Electrochromic structure, electrochromic device and preparation method thereof

Abstract

The present invention discloses an electrochromic structure, an electrochromic device and a preparation method thereof. The electrochromic structure includes an ion storage layer, an ion conductor layer and an electrochromic layer arranged in sequence; at least one of the ion storage layer, the ion conductor layer and the electrochromic layer contains rare earth elements. The technical solution of the present invention improves the color change effect of the electrochromic structure.

Description

Technical Field

[0001] The present invention relates to the technical field of electrochromic devices, and particularly relates to an electrochromic structure, an electrochromic device and a preparation method thereof. Background Art

[0002] Electrochromic glass is a common electrochromic device. Generally, electrochromic glass includes two glass substrates and a first transparent conductive layer (TC), an electrochromic structure, and a second transparent conductive layer (TC) which are sequentially arranged between the two glass substrates. Among them, the electrochromic structure in the inorganic electrochromic device contains a WOx-based functional material electrochromic layer. WOx has excellent coloring ability, optical modulation ability and durability, which is beneficial to the industrialization of electrochromic devices. During the electrochromic process, due to the action of an electric field, colorless WOx obtains electrons to form M x WOx compound, making the film change from transparent to blue; at the same time, applying a reverse voltage, electrons are deintercalated from M x WOx to form colorless WOx, so that the film is restored from blue to transparent, completing the electrochromic process.

[0003] The optical contrast and coloring efficiency of electrochromic devices depend on the lithium ion diffusion coefficient, WOx, the specific surface area of the lithium ion storage film layer, the lithium ion concentration, and the special structure of the film layer. As the number of cycles of electrochromic glass increases, its current density will decrease sharply, the color-changing effect of the film layer will become worse and worse, and the morphologies of the WOx and NiOx film layers will gradually become dense, eventually resulting in the complete intercalation or deintercalation of lithium ions in the electrochromic layer. Moreover, as the lithium ion concentration decreases, the chemical reaction of the WOx and NiOx film layers cannot be fully induced, and colorless WOx cannot be reduced to blue M x WOx compound, thus causing the electrochromic device to lose its function. Summary of the Invention

[0004] The main purpose of the present invention is to provide an electrochromic structure, an electrochromic device and a preparation method thereof, aiming to improve the color-changing effect of the electrochromic device.

[0005] To achieve the above object, the electrochromic structure proposed by the present invention includes:

[0006] An ion storage layer, an ion conductor layer, and an electrochromic layer arranged in sequence;

[0007] At least one of the ion storage layer, the ion conductor layer, and the electrochromic layer contains a rare earth element.

[0008] In an embodiment of the present invention, the electrochromic structure includes an ion storage layer, an ion conductor layer, and an electrochromic layer arranged in sequence;

[0009] At least one of the ion storage layer, the ion conductor layer, and the electrochromic layer contains a rare earth element.

[0010] In one embodiment of the present invention, the ion storage layer, the ion conductor layer, and the electrochromic layer all contain rare earth elements.

[0011] In one embodiment of the present invention, the electrochromic layer contains a rare earth element.

[0012] In one embodiment of the present invention, the material of the ion storage layer is NiOx;

[0013] And / or, the material of the ion conductor layer is LiNbO3;

[0014] And / or, the material of the electrochromic layer is WOx.

[0015] In one embodiment of the present invention, the thickness range of the ion storage layer is 20 - 100 nm;

[0016] And / or, the thickness range of the ion conductor layer is 50 - 150 nm;

[0017] And / or, the thickness range of the electrochromic layer is 50 - 130 nm.

[0018] In one embodiment of the present invention, the mass fraction range of the rare earth element in the electrochromic structure is 0.1% - 1%.

[0019] In one embodiment of the present invention, the rare earth element includes at least one of gadolinium, samarium, and thulium.

[0020] In one embodiment of the present invention, the rare earth element includes gadolinium.

[0021] The present invention also provides an electrochromic device, which includes two spaced substrates, a first transparent conductive layer, a second transparent conductive layer, and an electrochromic structure;

[0022] The opposite surfaces of the two substrates are a first side and a second side respectively,

[0023] The first transparent conductive layer, the electrochromic structure, and the second transparent conductive layer are sequentially stacked and arranged from the first side to the second side.

[0024] In one embodiment of the present invention, the material of the substrate is glass;

[0025] And / or, the materials of the first transparent conductive layer and the second transparent conductive layer are ITO.

[0026] The present invention also provides a method for preparing an electrochromic device, comprising the following steps:

[0027] Provide two substrates, with the two substrates arranged at intervals, and the opposite surfaces of the two substrates being the first side and the second side respectively;

[0028] Form a first transparent conductive layer on the first side surface and a second transparent conductive layer on the second side surface;

[0029] Use a target doped with rare earth elements between the first transparent conductive layer and the second transparent conductive layer, and utilize magnetron sputtering technology to form a rare earth element-containing electrochromic structure;

[0030] Among them, forming the rare earth element-containing electrochromic structure includes an ion storage layer, an ion conductor layer, and an electrochromic layer arranged in sequence.

[0031] In an embodiment of the present invention, after the step of forming a first transparent conductive layer on the first side surface and a second transparent conductive layer on the second side surface, it further includes:

[0032] Clean the substrates with polyacrylamide to remove the oil stains on the surfaces of the first transparent conductive layer and the second transparent conductive layer;

[0033] Clean the surfaces of the first transparent conductive layer and the second transparent conductive layer again with an acetone and ethanol solution;

[0034] Clean the substrates with an ultrasonic cleaner;

[0035] Dry the cleaned substrates with acetone and ethanol.

[0036] In an embodiment of the present invention, after the step of using a target doped with rare earth elements between the first transparent conductive layer and the second transparent conductive layer and utilizing magnetron sputtering technology to form a rare earth element-containing electrochromic structure, it further includes:

[0037] Inject a sealant at the joint of the two substrates to obtain a rare earth element-doped electrochromic device.

[0038] In the technical solution of the present invention, the electrochromic structure is applied to an electrochromic device. Since at least one layer in the electrochromic structure contains rare earth elements. The rare earth elements are doped in the electrochromic structure. Due to the large atomic radius of the rare earth elements, the crystal structure of the film layer in the electrochromic structure can be effectively improved. And the rare earth elements themselves have excellent polarization effects and an incompletely filled outer electron layer structure, which can directly cause a series of changes such as an increase in the lattice constant of the electrochromic structure, the system maintaining semiconductor properties, a reduction in the band gap energy, and the emergence of band edge states near the EF energy level. This enables the electrochromic structure to increase the lithium ion migration channels during the color change reaction, while reducing the energy during the migration process, effectively improving problems such as the incomplete embedding and poor deintercalation of lithium ions in the electrochromic device, enabling the electrochromic device to achieve rapid color change under the action of an electric field, with a visible light transmittance in the colored state of 20% - 30%, a visible light transmittance in the faded state of 70% - 90%, and a maximum transmittance difference of 30% - 70%. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or in the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on the structures shown in these drawings.

[0040] Figure 1 It is a schematic structural diagram of the electrochromic structure of the present invention;

[0041] Figure 2 It is a schematic structural diagram of an embodiment of the electrochromic device of the present invention;

[0042] Figure 3 is Figure 2 a partial enlarged view at the electrochromic device in;

[0043] Figure 4 It is a schematic diagram of the preparation process of the electrochromic device of the present invention.

[0044] Description of the reference numerals in the drawings:

[0045] Label Name Label Name 100 Electrochromic device 30 Electrochromic structure 10 Substrate 31 Ion storage layer 21 First transparent conductive layer 33 Ion conductor layer 23 Second transparent conductive layer 35 Electrochromic layer

[0046] The realization of the object of the present invention, functional features and advantages will be further described with reference to the embodiments and the drawings. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0047] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0048] It should be noted that all directional indications (such as up, down, left, right, front, back...) in the embodiments of the present invention are only used to explain the relative positional relationship and movement conditions between components in a specific posture (as shown in the accompanying drawings). If the specific posture changes, the directional indications will also change accordingly.

[0049] In the present invention, unless otherwise clearly defined and limited, terms such as "connection" and "fixation" should be understood in a broad sense. For example, "fixation" can be a fixed connection, a detachable connection, or integrated; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the communication inside two components or the interaction relationship between two components, unless otherwise clearly limited. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific situations.

[0050] In addition, in the present invention, descriptions such as "first" and "second" are only for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the quantity of the indicated technical features. Thus, features defined with "first" and "second" may explicitly or implicitly include at least one of such features. In addition, the meaning of "and / or" appearing throughout the text is to include three parallel solutions. Taking "electrochromic device and / or B" as an example, it includes the electrochromic device solution, or the B solution, or the solution where both the electrochromic device and B are satisfied. In addition, the technical solutions between various embodiments can be combined with each other, but it must be based on the fact that those of ordinary skill in the art can implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such a combination of technical solutions does not exist and is not within the protection scope required by the present invention.

[0051] The present invention provides an electrochromic structure 30.

[0052] Referring to Figure 1 , in an embodiment of the present invention, the electrochromic structure 30 includes an ion storage layer 31, an ion conductor layer 33, and an electrochromic layer 35 arranged in sequence;

[0053] At least one of the ion storage layer 31, the ion conductor layer 33, and the electrochromic layer 35 contains rare earth elements.

[0054] In the technical solution of the present invention, the electrochromic structure 30 is applied to the electrochromic device 100. Since at least one layer in the electrochromic structure 30 contains rare earth elements, the rare earth elements can be uniformly doped in the electrochromic structure 30. Due to the large atomic radius of the rare earth elements, the structure of the film layer in the electrochromic structure 30 can be effectively improved. Moreover, the rare earth elements themselves have excellent polarization effects and an outer electron layer structure that is not fully filled. This can directly cause a series of changes such as an increase in the lattice constant of the electrochromic structure 30, the system remaining semiconductive, a reduction in the band gap energy, and the emergence of band edge states near the EF energy level. As a result, when the electrochromic structure 30 undergoes a color change reaction, it can increase the lithium ion migration channels and reduce the energy during the migration process, effectively improving problems such as the incomplete insertion and extraction of lithium ions in the electrochromic device 100. This enables the electrochromic device 100 to achieve rapid color change under the action of an electric field. The visible light transmittance in the colored state reaches 20% - 30%, the visible light transmittance in the bleached state reaches 70% - 90%, and the maximum transmittance difference reaches 30% - 70%.

[0055] Referring to Figure 2 and Figure 3 , the main object of the present invention is to provide an electrochromic device 100, aiming to improve the color change effect of the electrochromic device 100.

[0056] To achieve the above object, the electrochromic device 100 proposed by the present invention includes:

[0057] Two spaced substrates 10, and the opposite surfaces of the two substrates 10 are respectively a first side (not marked) and a second side (not marked);

[0058] A first transparent conductive layer 21, an electrochromic structure 30, and a second transparent conductive layer 23 are sequentially provided from the first side to the second side;

[0059] Among them, the electrochromic structure 30 contains rare earth elements.

[0060] In this embodiment, the substrate 10 is glass, and the electrochromic device 100 thus formed is the electrochromic device 100. The first transparent conductive layer 21 and the second transparent conductive layer 23 are respectively the positive and negative electrodes when the electrochromic structure 30 is energized, so as to facilitate the connection of the electrochromic structure 30 to the circuit structure of the controller. The first transparent conductive layer 21 and the second transparent conductive layer 23 can be formed by depositing an ITO film on the glass substrate 10 using a magnetron sputtering method. They have good electrical conduction functions and good visible light transmittance, enabling the electrochromic device 100 to have good conductive functions and visible light transmittance.

[0061] Referring to Figure 2 andFigure 3 In an embodiment of the present invention, the electrochromic structure 30 includes an ion storage layer 31, an ion conductor layer 33, and an electrochromic layer 35 arranged in sequence;

[0062] At least one of the ion storage layer 31, the ion conductor layer 33, and the electrochromic layer 35 contains rare earth elements.

[0063] In an embodiment of the present invention, the ion storage layer 31 is a film layer containing NiOx, which is used to store ions and maintain the balance of ions in the electrochromic structure 30. The ion conductor layer 33 is a film layer containing LiNbO3, and the electrochromic layer 35 is a film layer containing WOx. In this solution, it can be that one of the ion storage layer 31, the ion conductor layer 33, and the electrochromic layer 35 contains rare earth elements, or two layers contain rare earth elements, or all three layers contain rare earth elements.

[0064] Among them, when only one of the ion storage layer 31, the ion conductor layer 33, and the electrochromic layer 35 contains rare earth elements, the rare earth elements can be doped into the film layer of the ion storage layer 31 during magnetron sputtering coating, or the rare earth elements can be doped into the film layer of the ion conductor layer 33 during magnetron sputtering coating, or the rare earth elements can be doped into the film layer of the electrochromic layer 35 during magnetron sputtering coating.

[0065] In another embodiment, when the ion storage layer 31, the ion conductor layer 33, and the electrochromic layer 35 all contain rare earth elements, at this time, the rare earth elements can be doped into the film layers of each layer respectively during magnetron sputtering coating.

[0066] In this embodiment, doping rare earth elements into the electrochromic structure 30 can improve the color change response efficiency of the electrochromic device. Hereinafter, taking the doping of rare earth elements into the electrochromic layer 35 as an example, how rare earth elements improve the color change response efficiency of the electrochromic device will be introduced in detail:

[0067] The rare earth elements can enter the WOx unit cells in the electrochromic layer 35 or enter the interstitial spaces of its unit cells. The atomic radius of the rare earth elements is relatively large and the polarization effect is obvious, which can effectively expand the channels for the insertion and extraction of lithium ions to flow, so as to facilitate the free passage of lithium ions through the channels to combine with WOx, or to facilitate the separation of lithium ions from M x The lithium ions separated from WOx leave through this channel, facilitating the free flow of ions in the electrochromic layer 35, thereby effectively improving the disadvantages such as the incomplete insertion and extraction of lithium ions in the electrochromic structure 30, and enhancing the color change response efficiency of the electrochromic device.

[0068] Understandably, in the electrochromic structure 30, the ion storage layer 31, the ion conductor layer 33, and the electrochromic layer 35 may be arranged in sequence. For example, the ion storage layer 31, the ion conductor layer 33, and the electrochromic layer 35 may be arranged in sequence from the first transparent conductive layer 21 to the second transparent conductive layer 23, or may be arranged in sequence from the second transparent conductive layer 23 to the first transparent conductive layer 21. No limitation is made here.

[0069] Among them, the target includes a ceramic target, and the mass fraction of the rare earth element doped in the ceramic target is 0.1% - 1%. The thickness range of the ion storage layer 31 is 20 - 100 nm, the thickness range of the ion conductor layer 33 is 50 - 150 nm; the thickness range of the electrochromic layer 35 is 50 - 130 nm.

[0070] In one embodiment, the visible light transmittance in the colored state, the visible light transmittance in the bleached state, and the maximum transmittance difference of the electrochromic device 100 are related to the thickness of each film layer in the electrochromic structure 30 and its rare earth content. Among them, in the electrochromic device 100 made according to the above parameters, the visible light transmittance in the colored state can reach 20% - 30%, the visible light transmittance in the bleached state can reach 70% - 90%, and the maximum transmittance difference reaches 30% - 70%. In this way, the national standard requirements of the industry can be met.

[0071] In one embodiment of the present invention, the rare earth element includes at least one of gadolinium, samarium, and thulium. In the embodiment of the present invention, the rare earth element may be gadolinium, may be samarium, or may be thulium. Or, the rare earth element may also be a combination of two or three of gadolinium, samarium, and thulium.

[0072] Refer to Figure 4 , the present invention also provides a preparation method of an electrochromic device 100, including the following steps:

[0073] S10: Provide two substrates 10, and the two substrates 10 are arranged at intervals. The opposite surfaces of the two substrates 10 are the first side and the second side respectively;

[0074] S20: Form a first transparent conductive layer 21 on the first side surface and a second transparent conductive layer 23 on the second side surface;

[0075] S30: Use a target doped with rare earth elements between the first transparent conductive layer 21 and the second transparent conductive layer 23, and use magnetron sputtering technology to form an electrochromic structure 30 containing rare earth elements;

[0076] Among them, forming the electrochromic structure 30 containing rare earth elements includes an ion storage layer 31, an ion conductor layer 33, and an electrochromic layer 35 arranged in sequence.

[0077] In the technical solution of an embodiment of the present invention, in step S10, when providing the two substrates 10, it is necessary to clean the substrates 10 in advance to reduce the stains on the surfaces of the substrates 10. In step S20, the first transparent conductive layer 21 and the second transparent conductive layer 23 can be formed separately or simultaneously. Among them, the first transparent conductive layer 21 and the second transparent conductive layer 23 are made by magnetron sputtering. The materials of the first transparent conductive layer 21 and the second transparent conductive layer 23 are ITO, which can make the first transparent conductive layer 21 and the second transparent conductive layer 23 have both good conductive and transparent functions. After the first transparent conductive layer 21 and the second transparent conductive layer are made, controller circuit contact points are reserved.

[0078] It can be understood that when manufacturing the electrochromic device 100, the first transparent conductive layer 21, the electrochromic structure 30, and the second transparent conductive layer 23 can be sequentially manufactured on the surface of one of the substrates 10 first, and finally the other substrate 10 is covered on the second transparent conductive layer 23 to form the electrochromic device 100. Or, the first transparent conductive layer 21 and the electrochromic structure 30 can be sequentially manufactured on the surface of one of the substrates 10, the second transparent conductive layer 23 is manufactured on the surface of the other substrate 10, and then the substrate 10 provided with the second transparent conductive layer 23 is covered on the electrochromic structure 30 to bond the electrochromic structure 30 and the second transparent conductive layer 23, thereby forming the electrochromic device 100. Or, part of the film layers of the first transparent conductive layer 21 and the electrochromic structure 30 can be sequentially manufactured on the surface of one substrate 10, the remaining film layers of the second transparent conductive layer 23 and the electrochromic structure 30 can be sequentially manufactured on the surface of the other substrate 10, and then the two substrates 10 are arranged opposite to each other, so that after the film layers of the electrochromic structure are bonded, the electrochromic device 100 is formed.

[0079] In an embodiment of the present invention, after the steps of forming the first transparent conductive layer 21 on the first side surface and the second transparent conductive layer 23 on the second side surface, it further includes:

[0080] Clean the substrate 10 with polyacrylamide to remove the oil stains on the surfaces of the first transparent conductive layer 21 and the second transparent conductive layer 23;

[0081] Clean the surfaces of the first transparent conductive layer 21 and the second transparent conductive layer 23 again with acetone and ethanol solution;

[0082] Clean the substrate 10 with an ultrasonic cleaner;

[0083] Dry the cleaned substrate 10 with acetone and ethanol.

[0084] In step S20, after the first transparent conductive layer 21 and the second transparent conductive layer 23 are fabricated, it is necessary to clean the first transparent conductive layer 21 and the second transparent conductive layer 23. When cleaning, polyacrylamide can be used to remove the oil stains on the ITO surface, and then acetone, ethanol and other solutions are used to remove the remaining oil stains and impurities that have not been cleaned thoroughly. Finally, the samples are taken out after being cleaned in an ultrasonic cleaning machine for 1 - 5 hours, and then dried with acetone and ethanol, waiting for the next processing step.

[0085] In an embodiment of the present invention, after the step of forming the rare earth element - containing electrochromic structure 30 by using a target doped with rare earth elements between the first transparent conductive layer 21 and the second transparent conductive layer 23 by means of magnetron sputtering technology, the following steps are further included:

[0086] Inject sealant at the joint of the two substrates 10 to obtain an electrochromic device doped with rare earth elements.

[0087] In step S30, each film layer in the electrochromic structure 30 is fabricated by magnetron sputtering. Among them, when performing magnetron sputtering, a target containing rare earth elements is used. In this way, the target can be bombarded during magnetron sputtering, enabling rare earth elements to be doped into the film layer, and a film layer containing rare earth elements is prepared. After the electrochromic structure 30 is fabricated, the joint of the two substrates 10 is sealed with a sealant. Among them, the sealant can be a sealant with ultraviolet - resistant performance to improve the ultraviolet - resistant performance of electrochromism. For example, the sealant is AB glue.

[0088] Example 1

[0089] Step S10, provide two glass substrates with a size of 10 cm * 10 cm as samples;

[0090] Step S20, respectively fabricate the first transparent conductive layer and the second transparent conductive layer on the opposite surfaces of the two 10 cm * 10 cm glass samples, while leaving contact points for the controller circuit. Then, successively use polyacrylamide to remove the oil stains on the first transparent conductive layer and the second transparent conductive layer, and then use acetone, ethanol and other solutions to remove the remaining oil stains and impurities that have not been cleaned thoroughly. Finally, after cleaning the glass samples in an ultrasonic cleaning machine for 3 hours, take out the glass samples and dry them with acetone and ethanol, waiting for the next step. Among them, both the first transparent conductive layer and the second transparent conductive layer are made of ITO material, and the glass samples with the first transparent conductive layer and the second transparent conductive layer fabricated are also called ITO glass samples.

[0091] Step S30, fabricate the electrochromic structure:

[0092] In step S30, an ion storage layer is prepared. Take a piece of ITO glass sample that has been cleaned, and use NiOx as the material for magnetron sputtering coating. It is carried out by controlling parameters such as sputtering power, coating rate, and flowmeter. The specific process parameters are as follows in the table:

[0093]

[0094] In step S30, an electrochromic layer is prepared. Take a piece of cleaned ITO conductive glass, and use WOx ceramic doped with 0.1% mass fraction of Gd rare earth element as the target, and carry out magnetron sputtering in an Ar environment. It is carried out by controlling parameters such as sputtering power, coating rate, and flowmeter. The specific process parameters are as follows in the table:

[0095]

[0096] In step S30, an ion conductor layer is prepared. Use magnetron sputtering ion conductor layer process LiNbO3 on the prepared ion storage layer. The specific process parameters are as follows in the table:

[0097]

[0098] Then assemble. During assembly, assemble the two glass substrates so that a transparent conductive layer, a second transparent conductive layer, and an electrochromic structure are located between the two glasses. Finally, evenly inject anti-ultraviolet AB glue at the joint of the two glass substrates to make electrochromic glass.

[0099] Among them, the physical parameters of the electrochromic glass prepared in the embodiment are as follows in the table:

[0100]

[0101] The visible light transmittance in the colored state of the electrochromic glass prepared according to the process parameters in Example 1 is 80%, the visible light transmittance in the bleached state is 23%, and the maximum difference in visible light transmittance is 57%, all of which meet the national standard requirements and meet the industry use standards.

[0102] Example 2

[0103] Step S10, provide two glass substrates with a size of 10 cm * 10 cm as samples;

[0104] Step S20: On the opposite surfaces of two 10 cm × 10 cm glass slides, a first transparent conductive layer and a second transparent conductive layer are respectively fabricated, while leaving contact points for the controller circuit. Then, polyacrylamide is used to remove the oil stains on the first transparent conductive layer and the second transparent conductive layer in sequence. Next, solutions such as acetone and ethanol are used to remove the remaining uncleaned oil stains and impurities again. Finally, the glass slides are cleaned in an ultrasonic cleaner for 3 h, taken out, and dried with acetone and ethanol, awaiting the next step. Among them, both the first transparent conductive layer and the second transparent conductive layer are made of ITO material, and the glass slides with the first transparent conductive layer and the second transparent conductive layer fabricated are also called ITO glass slides.

[0105] Step S30: Fabricate the electrochromic structure:

[0106] In step S30, prepare the ion storage layer. Take a piece of ITO glass slide that has been completed cleaning, and use Ni as the material for magnetron sputtering coating. The specific process is as follows by controlling parameters such as sputtering power, coating rate, and flowmeter:

[0107]

[0108] In step S30, prepare the electrochromic layer. Take a piece of cleaned ITO conductive glass, use WO3 ceramic doped with 0.5% by mass fraction of Gd rare earth element as the target, and perform magnetron sputtering in an Ar environment. The process is carried out by controlling parameters such as sputtering power, coating rate, and flowmeter. The specific process parameters are as follows in the table:

[0109]

[0110] In step S30, prepare the ion conductor layer. Use the magnetron sputtering ion conductor layer process (LiNbO3) on the previously prepared ion storage layer. The specific process parameters are as follows in the table:

[0111]

[0112] Then, assemble. When assembling, assemble the two glass substrates so that the first transparent conductive layer, the second transparent conductive layer, and the electrochromic structure are located between the two glasses. Finally, evenly inject anti-ultraviolet AB glue at the joint of the two glass substrates to make the electrochromic glass.

[0113] Among them, the physical parameters of the electrochromic glass prepared in the embodiment are as follows in the table:

[0114]

[0115] The visible light transmittance of the electrochromic glass prepared according to the process parameters in Example 2 is 70%, the visible light bleached state transmittance is 20%, and the maximum difference in visible light transmittance is 50%, all meeting the national standard requirements and meeting the industry use standards.

[0116] Example 3

[0117] Step S10: Provide two glass substrates with a size of 10 cm * 10 cm as sample pieces;

[0118] Step S20: On the opposite surfaces of the two 10 cm * 10 cm glass sample pieces, a first transparent conductive layer and a second transparent conductive layer are respectively fabricated, while leaving contact points for the controller circuit. Then, polyacrylamide is used to remove the oil stains on the first transparent conductive layer and the second transparent conductive layer in sequence. Then, solutions such as acetone and ethanol are used to remove the remaining oil stains and impurities that were not cleaned thoroughly. Finally, it is cleaned in an ultrasonic cleaner for 3 h. After taking out the glass sample pieces, they are dried with acetone and ethanol and waiting for the next step. Among them, both the first transparent conductive layer and the second transparent conductive layer are made of ITO material. The glass sample pieces with the first transparent conductive layer and the second transparent conductive layer fabricated are also called ITO glass sample pieces.

[0119] Step S30: Fabricate the electrochromic structure:

[0120] In step S30, prepare the ion storage layer. Take a piece of ITO glass sample piece that has been completed in cleaning, and use Ni as the material for magnetron sputtering coating. The specific process is as follows by controlling parameters such as sputtering power, coating rate, and flowmeter:

[0121]

[0122] In step S30, prepare the electrochromic layer. Take a piece of cleaned ITO conductive glass, use WO3 ceramic doped with 1% by mass fraction of Gd rare earth element as the target, and conduct magnetron sputtering in an Ar environment. It is carried out by controlling parameters such as sputtering power, coating rate, and flowmeter. The specific process parameters are as follows in the table:

[0123]

[0124] In step S30, prepare the ion conductor layer. Use the magnetron sputtering ion conductor layer process (LiNbO3) on the ion storage layer that has been prepared. The specific process parameters are as follows in the table:

[0125]

[0126] Then, assemble. During assembly, the two glass substrates are assembled so that a first transparent conductive layer, a second transparent conductive layer, and the electrochromic structure are located between the two glasses. Finally, anti-ultraviolet AB glue is evenly injected into the joint of the two glass substrates to make the electrochromic glass.

[0127] Among them, the physical parameters of the electrochromic glass prepared in the examples are as follows in the table:

[0128]

[0129] The visible light transmittance in the colored state of the electrochromic glass prepared according to the process parameters in Example 3 is 90%, the visible light transmittance in the bleached state is 30%, and the maximum difference in visible light transmittance is 60%, all of which meet the national standard requirements and satisfy the industry use standards.

[0130] The above are only the preferred embodiments of the present invention, and do not limit the patent scope of the present invention accordingly. Any equivalent structural transformation made under the inventive concept of the present invention by using the content of the specification and drawings of the present invention, or directly / indirectly applied in other related technical fields, is included in the patent protection scope of the present invention.

Claims

1. An electrochromic structure, characterized in that the electrochromic structure includes an ion storage layer, an ion conductor layer, and an electrochromic layer arranged in sequence; at least one of the ion storage layer, the ion conductor layer, and the electrochromic layer contains rare earth elements; the rare earth elements include at least one of gadolinium, samarium, and thulium; the material of the ion storage layer is NiOx; the material of the ion conductor layer is LiNbO3; the material of the electrochromic layer is WOx; the electrochromic layer contains rare earth elements; the mass fraction range of rare earth elements in the electrochromic structure is 0.1% - 1%; 2. The electrochromic structure according to claim 1, characterized in that, the ion storage layer, the ion conductor layer, and the electrochromic layer all contain rare earth elements.

3. The electrochromic structure according to claim 1, characterized in that the thickness range of the ion storage layer is 20 - 100 nm; and / or, the thickness range of the ion conductor layer is 50 - 150 nm; and / or, the thickness range of the electrochromic layer is 50 - 130 nm.

4. The electrochromic structure according to claim 1, wherein, The rare earth element is gadolinium.

5. An electrochromic device, characterized in that, The electrochromic device includes two spaced substrates, a first transparent conductive layer, a second transparent conductive layer, and the electrochromic structure according to any one of claims 1 to 4; the opposite surfaces of the two substrates are the first side and the second side respectively, the first transparent conductive layer, the electrochromic structure, and the second transparent conductive layer are sequentially arranged in a stacked manner from the first side to the second side.

6. The electrochromic device according to claim 5, characterized in that, The material of the substrate is glass; and / or, the materials of the first transparent conductive layer and the second transparent conductive layer are ITO.

7. A method for preparing an electrochromic device according to any one of claims 5 to 6, characterized in that, Including the following steps: Provide two substrates, make the two substrates spaced apart, and the opposite surfaces of the two substrates are the first side and the second side respectively; Form a first transparent conductive layer on the first side surface and a second transparent conductive layer on the second side surface; Use a target doped with rare earth elements between the first transparent conductive layer and the second transparent conductive layer, and use magnetron sputtering technology to form an electrochromic structure containing rare earth elements; Among them, forming the electrochromic structure containing rare earth elements includes an ion storage layer, an ion conductor layer, and an electrochromic layer arranged in sequence.

8. The method for preparing an electrochromic device according to claim 7, characterized in that, After the step of forming the first transparent conductive layer on the first side surface and the second transparent conductive layer on the second side surface, it further includes: Clean the substrate with polyacrylamide to remove the oil stains on the surfaces of the first transparent conductive layer and the second transparent conductive layer; Clean the surfaces of the first transparent conductive layer and the second transparent conductive layer again with acetone and ethanol solution; Clean the substrate with an ultrasonic cleaner; Dry the cleaned substrate with acetone and ethanol.

9. The method for preparing an electrochromic device according to claim 7, characterized in that, After the step of using a target doped with rare earth elements between the first transparent conductive layer and the second transparent conductive layer and using magnetron sputtering technology to form an electrochromic structure containing rare earth elements, it further includes: Inject a sealant at the joint of the two substrates to obtain an electrochromic device doped with rare earth elements.

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