraquinone as the anode material in the electrochromic composition, wherein the concentration of ester anthraquinone in the electrochromic composition solution is 0.05M. In Example 11, the concentration of alkylphenoxazine in the electrochromic composition solution is 0.05M, alkylphenoxazine is used as the cathode material in the electrochromic composition, wherein the concentration of alkylphenoxazine in the electrochromic composition solution is 0.05M, and cyclopentane is used as the solvent base; in Example 15, acylviologen is used as the anode material in the electrochromic composition, wherein the concentration of acylviologen in the electrochromic composition solution is 0.05M, ester-p-phenylenediamine is used as the cathode material in the electrochromic composition, wherein the concentration of ester-p-phenylenediamine in the electrochromic composition solution is 0.05M, and ethylene carbonate is used as the solvent base. The electrochromic devices prepared under the conditions of Examples 11 to 15 are respectively referred to as Devices A2 to A6.

[0068] Comparative Example 5, Comparative Example 6, Comparative Example 7

[0069] Please refer to Table 5 below. Comparative Examples 5, 6 and 7 are prepared in a similar manner to Example 10. The types and concentrations of the anode materials, cathode materials, solvent substrates and inorganic nanoparticles of Comparative Examples 5, 6 and 7 are the same as those of Example 10, Example 11 and Example 12, respectively. The only difference is that the concentration of inorganic nanoparticles in the electrochromic composition of Comparative Examples 5, 6 and 7 is less than 0.5 wt %. The electrochromic devices prepared under the conditions of Comparative Examples 5, 6 and 7 are respectively referred to as Device B1, Device B2 and Device B3.

[0070] Table 5

[0071]

[0072] [Penetration test]

[0073] At room temperature, the UV-Vis spectra of the electrochromic devices of the above embodiment and comparative example were detected using an Agilent 8453 UV-Vis spectrometer when no power was applied (neutral state) and when a working voltage of 1.2 V was applied (colored state). The transmittance spectra of device A1 and device B1 at wavelengths of 400nm-1000nm are shown in FIG. Figure 3 As shown. Figure 3 In the figure, line 301 and line 302 are the transmittance spectra of device B1 in the neutral state and the colored state, respectively; line 303 and line 304 are the transmittance spectra of device A1 in the neutral state and the colored state, respectively. The transmittances of device A1 and device B1 at wavelengths of 480nm and 550nm are shown in Table 6. After the device is powered on, the oxidizable compound and the reducible compound in the electrochromic composition undergo an oxidation-reduction reaction, resulting in a color change, causing the transmittance of the device to decrease.

[0074] Table 6

[0075]

[0076] As shown in Table 6 above, under the condition of the same electrochromic material and concentration, the transmittance is not significantly affected by increasing the concentration of nanoparticles.

[0077] [High temperature reliability test]

[0078] First, apply 1.2V voltage to device A2 and device B2 at room temperature (25°C) to test the transmission spectra of the colored state. Then, place device A2 and device B2 in an environment with a temperature of 85°C, apply 1.2V voltage (colored state) to device A2 and device B2 for 20s, and then apply 0V voltage (faded state) for 40s. Repeat the above cycle 5000 times, that is, perform a high-temperature cycle for 5000 minutes. Afterwards, allow device A2 and device B2 to return to room temperature, and then apply 1.2V voltage to them to test the transmission spectra of the colored state after the high-temperature cycle. The transmission spectra of the faded state and the colored state of device A2 and device B2 before and after the high-temperature cycle are shown as follows: Figure 4 , Figure 5 As shown. Figure 4 In FIG. 4 , line 401 and line 402 are the transmittance spectra of device A2 in the neutral state and the colored state at room temperature, respectively; line 403 and line 404 are the transmittance spectra of device A2 in the neutral state and the colored state at high temperature, respectively. Figure 5In the figure, line 501 and line 502 are the transmittance spectra of device B2 in the neutral state and the colored state at room temperature, respectively; line 503 and line 504 are the transmittance spectra of device B2 in the neutral state and the colored state at high temperature, respectively. At a specific wavelength, the subtraction value of the transmittance value of the device after high temperature cycle and the transmittance value before high temperature cycle is the decay value of the device at this specific wavelength (i.e., the transmittance value after high temperature cycle (%) - the transmittance value before high temperature cycle (%) = decay value (%)). The transmittance values ​​of device A2 and device B2 at wavelengths of 480nm and 550nm are shown in Table 7 and Table 8, respectively, and their decay values ​​are shown in Table 9.

[0079] Table 7

[0080]

[0081] Table 8

[0082]

[0083] Table 9

[0084]

[0085] Refer to Table 9 and Figure 4 , Figure 5 , comparing device A2 and device B2, it can be concluded from Table 9 that device A2 has a higher concentration of inorganic nanoparticles than device B2, so device A2 has lower decay values ​​at 480nm and 550nm wavelengths. This indicates that adding inorganic nanoparticles to the gel electrochromic composition can make the device more reliable at high temperatures.

[0086] The devices A3 and B3 were subjected to high temperature reliability tests in the same manner as described above. The transmission spectra of the devices A3 and B3 in the fading state and the colored state before and after the high temperature cycle were as follows: Figure 6 , Figure 7 As shown. Figure 6 In FIG. 6 , line 601 and line 602 are the transmittance spectra of device A3 in the neutral state and the colored state at room temperature, respectively; line 603 and line 604 are the transmittance spectra of device A3 in the neutral state and the colored state at high temperature, respectively. Figure 7 In the figure, line 701 and line 702 are the transmittance spectra of device B3 in neutral state and colored state at room temperature, respectively; line 703 and line 704 are the transmittance spectra of device B3 in neutral state and colored state at high temperature, respectively. The transmittance values ​​of device A3 and device B3 at wavelengths of 480nm and 550nm are shown in Table 10 and Table 11, respectively.

[0087] Table 10

[0088]

[0089] Table 11

[0090]

[0091] From the transmittance values ​​of device A3 and device B3 before and after high temperature cycling in Table 10 and Table 11 above, it can be seen that in the embodiments and comparative examples where the cathode or anode material is replaced with other alternative materials, it can still be concluded that when the electrochromic composition has a high concentration (for example, >20wt%) of inorganic nanoparticles, its high temperature operation stability is better than that with a low concentration (for example, >0.5wt%) of inorganic nanoparticles.

[0092] Embodiment 13, embodiment 14, embodiment 15 are provided as examples of other alternative anode materials, cathode materials and solvent bases. The devices A4, A5 and A6 corresponding to the embodiments 13, 14 and 15 are subjected to high temperature reliability tests in the same manner as described above. The transmission spectra of the neutral state and the colored state of the devices A4, A5 and A6 before and after the high temperature cycle are shown as follows: Figure 8 , Fig. 9 , Fig.10 As shown. Figure 8 In FIG. 8 , line 801 and line 802 are the transmittance spectra of device A4 in the neutral state and the colored state at room temperature, respectively; line 803 and line 804 are the transmittance spectra of device A4 in the neutral state and the colored state at high temperature, respectively. Fig. 9 In FIG. 1 , line 901 and line 902 are the transmittance spectra of device A5 in the neutral state and the colored state at room temperature, respectively; line 903 and line 904 are the transmittance spectra of device A5 in the neutral state and the colored state at high temperature, respectively. Fig.10 In the figure, line 1001 and line 1002 are the transmittance spectra of device A6 in neutral state and colored state at room temperature, respectively; line 1003 and line 1004 are the transmittance spectra of device A6 in neutral state and colored state at high temperature, respectively. The transmittance values ​​of device A4, device A5 and device A6 at wavelengths of 480nm and 550nm are shown in Table 12, Table 13 and Table 14, respectively.

[0093] Table 12

[0094]

[0095] Table 13

[0096]

[0097] Table 14

[0098]

[0099]

[0100] The above-mentioned Example 13, Example 14, and Example 15 provide alternative embodiments using other anode materials, cathode materials, and solvent substrates. It can be seen from the high temperature reliability test results of the corresponding devices A4, A5, and A6 that in the present disclosure, adding inorganic nanoparticles is also applicable to the case of using other alternative anode materials, cathode materials, and solvent substrates. In other words, Example 13, Example 14, and Example 15 illustrate that in the present disclosure, replacing the anode material, cathode material, and solvent substrate with other materials can also achieve the purpose of the present invention.

[0101] The above summarizes several embodiments or exemplary components so that those skilled in the art can more easily understand the concepts of the embodiments of the present invention. Those skilled in the art should understand that they can design or modify other processes and structures based on the embodiments of the present invention to achieve the same purposes and / or advantages as the embodiments introduced herein. Those skilled in the art should also understand that such equivalent processes and structures do not deviate from the spirit and scope of the present invention, and they can make various changes, substitutions and replacements without violating the spirit and scope of the present invention.

[0102]

Explanation of symbols

[0103] 20:Electrochromic element

[0104] 101: Inorganic Nanoparticles

[0105] 102:Solvent-based

[0106] 103: Dispersion

[0107] 104': Gel electrolyte

[0108] 104:Electrochromic materials

[0109] 1A: Enlarged view

[0110] 1B: Enlarged image

[0111] 201a: first substrate layer

[0112] 202a: first transparent conductive layer

[0113] 201b: second substrate layer

[0114] 202b: second transparent conductive layer

[0115] 203: Gap glue

[0116] 204:Electrochromic composition (liquid)

[0117] 204': Electrochromic composition (gel state)

[0118] 301 / 302 / 303 / 304: Penetration curve

[0119] 401 / 402 / 403 / 404: Penetration curve

[0120] 501 / 502 / 503 / 504: Penetration curve

[0121] 601 / 602 / 603 / 604: Penetration curve

[0122] 701 / 702 / 703 / 704: Penetration curve

[0123] 801 / 802 / 803 / 804: Penetration curve

[0124] 901 / 902 / 903 / 904: Penetration curve

[0125] 1001 / 1002 / 1003 / 1004: Penetration curve.

Claims

1. A gel electrolyte, characterized in that: include: Solvent based; as well as A plurality of spherical inorganic nanoparticles are dispersed in the solvent matrix, wherein the spherical inorganic nanoparticles are bonded to each other via a MOM structure, wherein M is selected from Ti, Si, Al, Zr, V, Fe, Ni, Zn, or a combination thereof.

2. The gel electrolyte according to claim 1, further comprising an electrochromic material dispersed in the solvent matrix. 3 . The gel electrolyte according to claim 1 , wherein the size of the spherical inorganic nanoparticles is 10-40 nm.

4. The gel electrolyte according to claim 1, wherein the solvent base is selected from ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, butyrolactone, valerolactone, sulfolane, N-methylpyrrolidone, dimethylformamide, dimethylacetamide or a combination thereof.

5. The gel electrolyte according to claim 1, wherein the solid content of the gel electrolyte is 0.5-40 wt%.

6. An electrochromic element, characterized in that: include: A first substrate, wherein a surface of the first substrate has a first conductive layer; A second substrate, wherein a second conductive layer is formed on a surface of the second substrate, wherein the first conductive layer and the second conductive layer are oppositely assembled; A gap glue is bonded between the first conductive layer and the second conductive layer to form a receiving area between the first substrate, the second substrate and the gap glue; as well as An electrochromic composition is filled into the containing area, wherein the electrochromic composition comprises: A gel electrolyte, the gel electrolyte comprising: Solvent based; A plurality of spherical inorganic nanoparticles are dispersed in the solvent matrix, wherein the spherical inorganic nanoparticles are bonded to each other via a MOM structure, wherein M is selected from Ti, Si, Al, Zr, V, Fe, Ni, Zn, or a combination thereof; at least one cathode material; and at least one anode material; At least one of the at least one cathode material and the at least one anode material is an electrochromic material. 7 . The electrochromic element according to claim 6 , wherein the size of the spherical inorganic nanoparticles is 10-40 nm.

8. The electrochromic element according to claim 6, wherein the solvent base is selected from ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, butyrolactone, valerolactone, sulfolane, N-methylpyrrolidone, dimethylformamide, dimethylacetamide or a combination thereof.

9. The electrochromic element according to claim 6, wherein the at least one cathode material is selected from C1-C10 alkyl viologen, phenyl viologen, ester viologen, acyl viologen, carboxyanthraquinone, C1-C8 alkyl anthraquinone, ester anthraquinone, acyl anthracene or a combination thereof.

10. The electrochromic element according to claim 6, wherein the at least one anode material is selected from acyl triphenylamine, carbazole triphenylamine, C1-C10 alkyl phenazine, phenothiazine, ester phenothiazine, acyl phenothiazine, C1-C8 alkyl phenothiazine, alkoxyphenyl phenothiazine, phenoxazine, ester phenoxazine, acyl phenoxazine, C1-C10 alkyl phenoxazine, p-phenylenediamine, C1-C10 alkyl p-phenylenediamine, ester p-phenylenediamine, acyl p-phenylenediamine, thiophene, C1-C10 alkyl thiophene, ester thiophene, acyl thiophene, nitrile thiophene or a combination thereof.

Images