Electrochromic device

Abstract

An embodiment of the present invention provides a catalyst composition comprising: a catalyst comprising a platinum group element; and a support comprising a post-transition metal and a metal oxide. In addition, other embodiments of the present invention provide: an anode comprising the catalyst composition; and water electrolysis comprising the anode.

Description

electrochromic devices

[0001] The present invention relates to an electrochromic device.

[0002] Electrochromic materials are materials that reversibly change color depending on the direction of the electric field when voltage is applied from an external power source. These materials change color reversibly through an electrochemical redox reaction. They have the characteristic of changing color when an electrical signal is applied from outside or when no electrical signal is applied, and then fading.

[0003] A typical electrochromic device includes an electrochromic (EC) electrode layer and a counter electrode (CE) layer, which are separated by an ionically conductive layer that is highly resistive to electrons and highly conductive to ions.

[0004] Electrochromic elements can be formed in various ways, but for example, a method that includes a layer formation process using adsorption has the problem of a complicated manufacturing process and increased cost, and has limitations in applying it to flexible elements because it requires a high-temperature heat treatment process.

[0005] In addition, the solution type in which the electrochromic material is dissolved in the electrolyte solution has limitations in the precise control capability and stability improvement of the device.

[0006] The present invention seeks to provide a catalyst composition comprising a catalyst and a support comprising a post-transition metal and a metal oxide.

[0007] The novel catalyst composition of the present invention comprises a catalyst; and a support comprising a post-transition metal and a metal oxide, wherein the catalyst may comprise a platinum group element.

[0008] The catalyst composition according to the present invention has the advantages of being economical by reducing the content of the precious metal catalyst, being stable, and having excellent conductivity.

[0009] FIG. 1 is a schematic drawing showing a catalyst composition according to one embodiment of the present invention.

[0010] FIG. 2 is a drawing showing the results of evaluating the performance of a catalyst composition according to one embodiment of the present invention.

[0011] One embodiment of the present invention provides a catalyst composition comprising a catalyst and a support comprising a post-transition metal and a metal oxide, wherein the catalyst comprises a platinum group element.

[0012] In one embodiment of the present invention, the platinum group element may include Ir, Ru, Rh, Pd, Os, Re, Au or Pt.

[0013] In one embodiment of the present invention, the post-transition metal may include a Group 13 element.

[0014] In one embodiment of the present invention, the post-transition metal may include Ga, In, Al or B.

[0015] In one embodiment of the present invention, the metal oxide may include an oxide of a transition metal.

[0016] In one embodiment of the present invention, the metal oxide may include an oxide of one or more metals selected from Ti, Sn, W, Ta, Si, Co, Ni, Nb, Zn, Mo, Mn, Cr, V, Cu, Zr, Fe, Bi and Sb.

[0017] In one embodiment of the present invention, the first post-transition metal can be doped into the metal oxide at 0.1 to 20 mol%.

[0018] In one embodiment of the present invention, the particle size of the support may be 5 to 500 nm.

[0019] In one embodiment of the present invention, the relationship between the particle size (x) of the catalyst composition and the platinum group element content (y) of the catalyst may be as shown in Equation 1 below:

[0020] [Formula 1]

[0021] y≥175x -0.471 ,

[0022] The unit of the above x is nm, and the unit of y is wt%.

[0023] In one embodiment of the present invention, the specific surface area of ​​the support is 5 to 200 g / cm 3 It could be.

[0024] Another embodiment of the present invention provides an anode comprising the catalyst composition.

[0025] Another embodiment of the present invention provides a water electrolysis device comprising the anode.

[0026] One embodiment of the present invention is illustrated in the accompanying drawings. However, the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the present invention to those skilled in the art. Like reference numerals in the drawings indicate like elements.

[0027] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms including "at least one," unless the content clearly dictates otherwise. "At least one" should not be construed as limiting to the singular. As used herein, the term "and / or" includes any and all combinations of one or more of the listed items. The terms "comprises" and / or "comprising" as used in the detailed description specify the presence of stated features, regions, integers, steps, operations, components, and / or ingredients, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, components, ingredients, and / or groups thereof.

[0028] In this specification, reference to "on" or "on" another object includes not only directly on top of the other object, but also cases where an object is interposed between the other object.

[0029] Throughout the specification, when a part is said to be "connected (connected, contacted, coupled)" to another part, this includes not only cases where it is "directly connected" but also cases where it is "indirectly connected" with another part in between.

[0030] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. Furthermore, it will be understood that terms defined in commonly used dictionaries should be interpreted to have a meaning consistent with their meaning within the context of the relevant art and the present disclosure, and not in an idealized or overly formal sense.

[0031] While specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are not currently anticipated or unforeseen may occur to the applicant or those skilled in the art. Accordingly, the appended claims, as filed and as amended, are intended to encompass all such alternatives, modifications, variations, improvements, and substantial equivalents.

[0032] In the examples below, the terms first, second, etc. are not used in a limiting sense, but are used for the purpose of distinguishing one component from another.

[0033] In the examples below, singular expressions include plural expressions unless the context clearly indicates otherwise.

[0034] For convenience of explanation, the sizes of components in the drawings may be exaggerated or reduced. For example, the sizes and thicknesses of each component shown in the drawings are arbitrarily indicated for convenience of explanation, and thus the present invention is not necessarily limited to what is shown.

[0035] In some embodiments, where implementations are otherwise feasible, specific process sequences may be performed in a different order than described. For example, two processes described in succession may be performed substantially simultaneously, or in a reverse order from the described order.

[0036]

[0037] A catalyst composition according to one embodiment of the present invention may include a catalyst and a support including a post-transition metal and a metal oxide.

[0038] FIG. 1 is a schematic drawing showing a catalyst composition according to one embodiment of the present invention.

[0039] According to FIG. 1, a catalyst composition according to one embodiment of the present invention may include a catalyst and a support.

[0040] The catalyst may include a transition metal, and the transition metal may include, but is not limited to, a platinum group element.

[0041] The platinum group element may include Ir, Ru, Rh, Pd, Os, Re, Au or Pt, but is not particularly limited as long as it is an element that can act as a catalyst as a platinum group element. According to one embodiment of the present invention, the platinum group element may be Ir or Ru.

[0042] The above transition metal may include a Group 13 element, specifically, but not limited to, Ga, In, Al or B.

[0043] The metal oxide may include an oxide of a transition metal. Specifically, the metal oxide may include an oxide of one or more metals selected from Ti, Sn, W, Ta, Si, Co, Ni, Nb, Zn, Mo, Mn, Cr, V, Cu, Zr, Fe, Bi, and Sb, but is not limited thereto. According to one embodiment of the present invention, the metal oxide may be an oxide of Ti.

[0044] The above-described post-transition metal may be in a form doped into the metal oxide, and may be doped at 0.1 to 20 mol%; 0.1 to 15 mol%; 0.1 to 10 mol%; 0.1 to 5 mol%; 0.1 to 1 mol%; 0.1 to 0.5 mol%; 0.5 to 20 mol%; 0.5 to 15 mol%; 0.5 to 10 mol%; 0.5 to 5 mol%; 0.5 to 1 mol%; 1 to 20 mol%; 1 to 15 mol%; 1 to 10 mol%; 1 to 5 mol%; 5 to 20 mol%; 5 to 15 mol%; 5 to 10 mol%; 10 to 20 mol%; 10 to 15 mol%; or 15 to 20 mol%, but is not limited thereto.

[0045] The particle size of the support is 5 to 500 nm; 5 to 400 nm; 5 to 300 nm; 5 to 200 nm; 5 to 100 nm; 5 to 50 nm; 5 to 20 nm; 10 to 500 nm; 10 to 400 nm; 10 to 300 nm; 10 to 200 nm; 10 to 100 nm; 10 to 50 nm; 10 to 20 nm; 20 to 500 nm; 20 to 400 nm; 20 to 300 nm; 20 to 200 nm; 20 to 100 nm; 20 to 50 nm; 50 to 500 nm; 50 to 400 nm; 50 to 300 nm; 50 to 200 nm; 50 to 100 nm; 100 to 500 nm; 100 to 400 nm; 100 to 300 nm; 100 to 200 nm; 200 to 500 nm; 200 to 400 nm; 200 to 300 nm; 300 to 500 nm; 300 to 400 nm; or 400 to 500 nm, but is not limited thereto.

[0046] As the particle size of the support increases, the specific surface area decreases, and in the present invention, the performance can be improved within a range that satisfies the conditions of the following equation regarding the relationship between the particle size of the support and the content of the catalyst. A relationship such as the following equation 1 can be established between the particle size (x) of the catalyst composition and the content (y) of the platinum group element of the catalyst:

[0047] [Formula 1]

[0048] y≥175x -0.471 ,

[0049] The unit of the above x is nm, and the unit of y is wt%.

[0050] The specific surface area of ​​the above support is 5 to 200 g / cm 3 ; 5 to 150 g / cm 3 ; 5 to 100 g / cm 3 ;5 to 50 g / cm 3 ; 10 to 200 g / cm 3 ; 10 to 150 g / cm 3 ; 10 to 100 g / cm 3 ; 10 to 50 g / cm 3 ; 50 to 200 g / cm 3 ; 50 to 150 g / cm 3 ; 50 to 100 g / cm 3 ; 100 to 200 g / cm 3 ; 100 to 150 g / cm 3 ; or 150 to 200 g / cm 3 It may include, but is not limited to.

[0051] The morphology of the above support may be spherical, cubic, tubular, rod-shaped, spherical, hollow spherical, or plate-shaped, but is not particularly limited thereto as long as it has a structure that can function as a support.

[0052] The above catalyst composition can be represented by the following chemical formula 1:

[0053] [Chemical Formula 1]

[0054] M a @N b -L 100-b

[0055] In the above chemical formula 1,

[0056] The above M is a metal oxide or alloy containing one or more platinum group elements,

[0057] N contains post-transition metals,

[0058] L is a metal oxide,

[0059] a and b are each independently rational numbers,

[0060] The above M may include one or more of Ir, Ru, Rh, Pd, Os, Re, Au, or Pt, but is not particularly limited as long as it is a metal that can act as a catalyst. According to one embodiment of the present invention, the above M may be Ir or Ru.

[0061] The above N may include, but is not limited to, Ga, In, Al or B.

[0062] The above L may include an oxide of one or more metals selected from Ti, Sn, W, Ta, Si, Co, Ni, Nb, Zn, Mo, Mn, Cr, V, Cu, Zr, Fe, Bi, and Sb, but is not limited thereto. According to one embodiment of the present invention, the L may be an oxide of Ti.

[0063] The above a may be a rational number of 1 to 10; 1 to 5; or 1 to 3, but is not limited thereto. The above b may be a rational number of 0.1 to 20; 0.1 to 10; 0.1 to 5; or 0.1 to 3, but is not limited thereto. According to one embodiment of the present invention, the above a may be 1.

[0064] The above @ may mean that a catalyst is formed on the surface of the support.

[0065]

[0066] Another embodiment of the present invention provides an electrode comprising the catalyst composition and a water electrolysis device comprising the same.

[0067] An electrode comprising the above catalyst composition may be applied to either or both of the anode and the cathode. According to one embodiment of the present invention, the electrode comprising the above catalyst composition may be an anode.

[0068] The above catalyst composition can be applied in the same manner as the above-described example or modified as needed, and a more detailed description is omitted.

[0069]

[0070] Hereinafter, the present invention will be described in detail through examples and experimental examples.

[0071] However, the examples and experimental examples described below are only specific examples of one aspect of the present invention, and the present invention is not limited thereto.

[0072]

[0073] <Example> Preparation of catalyst composition

[0074] Manufacturing of supports

[0075] Titanium isopropoxide, gallium nitrate, ethanol, deionized water (DIW), and acetic acid were added to a beaker and stirred. After sufficient stirring, heating was applied at 80°C to form a white precipitate. The white precipitate was separated using a centrifuge and washed. After drying in an oven, heat treatment was performed to obtain a support.

[0076]

[0077] Preparation of catalyst composition

[0078] The support, hydrogen hexachloroiridate hydrate, sodium nitrate, and IPA prepared in a beaker were added and stirred. After sufficient stirring, brown particles were obtained through heat treatment at 80°C. After obtaining the brown particles, the surface was washed, further heat treated at 350°C, and dried in an oven to obtain the catalyst.

[0079]

[0080] <Experimental Example 1> Performance Evaluation According to the Introduction of Ga Support

[0081] The performance of a catalyst composition manufactured according to one embodiment of the present invention was evaluated according to the introduction of a Ga support. A 2 μL drop of the catalyst composition dispersed on the electrode was then connected to the RDE device. 0.1 M HClO4 was used as the electrolyte, and the LSV was measured at 1.2 to 1.7 V. The evaluation results are shown in Table 1 and Figure 2 below.

[0082] Catalyst composition Support Catalyst content (%) Performance (@1.6V) Comparative example 1 IrOxX9020 Comparative example 2 IrOx@TiO2O6520 Comparative example 3 IrOx@SnO2O6520.4 Example 1 IrOx@Ga-TiO2O6524 Example 11 IrOx@Ga-TiO2O4526.6

[0083] Comparing Comparative Examples 1 and 2 in Table 1, it can be seen that the catalyst content decreased with the introduction of the support. In addition, unlike the Comparative Examples, it can be seen that when a Ga support was introduced, as in Example 1 or Example 11, the performance was significantly improved by about 20% and 33%, respectively.

[0084]

[0085] <Experimental Example 2> Performance Evaluation According to Ga Support Content

[0086] The performance of a catalyst composition manufactured according to one embodiment of the present invention was evaluated according to the content of the Ga support. The performance evaluation method was the same as that of Experimental Example 1, and the evaluation results are shown in Table 2 below.

[0087] Catalyst compositionGa content (mol%)Precious metal content of catalyst (%)Performance (@1.6V)Example 2IrOx@Ga-TiO20.036520Example 30.120.4Example 40.520.6Example 51212Example 6323.1Example 1524Example 71022.3Example 82020.5Example 92518.1

[0088] As shown in Table 2 above, high performance was observed in all examples, and it can be confirmed that the performance was significantly improved, especially when the Ga content was 3 to 10 mol%.

[0089]

[0090] <Experimental Example 3> Performance evaluation according to particle size, specific surface area, and catalyst content of the support

[0091] The performance of a catalyst composition manufactured according to one embodiment of the present invention was evaluated according to the particle size, specific surface area, and catalyst content of the support. The performance evaluation method was the same as that of Experimental Example 1, and the evaluation results are shown in Table 3 below.

[0092] Distinctive particle size (nm) Specific surface area (m 2 / g) Precious metal content (wt%) of catalyst Performance (@1.6V) Example 10101518023.5 Example 10-16022.4 Example 10-24515.9 Example 115936524 Example 1-15023.5 Example 1-23515 Example 1150294526.6 Example 11-13026.2 Example 11-22018.8 Example 12100153024 Example 12-12023.7 Example 12-21517.3 Example 1320082524 Example 13-11522.8 Example 13-21016.7

[0093] In Table 3 above, the catalyst composition of the example was IrOx@Ga-TiO2, and it can be seen that the specific surface area decreases as the particle size of the support increases. At this time, it was confirmed that there exists a minimum catalyst content for exhibiting excellent performance depending on the particle size. As a result of analyzing the relationship between the particle size (x) exhibiting excellent performance and the platinum group element content (y) of the catalyst, the following relationship was derived: [Equation 1]

[0094] y≥175x -0.471 .

[0095]

[0096] <Experimental Example 4> Performance Evaluation by Catalyst Type

[0097] The performance of the catalyst composition manufactured according to one embodiment of the present invention was evaluated according to the type of catalyst. The performance evaluation method was the same as Experimental Example 1, and the evaluation results are shown in Table 4 below.

[0098] Catalyst composition Catalyst precious metal content (wt%) Performance (@1.6V) Comparative example 1 IrOx 90 20 Example 1 4 Ru@Ga-TiO 2 6 5 2 4.6 Example 1 IrOx@Ga-TiO 2 6 5 2 4

[0099] As shown in Table 4 above, when the catalyst is Ir or Ru, it can be seen that the performance is improved by about 20% or more compared to Comparative Example 1. This confirms that the catalyst composition according to the present invention has improved performance despite having a catalyst content of 65 wt% by introducing a novel support.

[0100]

[0101] <Experimental Example 5> Performance Evaluation by Type of Support

[0102] The performance of the catalyst composition manufactured according to one embodiment of the present invention was evaluated according to the type of support. The performance evaluation method was the same as Experimental Example 1, and the evaluation results are shown in Table 5 below.

[0103] Catalyst composition Doping content (mol%) Precious metal content of catalyst (wt%) Performance (@1.6V) Example 6 IrOx@Ga-TiO2 36 5 23.1 Example 15 24 Example 15 IrOx@In-TiO2 3 22.4 Example 16 5 22.1 Example 17 IrOx@B-TiO2 5 22.5 Example 18 IrOx@Al-TiO2 5 23 Example 19 IrOx@In-SnO2 10 21

[0104] As shown in Table 5 above, it can be seen that excellent performance is achieved even when the doping content of transition metals and / or post-transition metals in the support is changed. This confirms that when preparing a catalyst composition according to one embodiment of the present invention, particularly when using Ga, In, B, or Al as the support, excellent performance is achieved.

[0105] The foregoing description of the present invention is for illustrative purposes only, and those skilled in the art will readily appreciate that the present invention can be readily modified into other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single entity may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined manner.

[0106] The scope of the present invention is indicated by the claims described below, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

Claims

1. Catalyst; and A support comprising a post-transition metal and a metal oxide, The catalyst is a catalyst composition comprising a platinum group element.

2. In paragraph 1, A catalyst composition wherein the platinum group element comprises Ir, Ru, Rh, Pd, Os, Re, Au or Pt.

3. In paragraph 1, A catalyst composition wherein the above transition metal contains a group 13 element.

4. In paragraph 1, A catalyst composition wherein the above transition metal comprises Ga, In, Al or B.

5. In paragraph 1, A catalyst composition wherein the metal oxide comprises an oxide of a transition metal.

6. In paragraph 1, A catalyst composition, wherein the metal oxide comprises an oxide of one or more metals selected from Ti, Sn, W, Ta, Si, Co, Ni, Nb, Zn, Mo, Mn, Cr, V, Cu, Zr, Fe, Bi and Sb.

7. In paragraph 1, A catalyst composition wherein the above transition metal is doped into the metal oxide at 0.1 to 20 mol%.

8. In paragraph 1, A catalyst composition wherein the particle size of the support is 5 to 500 nm.

9. In paragraph 1, The relationship between the particle size (x) of the catalyst composition and the platinum group element content (y) of the catalyst is as follows: [Formula 1] y≥175x -0.471 , The unit of the above x is nm, and the unit of y is wt%.

10. In paragraph 1, The specific surface area of ​​the above support is 5 to 200 g / cm 3 A catalyst composition.

11. An anode comprising a catalyst composition according to any one of claims 1 to 10.

12. Electrolysis, including the anode of clause 11.

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