RU2692951C1 - Stable multilayer electrochromic module (embodiments) - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to devices providing change of light transmission value under effect of electric current, namely to stable electrochromic modules consisting of several separate layers of different materials. Essence of the invention consists in the fact that the versions of the product with the electrochromism-producing effect are provided when the voltage from the external source is applied with a coating, which includes a multilayer coating on the optically transparent substrate, which comprises a set of directly contacting thin film layers of different materials of the thickness range from several tens of nanometers to several hundreds of micrometers, arranged in a certain order from the surface of the optically transparent substrate. At that, materials of individual layers, their thickness and order are designed so that end product for each of proposed versions has set of required spectrophotometric properties from the point of view of range of location and width of maximum absorption band, along with stability of electrochromic characteristic parameters with respect to cyclic switching of its optical state between contrast positions.

EFFECT: technical result of the invention is directed to the implementation of a stable multilayer electrochromic module with a wide absorption maximum band, providing a neutral shade of the product in coloured state and displaced, while in the wavelength range of the visible part of the spectrum, in order to minimize the risk of thermal shock of translucent structures based on the electrochromic module exposure to intense fluxes of infrared solar radiation.

12 cl, 7 dwg, 2 tbl

Description

The present invention relates to the field of devices providing a change in the amount of light transmission under the influence of electric current, namely, to stable electrochromic modules consisting of several separate layers of different materials.

Electrochromic modules are known for use in assemblies of electrochromic devices with varying intensity values of transmission of electromagnetic radiation of various wavelength ranges, including the visible part of the spectrum, depending on the magnitude and polarity of the voltage applied to the device. Such electrochromic devices can be used in a wide range of different applications, in particular as light filters, displays, non-glare rear-view mirrors for transport, etc.

Of particular interest is the possibility of using devices based on electrochromic modules as part of translucent structures for architectural and transport applications (both interior and exterior). T.N. Smart windows with electroactive devices based on electrochromic modules integrated into them can be customized by the user through the adjustment of the magnitude and / or polarity of the applied voltage to transmit that part of the incoming solar radiation at which an optimum level of comfort in using the room will be achieved. Similarly, interior solutions with electrochromic modules can be transferred from the light-transmitting state to the state of an opaque partition at the request of the user. The specificity of the installation and operation conditions imposes on the electrochromic modules used in architectural and transport applications special requirements for the stability of the manifested qualities of chrome plating during numerous switching cycles between the extreme ones - the so-called. contrast - the values of the achieved light transmission in conditionally colored and conditionally transparent states. Modern electrochromic modules used in the composition of translucent design for construction applications and in vehicles are stable enough to withstand from several thousand to tens of thousands of switching between extreme positions of contrast without losing the value of chromium contrast. Examples of such devices are described, for example, in US patents No. 5598293, No. 9759975, No. 5699192, No. 6277523, and also patents of the Russian Federation No. 2569913; No. 2224275.

In principle, electrochromic modules often represent a multilayer thin-film structure of several individual functional layers of various materials deposited on a translucent substrate, or enclosed between two adjacent substrates of translucent material. The principle of operation of an electrochromic device made on the basis of such a multi-layer electrochromic module is based on the reversible electrochemical intercalation of a layer functioning as an acceptor electrode with a given polarity of applying voltage to an electrochromic module from an external source the polarity of the applied voltage function of the counter electrode. The intercalation-tolerant layer of the module has significantly different values of the refractive indices (n) and extinction (k) in the intercalated and reconstructed states. As a result, when an electrochemical reaction occurs, a so-called occurs. the process of “staining” the electrochromic module — either with a decrease in the aggregate value of the intensity of light transmission of the entire thin-film structure (if the acceptor electrode shows a higher absorption in the intercalated state, in this case, we can say that the electrochromic module is “default” —that is, without application of the response potential - “transparent”), or, on the contrary, with an increase in the aggregate value of the intensity of light transmission of the entire thin-film structure (if the acceptor electrode exhibits a large its high absorption in the restored state, in this case, we can say that the electrochromic module is “default” —that is, without applying the response potential — “colored”. The wide distribution of precisely multilayer thin-film electrochromic devices operating according to the above principle is connected with the advantages of their production - substances from a wide range of suitable materials can be chosen as components of the functional layers, and their various combinations allow implementing solutions of various sets of resulting characteristics. Examples of solutions based on multilayer thin-film electrochromic modules include inventions described, for example, in US Patent Nos. 9,939,662; №9921450; No. 7372610, patents of the Russian Federation No. 2528841; No. 2587079.

The term "electrochromic module" in the following description and claims refers to a directly finished product, having the ability to manifest electrochromism through changes in intensity, color, phase, polarization, optical functions and / or direction of light, during application of electrical voltage to its elements. In turn, the term “electrochromic device” in the following description and claims refers to a composite device, including both the electrochromic module itself — one or more — as an element of its design, directly exhibiting electrochromic functions, as well as all the auxiliary units required for operation. devices within the framework of a specific possible application - architectural-glassing, automotive, display and other possible. These include, for example, current leads for the application of external voltage to the electrochromic device modules, structural elements used to mount the device, for example, structural frames, frame fittings, dampers, guides, etc.

The use of electrochromic modules in the composition of active functional devices of translucent structures for interior and, in particular, exterior solutions in architectural and transport applications also imposes on them additional specific operational requirements. Such electrochromic modules should be characterized from the point of view of their spectral characteristics of the “colored” state by the absorption band, which is as much as possible offset from the infrared wavelength range of electromagnetic radiation to visible light with a wavelength range from about 380 nm to about 780 nm. This minimizes the absorption of the thermal component of the reaching the Earth’s surface of the solar radiation in the near and middle infrared (IR) ranges, which, in turn, reduces the risk of deformation of the translucent structure, including electrochromic modules, during uneven thermal expansion of individual, having significantly different integral absorption coefficients of ultraviolet radiation A _uv , structural elements and its subsequent thermal shock. At the same time, it is desirable that the degree of broadening of the absorption band in the range of maximum absorption capacity of electrochromic modules that make up the devices for transport and interior applications is maximum, and preferably covers the entire wavelength range of the visible part of the spectrum of electromagnetic radiation. The latter ensures the achievement of the most neutral hue of transmission and internal reflection of the module in the colored state and minimizes the filter effect with respect to transmitted radiation, which is preferable from the point of view of optimizing aesthetic means of expression when using devices based on such modules when designing architectural projects and vehicles. In addition, it helps to optimize the comfort of using exterior translucent structures with electrochromic modules while ensuring the interiors only with external sunlight during the daylight hours - i.e. when the use of electrochromic modules in the course of bringing them into a colored state is most effective.

However, of the known solutions of multilayer electrochromic modules, only a few demonstrate the maximum spectral absorption band located in the wavelength range of the visible part of the spectrum of electromagnetic radiation and not affecting the IR region. Even fewer of them combine with this quality also the broadening of the absorption band, sufficient to provide a neutral shade of the electrochromic module in the colored state. Rare examples of such electrochromic modules are the inventions described in the patents and applications of the US No. 14712389; No. 20110006272; EU No. 1204898. Due to the specificity of the methods of manufacturing the devices described in them based on electrochromic modules, namely the restrictions imposed by the methods of manufacturing on the maximum surface scaling area of such electrochromic modules, these devices, however, are not applicable to the application of modern architectural and transport niches. Products that are multi-layered electrochromic modules that simultaneously meet the qualities of stability in terms of maintaining the level of contrast during numerous switching cycles between the extreme positions of the contrast achieved during intercalation / restoration, as well as the width and location of the maximum absorption band of the module in the colored state on the electromagnetic spectrum radiation required in the framework of the current level and dynamics of development of the direction of use of translucent exterior structures ktsy in transport applications and architecture - existent.

Thus, currently in this area there is a need for a product, which is a stable multi-layer electrochromic module, which is collectively wide enough to provide a neutral shade of the product in the colored state with an absorption maximum band shifted, in this case, to the wavelength range of the visible part of the spectrum .

The closest to the claimed solution on the totality of signs is the RF patent No. 2587079, which describes a stable electrochromic module, comprising: the first substrate, the second substrate, where the first and / or second substrates have electrical conductivity or acquire electrical conductivity due to respectively the first electrically conductive coating , coating based on electrochromic polymer, deposited on the first substrate or first conductive coating, ion accumulation layer, placed a second substrate or second conductive coating, and electrically connected in series electrolyte is sandwiched between electrochromic coating and ion accumulation layer. Moreover, the specified electrochromic polymer is a substantially linear condensation polymer obtained from tetraarylbenzidine and (hetero) aromatic diol, and during voltage regulation can reversibly switch between more than two redox states. While the specified condensation polymer is colorless in one redox state and painted in at least two redox states, and the electrolyte is an electrolyte in the form of a polymer gel.

This product, however, does not have an absorption band, in a sufficiently shifted to the wavelength range of the visible part of the spectrum, and is also characterized by a too low contrast value, which is a limitation of its applicability. Thus, according to the formula of the above patent, the electrochromic module described in it is characterized by an absorption band having an absorption maximum in the wavelength range from 1200 to 1400 nm, i.e. in the near infrared range, which according to the spectrum of solar radiation near the Earth’s surface directly accounts for the left edge of the peak of thermal solar radiation, with an optical contrast of only 13% to 15% at the absorption maximum.

The technical result of the present invention is aimed at providing the following set of characteristics of a stable multi-layer electrochromic module: a wide absorption band with an absolute width from 250 nm to 500 nm, having a maximum in the wavelength range of the electromagnetic spectrum from 400 nm to 800 nm, and an optical contrast from 60% to 95% at maximum absorption.

The achievement of the technical result in the first embodiment of the present invention is ensured by the fact that a stable multilayer electrochromic module is proposed that contains at least one optically transparent substrate and includes a multilayer thin film coating on the substrate, which in turn contains directly contacting layers in the following order from the surface substrates:

the first separator layer adjacent to the substrate surface and containing a material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb , Mo, Hf, Ta and W,

the next layer, which is the first electrically conductive layer and contains oxide of a bi-metal alloy of elements selected from the group consisting of In, Sn, F, Zn, Al, Ga, Ti,

the next layer, which is an intermediate separator layer and contains a material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W,

the first electrode layer next to it, containing a material selected from the group of transition metal oxides and hydroxides of 5-10 groups of the periodic table and oxides and hydroxides of transition metal alloys of 5-10 groups of the periodic table,

the next layer, which is an intermediate separator layer containing a material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo , Hf, Ta and W,

the next layer, which is an electrolyte layer and consists of a material selected from the group of oxides, nitrides and hydrides of elements of even rows of 4-6 periods of the IV and V groups of the periodic table, immediately following the electrolyte layer is an intermediate separator layer containing a material selected from groups of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W,

the next layer, which is the second electrode layer, which contains a material selected from the group of transition metal oxides and hydroxides of 5-10 groups of the periodic table and oxides and hydroxides of transition metal alloys of 5-10 groups of the periodic table,

the next intermediate layer separator containing material selected from the group of oxides, nitrides and oxonitrides of mono metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo Hf, Ta and W,

the next layer, which is the second electrically conductive layer and containing oxide of a bi-metal alloy of elements selected from the group consisting of In, Sn, F, Zn, Al, Ga, Ti,

the next layer-separator external to the entire thin-film multilayer structure of the electrochromic module contains a material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al , Cr, Nb, Mo, Hf, Ta and W,

the thickness of all intermediate layers separators are in the range from 2 to 50 nm, and the thickness of the first adjacent directly to the surface of the substrate and the outer layer of separators are from 2 to 43 nm, besides the thickness of the first and second electrically conductive layers are from 40 to 210 nm, and the thickness of the first and second electrode layers are in the range from 80 to 1000 nm, while the thickness of the electrolyte layer is from 80 nm to 1200 nm.

In addition, in the particular case of the first embodiment of the present invention, it is proposed to use as the material of an optically transparent substrate on which a multilayer thin film coating of the described electrochromic module is applied, glass, for example, fluorine-silicate, sodium silicate or quartz glass.

In another particular case of the first embodiment of the present invention, it is proposed to use an optically transparent substrate coated with a multilayer thin film coating of the described electrochromic module as a material, a polymer film, for example, polyethylene terephthalate, polyvinyl butyral, ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride

polymethyl methacrylate or cellulose acetate.

Moreover, in another particular case of the first embodiment of the present invention, a compound of an optically transparent substrate coated on its surface with a multilayer thin film coating with at least one additional transparent substrate that faces the outer layer of the coating separator containing a material selected from the group of oxides is proposed. , nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, while as an additional transparent substrate This is used glass, for example, fluoro-silicate, sodium silicate or quartz glass.

In addition, in another particular case of the first embodiment of the present invention, a compound of an optically transparent substrate coated on its surface with a multilayer thin film coating with at least one additional transparent substrate that faces the outer layer of the coating separator containing a material selected from the group of oxides is proposed. , nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, while as an additional transparent substrate This is used a resin film such as polyethylene terephthalate, polyvinyl butyral, ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate or cellulose acetate.

In another particular case of the first embodiment of the present invention, it is proposed that the intermediate separator layers adjacent to the first and second electrode layers have a non-uniform thickness partial concentration of the gas component in such a way that from 7% to 22% of the total thickness of the separator layer from the side directly in contact with the electrode layer, were a substoichiometric material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following ments: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W.

In the second embodiment of the present invention, the technical result is achieved by the fact that a stable multilayer electrochromic module is proposed, also containing at least one optically transparent substrate and including a multilayer thin film coating on the substrate, which in turn contains directly contacting layers in the following order from the surface substrates:

the first separator layer adjacent to the substrate surface, as in the first embodiment of the invention, contains a material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W,

the next layer, which is the first electrically conductive layer and contains oxide of a bi-metal alloy of elements selected from the group consisting of In, Sn, F, Zn, Al, Ga, Ti,

the next layer, which is an intermediate separator layer and contains a material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W,

the first electrode layer next to it, containing a material selected from the group of transition metal oxides and hydroxides of 5-10 groups of the periodic table and oxides and hydroxides of transition metal alloys of 5-10 groups of the periodic table,

the next layer, which is an intermediate separator layer containing a material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo , Hf, Ta and W,

the next layer, which is an electrolyte layer and consists of a polymer gel containing at least one cross-linked polymer selected from the group: polystyrene (PS), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyvinylpyrrolidone (PVP), at least one RTIL - an ionic liquid from the group of chlorides, tetrafluoroborates, hexafluorophosphates and alkylphosphonium perchlorates, N-alkylpyrillinium, N, N'-dialkylimidazolium, N-alkylisoquinolinium, at least one polyethylene glycol (PEG) with molecular weight from 62 to 4000 g / mol as well at least one and an inert solvent selected from the group consisting of: propylene carbonate, γ-butyrolactone, ethylene carbonate, diethyl carbonate, dimethyl sulphoxide, acetonitrile, and at least one salt selected from the group of perchlorates, tetrafluoroborates, hexafluorophosphates and triphenyl cyantehbehteh dextraf dextrante dehydrate, and a complex of nitrf dextrante dextra dextra dextra dextra dextra dextra dextra dextra dextra dextra dextra dextra dextra dextra dextra dextra dextra dextra dextra dextra dextra dextra de aura de ointment de aryte dehydroxycarboxylic acid dyes. alkyl groups with 1-4 carbon atoms,

an intermediate separator layer immediately following the electrolyte layer, containing a material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb , Mo, Hf, Ta and W,

the next layer, which is the second electrode layer, which contains a material selected from the group of transition metal oxides and hydroxides of 5-10 groups of the periodic table and oxides and hydroxides of transition metal alloys of 5-10 groups of the periodic table,

the next intermediate layer separator containing material selected from the group of oxides, nitrides and oxonitrides of mono metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo Hf, Ta and W,

the next layer, which is the second electrically conductive layer and containing oxide of a bi-metal alloy of elements selected from the group consisting of In, Sn, F, Zn, Al, Ga, Ti,

a separator layer that is external to the entire thin-film multilayer structure of the electrochromic module contains a material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr , Al, Cr, Nb, Mo, Hf, Ta and W,

the thickness of all intermediate layers separators are in the range from 2 to 50 nm, and the thickness of the first adjacent directly to the surface of the substrate and the outer layer of separators are from 2 to 43 nm, besides the thickness of the first and second electrically conductive layers are from 40 to 210 nm, and the thickness of the first and second electrode layers are in the range from 80 to 1000 nm, while the thickness of the electrolyte layer is from 10 μm to 600 μm.

In addition, in the particular case of the second embodiment of the present invention, it is proposed to use as a material of an optically transparent substrate on which a multilayer thin film coating of the described electrochromic module is applied, glass, for example, fluorine-silicate, sodium silicate or silica glass.

In another particular case of the second embodiment of the present invention, it is proposed to use as a material of an optically transparent substrate on which a multilayer thin film coating of the described electrochromic module is applied, a polymer tape, such as polyethylene terephthalate, polyvinyl butyral, ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate or polyethylene vinyl acetate or polyethylene vinyl acetate or polyethylene vinyl acetate.

Moreover, in another particular case of the second embodiment of the present invention, a compound of an optically transparent substrate coated on its surface with a multilayer thin film coating with at least one additional transparent substrate that faces the outer layer of the coating separator containing a material selected from the group of oxides , nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, as an additional transparent substrate This is used glass, for example, fluoro-silicate, sodium silicate or quartz glass.

In addition, in another particular case of the second embodiment of the present invention, a compound of an optically transparent substrate coated on its surface with a multilayer thin film coating with at least one additional transparent substrate that faces the outer layer of the coating separator containing a material selected from the group of oxides is proposed. , nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, while as an additional transparent substrate This is used a resin film such as polyethylene terephthalate, polyvinyl butyral, ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate or cellulose acetate.

In another particular case of the second embodiment of the present invention, it is proposed that the intermediate separator layers adjacent to the first and second electrode layers have an uneven thickness of the partial concentration of the gas component in such a way that from 7% to 22% of the total thickness of the separator layer from directly in contact with the electrode layer, were a substoichiometric material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following ments: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W.

It should be noted that both variants of the invention described in the framework of this patent are united by a single creative idea and are aimed at ensuring the achievement of one technical result. At the same time, the key difference between the multilayer electrochromic modules described in the embodiments of the present invention is the material and the ranges of permissible thickness of the electrolyte layer, the reasons for which are given below. The materials, sequences, and ranges of allowable thicknesses of other thin film layers according to embodiments of the present invention are similar. At the same time, special cases of the implementation of the present invention are similar in each of the two options, describing the preferred for use of the substrate electrochromic modules according to this invention, both the first substrate onto which layers of a multilayer thin-film functional electrochromic coating are directly applied successively, and a second substrate, optionally adjacent to the first substrate on the side, on which the multilayer thin-film functional electrochromic coating is applied, does not osredstvenno contacting the outer layer-separator coating; as well as the preferred features of the distribution of the partial composition of the intermediate layers-separators of the multilayer thin-film coating of the electrochromic module throughout the thickness of the layer-separator.

The use of separator layers in the first embodiment of the present invention — namely, the first separator layer immediately adjacent to the optically transparent substrate; a separator layer external to the entire structure of thin-film layers of a multilayer stable electrochromic module relative to an optically transparent substrate; as well as intermediate separator layers that separate all other functional layers of the module in pairs, due to a number of functions performed by a combination of these separator layers aimed at ensuring the stability of the electrochromic module during numerous operational switching cycles between contrast-extreme transparency states. These layer separators are necessary to maximize the adhesion between all other functional layers of the thin-film coating of the electrochromic module, as well as maximize the adhesion of the multilayer thin-film stack of layers to the optically transparent substrate. Due to this, the effect of mutual defoliation of individual layers during the accumulation of interstitial defects in them is minimized when the module is switched during intercalation reactions and subsequent restoration of the electrode layers, which, in turn, leads to an increase in parasitic electrical resistance at the boundaries of the contact interfaces of the individual layers, and As a result, a consistent decrease in the magnitude of the electrochromic efficiency of the module and the level of contrast in the maximum of its absorption. In addition, the materials of the layer-separators of the described electrochromic module should also be barrier to the transport of radicals during the cyclical switching of the state of the diffusion processes during the operation of the module, namely: to the diffusion of radicals from an optically transparent substrate or several optically transparent the substrate of the product into the first and second electrically conductive layers, respectively, leading to their restructuring during the removal of such transport accumulated during the flow tny processes of stresses and, as a result, decrease in size of a conductivity of layers due to disturbance of initial uniformity of their structure; and also with respect to the entry of radicals into the electrode layers, with their replacement of vacant bonds that are free for interpolation acts, as a result of which there will also be a degradation of the level of the electrochromic efficiency of the described module. At the same time, layer separators should not excessively inhibit ion transport during the directly exchange processes of intercalation and recovery of the materials of the electrode layers of the module so as not to lead to a decrease in the magnitude of its electrochromic efficiency. It was found that, from the point of view of combining all the above qualities, the materials of the separator layers for use within the stable electrochromic module of the multilayer thin-film stack along with its other functional layers of materials, the reasons for which are given below, are the materials from the group preventing the propagation of cracks ( PRT) materials, including oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W. ak generally GOT materials inhibit crack propagation in a brittle, vitreous outer layer of various optical coatings during the process of heat treatment and while temperature of heating during operation, connected with the diffusion of aggressive with respect to the structure of the thin film optical coatings of oxygen radicals. In particular, it is known that ORT materials, such as oxides and nitrides of Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, are suitable for use on silicon nitride layers (for example, Si ₃ N ₄ ). In the case of the present invention, the adhesion qualities of PRT materials used to form separator layers with respect to the other layers of the thin film stack and the optically transparent substrate or several substrates of the multilayer stable electrochromic module are provided by the formation of predominantly covalent polar bonds with the atoms of the separator layer, moreover, the use of more complex doped compounds, rather than bi-metals, will adversely affect the level of achievable adhesion due to the fact that the free chemical bonds of the layer-separator will tend to lock on each subsequent metal component introduced into the composition of the layer. At the same time, the inclusion of gas components into the separator layers and their final realization as oxides, nitrides, and oxynitrides of the listed metal group and their alloys ensures the required balance of barrier properties of layers in terms of diffusion of unwanted radicals and ion-exchange members through them. reactions that implement the operation of the electrochromic module. Thus, the layer-separators of the multilayer electrochromic module according to the first embodiment of the present invention are as the first separator layer adjacent to the substrate surface, external to the entire thin-film multilayer structure of the electrochromic module relative to the optically transparent substrate layer-separator, and all intermediate layers - separators separating other thin-film layers of the described electrochromic module in pairs - must contain a material selected from the group of oxides, nitrides and oxonitrido in mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W.

The first and second electrically conductive layers of a multilayer stable electrochromic module are needed to provide current transfer when the module is connected to an external power source to realize its operation within the framework of the final device being operated. These layers must simultaneously have a high electrical conductivity, characterized by a low surface resistance coefficient not exceeding several tens of Ohms per square, as well as transparency with respect to visible light, in order to be able to maximize the contrast of the electrochromic module by reducing the contribution from absorption of radiation of the visible spectrum on electrically conductive layers in the restored state of the module. According to the first embodiment of the present invention, the first and second electrically conductive layers should contain a bi-metal alloy oxide of elements selected from the group consisting of In, Sn, F, Zn, Al, Ga, Ti. These materials make up a group of so-called. transparent conductive oxides (TCO) meet two key requirements for electrically conductive layers in the framework of the present invention: transparency with respect to radiation of the visible spectrum, due to the large band gap from about 3.5-4 eV, as well as their high electrical conductivity, comparable to metal, characterized by surface resistance from a few units of Ω per square, to about 20-30 Ω per square, due to the alloying component of the oxide alloy playing the role of donor free bottom electrons. In addition to ensuring the required qualities of electrical conductivity, the use of bi-metal alloys of the listed elements also provides additional stabilization of the main metal component of the alloy by doping, which contributes to the enhanced resultant stability of the described multilayer electrochromic module. Thus, the first and second electrically conductive layers of the described stable multilayer electrochromic module according to the first embodiment of the present invention should contain an oxide of a bi-metal alloy of elements selected from the group consisting of In, Sn, F, Zn, Al, Ga, Ti.

The reactionary qualities of the electrode layers from the point of view of donor-acceptor behavior during the electrochemical reaction of intercalation and subsequent recovery during the operation of the electrochromic module ensure its actual functioning. The level of their rechargeability and the depth of coloring, as a conditional function of the number of vacant bonds for intercalation, determines, respectively, the stability and the amount of working contrast of the electrochromic module, of which they are included in the multilayer thin-film stack. The choice as materials of the electrode layers of the described stable multilayer electrochromic module according to the first embodiment of its implementation is a group of transition metal oxides and hydroxides of 5-10 groups of the periodic table and oxides and hydroxides of transition metal alloys of 5-10 groups of the periodic table is primarily associated with these materials reactivity with respect to intercalation-recovery electrochromination processes supported by the fact of the presence of a variable degree of oxide Ia metal component layers. In addition, these materials exhibit high stability in terms of functioning as part of the electrochromic module as electrode layers due to the reduced degree of crystallinity of the films when they are deposited as oxides, and, even more so, when they are doped with secondary alloying components. At the same time, it was found that the degradation of the electrode layers directly during the prolonged cycling of the potential due to the conditional selective “leaching” of both the main and alloying layers in the case of using oxides and hydroxides of transition metal alloys of 5-10 groups of the periodic table — metal components of layers This group of materials is not peculiar. It was also empirically determined that using concretely given materials of the listed group while ensuring the thickness of the electrode layers in the allowable range according to the first embodiment of the present invention, the reasons for which are given below, realizes the possibility of achieving a minimum transmittance level characterized by an intensity of about 70-90% at the extremum at waves from about 450 nm to about 800 nm. Thus, in turn, the principal achievement of the contrast level of the resulting multilayer stable electrochromic module in the range from about 60% to about 95% at the absorption maximum is ensured, which corresponds to the achievement of the technical result of the present invention. Thus, the first and second electrode layers of the described stable multilayer electrochromic module according to the first embodiment of the present invention should consist of materials from the group of transition metal oxides and hydroxides of 5-10 groups of the periodic table and oxides and hydroxides of transition metal alloys of 5-10 groups of the periodic table.

In this case, the electrolyte layer of the multilayer thin-film structure of the proposed electrochromic module according to the first embodiment of the present invention should consist of a material selected from the group of oxides, nitrides and hydrides of the elements of even rows 4-6 of periods IV and V of the periodic table. In the composition of the multilayer electrochromic module, the electrolyte is the medium of ion transport during the electrochemical reaction of the module. The material of this layer must first of all be an insulator with respect to the electric current, on the one hand, and on the other hand, it must have the qualities of ionic conductivity. In addition, the material of the electrolyte layer must have the values of optical functions, at which, for the thickness of the electrolyte layer lying in the range of acceptable values, defined and explained below, interference processes will occur during the passage through the multilayer structure of the electrochromic electromagnetic radiation module from external sources, contributing to the possibility of achieving the technical result declared in the present invention in terms of the width and range of the spectral position of the maximum absorption of the electrochromic module when transforming it by applying a voltage to a colored state. These qualities are possessed by the materials of the indicated group of suitable electrolytes, where dielectrics of metals of even rows 4–6 of periods IV and V of the periodic table are characterized by ionic conductivity in the range from about 20 Ohm ^-1 ⋅m ^-1- to about 70 Ohm ^-1 ⋅m ^-1 in the temperature range of 20-250 ° C, and their poisoning by the reaction gas component in turn ensures the achievement of the qualities of an electrical insulator. In addition, ensuring the presence of the gas component of the layer through oxidation, nitriding or hydrating the metal component, respectively, allows to achieve a balance between the values of the refractive index and extinction of the layer material from about 1.75 units to about 2.93 units and from about 7⋅10 ^-5 units to about 5.82 units, respectively, at a wavelength of 578 nm. This, in turn, allows the broadening of the maximum spectral absorption band of the described multilayer stable electrochromic module to values of the order of 400 nm along the left edge of the absorption intensity spectrum, where the absorption intensity reaches 75% or less, of the module electrolyte layer in the limit from 80 nm to 1200 nm, which makes it possible to achieve a general broadening of the absorption band in the maximum to absolute values of no more than 500 nm with the location of the band boundaries in the range e from about 400 nm to about 800 nm, and the contrast level of the module at the absorption maximum technical result according to the present invention. Thus, the electrolyte layer of the described stable multilayer electrochromic module according to the first embodiment of the present invention should consist of a material selected from the group of oxides, nitrides and hydrides of elements of even rows 4-6 of periods IV and V of the periodic table.

At the same time, in order to ensure alternating switching of the described electrochromic module between extreme optical states by cycling through the application of a potential of different polarity, i.e. by actually alternately moving ions between the electrode layers through the electrolyte layer and the separator layers adjacent to them during the electrochemical reaction of donor-acceptor character, the thin-film structure of the electrochromic module located on the surface of the optically transparent substrate is performed in a symmetrical form of a sequence of functional layers relative to the layer electrolyte. This symmetric structure is shown in FIG. 1 and described by the conditional symmetric sequence layer separator (1) - electrically conductive layer (2) - layer separator (1) - electrode layer (3) - layer separator (1) - layer electrolyte (4) - layer separator ( 1) - electrode layer (3) - layer separator (1) - electrically conductive layer (2) - layer separator (1).

In this case, the thicknesses of all intermediate layers-separators of the described multi-layer stable electrochromic module according to the first embodiment of the present invention should be from 2 to 50 nm. The indicated limit on the lower limit of the range of permissible thicknesses is related to the fact that, with a layer thickness of less than 2 nm, these layers are not sufficiently long in thickness to exhibit the necessary barrier qualities with respect to the diffusion of aggressive radicals. In turn, when the upper limit is exceeded over the allowable thickness range of 50 nm, the extinction effects from accumulation with increasing internal stress in the layers described will lead, due to concomitant recrystallization, to the transmission of structure defects into their adjacent functional electrode layers, electrically conductive layers and layer electrolyte, which in turn will lead to a violation of the required qualities of adhesion and, as a result, the final defoliation of the individual layers within the thin film stack with loss of trochrome stability module as part of the cycling application of voltage.

In turn, the thickness of the first adjacent directly to the surface of the substrate and the outer layers of the separators described multilayer stable electrochromic module according to the first embodiment of the present invention should be from 2 to 43 nm. The specified limit on the lower limit of the range of permissible thicknesses is similar to the case of intermediate separator layers due to the fact that, with a layer thickness of less than 2 nm, these layers are not sufficiently long in thickness to exhibit the necessary barrier qualities with respect to the diffusion of aggressive radicals. In turn, when the upper limit of the admissible thickness range of 43 nm is exceeded, the extinction effects from accumulation with an increase in the thickness of the internal stresses in the described layers will, due to concomitant recrystallization, lead to the transmission of structural defects to their adjacent functional electrically conductive layers, which will be the turn to lead to the violation of the required qualities of adhesion and, as a result, the final defoliation of individual layers within the thin film stack with the loss of the electrochromic stability module in p amka cycling by applying voltage. It should be noted that the upper limit of the range of permissible thickness of the first adjacent directly to the surface of the substrate and the outer layers of separators described multilayer stable electrochromic module according to the first embodiment of the present invention is less than the value of this value for the case of intermediate layers of separators for the reason that An increased diffusion intensity of molecular radicals from the optically transparent substrate of the electrochromic module into the first, adjacent but the substrate surface, a layer separator, and from the external medium or the second soprilegayuschey optically-transparent substrate in the outer layer of separator promotes an earlier initiation of the extinction process, the first adjacent directly to the substrate surface and outer layers separators when they reach the lower boundary thickness.

In addition, the thickness of the first and second conductive layers should be from 40 to 210 nm. If the thickness of the electrically conductive layers is less than 40 nm, the conductivity provided by these layers will be too small to implement effective current transfer to the described multi-layer stable electrochromic module from an external power source necessary to maintain the electrochemical exchange processes between the individual layers of the module for its operation. Moreover, if the thickness of the electrically conductive layers exceeds 210 nm, electrically conductive layers of such thicknesses as conductors of the first kind will be characterized by an extremely high spectral absorption characteristic at wavelengths of the order of 450 nm as a result of acts of resonant oscillation processes at in the course of overcoming electromagnetic radiation from external sources of the thickness of the electrically conductive layers. As a result, the integrated light transmission value of the described stable multilayer electrochromic module in a transparent state will be lower than 60%, due to which the achievement of the level of optical contrast shown by the module, characterized by a value in the range from 60% to 95% at the maximum absorption, according to the technical result , to ensure the implementation of which the present invention is directed, at the lower boundary of the presented two-sided limit of values it will be fundamentally impossible. Based on these factors, a requirement was developed for the range of permissible thicknesses of the first and second electrically conductive layers, which should lie in the limit from 40 nm to 210 nm.

In this case, the thicknesses of the first and second electrode layers of the multilayer stable electrochromic module, according to the first embodiment of the present invention, should be in the range from 80 to 1000 nm. The requirement for maintaining the thickness of the electrode layers in the specified range of values is dictated by the fact that when the limit at the upper limit of 1000 nm is exceeded, the contribution of extinction coefficients permissible to use according to the previously listed reasons for the materials of the electrode layers with the optical path lengths of the visible spectrum in them, corresponding to such high values of the thickness of the electrode layers, will have a bias in relation to the extremum of the minimum intensity of the spectrum lowering the resultant multilayer stable electrochromic module in the wavelength direction less than 450 nm, which will result in the violation of the effective broadening of the absorption maximum band of the electrochromic module, converted to a colored state. In turn, on the thickness of the electrode layers less than 80 nm, there is a dynamic decrease in the staining efficiency of the described multilayer stable electrochromic module, as a result of a decrease in the conditional density of association of the materials of the electrode layers during acceptance or restoration, respectively, by intercalating and reduced transmitted ions. As a result, the thickness of the first and second electrode layers of the described electrochromic module should be in the range of values from 80 nm to 1000 nm.

In turn, the thickness of the electrolyte layer, according to the first embodiment of the present invention, should be from 80 to 1200 nm. If the maximum permissible thickness of the electrolyte layer exceeds 1200 nm, the ionic conductivity of the layer material decreases significantly at temperatures in the range of 20-60 ° C and, as a result, the optical contrast loss by the electrochromic module in the range of the result of the present invention, from 60% to 95% at the maximum absorption, during the switching module in a colored state. At the same time, the electrolyte layer thickness is less than 80 nm, as it was empirically revealed, insufficient both from the point of view of ensuring the principal response of the electrochromic mechanism of the described module when the voltage is applied from an external source, and from the point of view of maintaining the spectral band of the absorption maximum of the electrochromic module in the wavelength range of the electromagnetic spectrum from 400 nm to 800 nm, according to the technical result of the present invention.

In this case, in the particular case of the first embodiment of the present invention, it is proposed to use as an optically transparent substrate a stable electrochromic multilayer module, on which a multilayer coating is applied directly in contact with each other thin film layers, such as fluorine-silicate, sodium silicate or silica glass. The use of glass as a otpicically transparent substrate of the described stable electrochromic multilayer module according to the first embodiment of the present invention is preferable in those cases where the additional performance requirements for the final assemblies of electrochromic devices based on the described stable multilayer electrochromic modules are their compressive strength, i.e. ., for example, when it is assumed that excessive wind loads will affect the device in a number of exterior arches texture and transport applications in assemblies of translucent structures, as well as hardness as a characteristic of scratch resistance, which is of great importance, for example, in terms of the stability of assemblies of translucent structures using electrochromic devices based on the described stable multilayer electrochromic modules with respect to the eroding effect of finely dispersed suspended solids - for example, sand - in the air, which also occurs in certain particular cases of potential ex Terrier architectural and transport applications. In the case of using glass as a transparent transparent substrate of the described stable electrochromic multilayer module according to the first embodiment of the present invention, it is possible to achieve values of the ultimate compressive strength of the final module from about 1000 MPa to about 8000 MPa, as well as surface hardness values of a stable multilayer electrochromic module sides of the optically transparent substrate is the reverse of the one on which the multilayer coating is applied directly contacting between in a thin film layer is about 5-8 Mohs' scale units, depending on the type used as optically-prozrachnoypodlozhki glass. However, when using glass, for example, fluorine-silicate, sodium-silicate or quartz glass, as an optically transparent substrate of the described stable electrochromic multilayer module according to the first embodiment of the present invention, is provided sufficient to maintain the stability of the module from the point of view of preventing possible delamination multilayer thin-film structure during functional cycling of the module by applying voltage from an external power source, the level of adhesion between do the optically transparent substrate and the first separator layer directly adjacent to the substrate surface, containing a material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, for the reasons given above. At the same time, it remains possible to achieve a combination of other characteristics of a stable multi-layer electrochromic module that provides the implementation of the technical result according to the present invention.

Moreover, in another particular case of the first embodiment of the present invention, it is proposed to use as an optically transparent substrate a stable electrochromic multilayer module, on which a multilayer coating is applied directly in contact with each other thin film layers of a polymer film, for example polyethylene terephthalate, polyvinyl butyral, ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate or cellulose acetate. The use of a film as a otpicically transparent substrate of the described stable electrochromic multilayer module according to the first embodiment of the present invention is preferable in cases where the additional performance requirement in relation to the final assemblies of electrochromic devices based on the described stable multilayer electrochromic modules is elasticity, which in turn ensures the possibility of using electrochromic devices based on the described stable oynyh electrochromic modules in translucent structures of complex, three-dimensionally curved geometries, and the incorporation of such devices in the laminated glass constructions. However, when using a polymer film, for example, polyethylene terephthalate, polyvinyl butyral, ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate or acetylcellulose, as an optically transparent substrate of the described stable electrochromic multilayer module according to the first variant of the present invention, I did a subject. As an optically transparent substrate of the described electrochromic glass module, it suffices From the point of view of preventing possible delamination of the multilayer thin-film structure during the functional cycling of the module by applying voltage from an external power source, the adhesion level between the optically transparent substrate and the first separator layer adjacent to the substrate surface, containing a material selected from groups of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, for reasons am above. At the same time, it also remains possible to achieve a combination of other characteristics of a stable multi-layer electrochromic module that provides the implementation of the technical result according to the present invention.

In another particular case of the first embodiment of the present invention, a compound of an optically transparent substrate coated with a multilayer thin film coating with at least one additional transparent substrate that faces the outer layer separator of the coating comprising a material selected from the group of oxides, nitrides is proposed. and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta, and W; however, it is proposed to use glass, such as fluorine-silicate, sodium silicate or quartz glass, as an additional transparent substrate. This solution makes it possible to further increase the stability of the described multilayer electrochromic module from the point of view of the chemomechanical stability of the product as a whole, since the entire structure of the thin-film electrochromic module on the primary optically transparent substrate turns out to be protected from negative external influences and contact with the external environment. the thickness of the additional glass substrate or the thickness of the first of the group of additional transparent substrates directly in contact with the external it relative to the primary optically transparent substrate surface of the outer layer of the separator containing a material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr , Nb, Mo, Hf, Ta and W. This solution also makes it possible to additionally ensure the surface hardness of a stable multi-layer electrochromic module on the side of an optically transparent substrate, on which a multi-layer coating is deposited directly in contact with each other thin-film Loew, constituent units of about 5-8 Mohs' scale, depending on the type used as an additional optically transparent substrate facing the outer layer-the electrochromic separator module window. At the same time, the set of other characteristics of the described stable multilayer electrochromic module from the point of view of the bandwidth of its absorption maximum, its position on the spectrophotometric characteristic of the module relative to the visible range of wavelengths of electromagnetic radiation, as well as the contrast level of the described stable multilayer electromagnetic module at maximum absorption, ensuring technical result according to the present invention.

In this case, in another particular case of the first embodiment of the present invention, a compound of an optically transparent substrate coated on its surface with a multilayer thin film coating with at least one additional transparent substrate that faces the outer layer of the coating separator containing a material selected from the group of oxides is proposed. , nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W; it is proposed to use a polymer film, for example, polyethylene terephthalate, polyvinyl butyral, ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate or cellulose acetate, as an additional transparent substrate. This solution makes it possible to further increase the stability of the described multilayer electrochromic module from the point of view of the chemomechanical stability of the product as a whole, since the entire structure of the thin-film electrochromic module on the primary optically transparent substrate turns out to be protected from negative external influences and contact with the external environment. the thickness of an additional transparent, primer-like substrate or the thickness of the first of a group of additional transparent substrates directly contacting with the outer relative to the primary optically transparent substrate surface of the outer layer of the separator containing material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al , Cr, Nb, Mo, Hf, Ta and W. This solution also makes it possible to preserve additionally the qualities of elasticity of a stable multi-layer electrochromic module to enable its use in electrochromic devices as part of translucent structures of complex, three-dimensional bending geometry, as well as the inclusion of such devices in the composition of translucent structures by lamination, if, as the primary optically transparent substrate of the described stable multilayer electrochromic module, is also used, according to the second special case of the first embodiment of the present invention, a polymer film, for example polyethylene terephthalate , polyvinyl butyral, ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate or cellulose acetate. At the same time, the set of other characteristics of the described stable multilayer electrochromic module from the point of view of the bandwidth of its absorption maximum, its position on the spectrophotometric characteristic of the module relative to the visible range of wavelengths of electromagnetic radiation, as well as the contrast level of the described stable multilayer electromagnetic module in the maximum absorption, providing achieving a technical result according to the present invention.

In addition, in another particular case of the first embodiment of the present invention, it is proposed to ensure the non-uniformity of the partial concentration of the gas component of the intermediate separator layers adjacent to the first and second electrode layers, in thickness such that from 7% to 22% of the total thickness of the separator layer sides directly in contact with the electrode layer are a substoichiometric material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys with the elements of Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W. As it was empirically determined, the increase in the partial concentration of the metal components of the separator layer near the contact boundary with the adjacent electrode layer ensuring local substoichiometry of the corresponding oxide, nitride, or oxonitride, which constitutes the material of the separator layer, contributes to the formation of additional chemical bonds between the materials of the adjacent electrode layers and intermediate separator layers. This ensures an increase in the degree of adhesion between the layer-separator-electrode layer groups of the multi-layer electrochromic module, which contributes to an additional increase in the stability of the latter in terms of defoliation of individual stack layers during numerous cyclic switching between the optical states of the module by changing the polarity of the applied external voltage. Moreover, the specified range of the fraction of the total thickness of the intermediate separator layers adjacent to the first and second electrode layers, which should be subjected to substochiometry, ranging from 7% to 22% of the total thickness of the separator layer on the side in direct contact with the electrode layer, was based on of the following factors. On the one hand, as was also established empirically, if less than 7% of the total thickness of the separator layer, from the side directly in contact with the electrode layer, is a substoichiometric material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi -metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, the gradient of the degree of metallization of the described layer-separator in thickness is too large. As a result, the accumulation of parasitic intralayer stresses in the intermediate layer-separator will have the opposite effect to the observed catalysis of the adhesion of the layer-separator with the electrode layer adjacent to it, due to which the expected effect of an increase in the affinity of the individual layers of the thin-film structure of the multilayer coating of the growth of the cyclic stability of the described electrochromic module will not register. If, on the contrary, more than 22% of the total thickness of the separator layer from the side directly in contact with the electrode layer is a substoichiometric material, the contribution to the total integrated absorption value of the described electrochromic module in its conditionally “transparent” state from the substochiometric fractions the thickness of the intermediate layer separators adjacent to the first and second electrode layers is so large that the achievement of a stable optical optical contrast level osloynogo electrochromic modulus in the range from 60% to 95% at the maximum of spectral absorption of the module becomes impossible for the upper boundary of the integral value of the light transmission module T _vis, of less than 60% in the reduced state, due to which no longer provides the realization of the proposed technical solution of the present invention.

As also indicated above, the reasons for the choice of materials and thickness ranges of the individual thin film layers of the multilayer structure of the described electrochromic module in the second embodiment of the present invention for the following cases: the first separator layer adjacent to the substrate surface; the first and second electrically conductive layers; the first and second electrode layers; all intermediate layers-separators and a layer-separator external to the entire thin-film multilayer structure of the electrochromic module of the layer are similar to those for the corresponding layers given in relation to the first embodiment of the present invention.

At the same time, the electrolyte layer according to the second embodiment of the present invention, serving together with all the other layers of the layer structure of the described multilayer thin-film electrochromic module to achieve this technical result, is an electrolyte in the form of a polymer-based gel, containing at least one dissolved salt chosen from groups of perchlorates, tetrafluoroborates, hexafluorophosphates and triphenyl cyanoborates of alkali and alkaline earth metals, as well as tetraalkylammonium with alkyl grams ppami with 1-4 carbon atoms, an ion conductor. The polymers directly forming the gel are, in turn, cross-linked polymers, presented individually, or as mixtures of several cross-linked polymers, selected from the group: polystyrene (PS), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyvinylpyrrolidone (PVP). Along with high ionic conductivity, which is less than 10 Om ^-1 ⋅m ^-1 in the room temperature range, electrolytes in the form of polymer gels of these polymers and salts dissolved in them are characterized by good transparency in the visible range, along with the values of the optical functions at which, for the thickness of the electrolyte layer lying in the range of permissible values, defined and explained below, will ensure the occurrence of interference processes when passing through the multilayer structure of the electrochromic module electromagnetic radiation from external sources that contribute to the possibility of achieving in the claimed invention the technical result in terms of band width and spectral position of the absorption maximum of the electrochromic translation module when its voltage application in the colored state. In addition, the use of cross-linked polymers provides, due to the effect of cross-linking itself, a high degree of mechanical stability of the electrolyte layer itself with respect to tensile stresses, along with high adhesion between the electrolyte layer and adjacent intermediate separator layers. Suitable for the preparation of a polymer gel used as the material of the electrolyte layer according to the second embodiment of the present invention, the solvents are inert solvents from the group of propylene carbonate, ubutirolactone, ethylene carbonate, diethyl carbonate, dimethyl sulfoxide and acetonitrile, and mixtures thereof. The use of inert solvents of the indicated group of substances is due to the combination of a number of factors characterizing them, namely, the inertness of these solvents directly, along with the characteristic qualities of polar, aprotic solvents, as well as a high dielectric constant and high dielectric constant, due to which they are good solvents for selected gel-forming cross-linked polymers of the group: polystyrene (PS), polymethyl methacrylate (PMMA), polyethylene nftalatalat (PET), polyvinylpyrrolidone (PVP), and their relatively high polarity allows them to create a generally inert solvating shells relative to the ions of the salts of perchlorates, tetrafluoroborates, tetrafluoroborates, alkaline and alkaline-earth-alkaline and alkaline-earth-alkaline metals, and alkaline and alkaline-earth-alkaline metals, and tetrafluoroborate groups, as well as I and I, I’m like, I’m also like, I’m like, I’m also like, I’m like, I’m not altogether groups with 1-4 carbon atoms, thus preserving the level of electrolyte conductivity. At the same time, as a binder, the components of the inert electrolyte layer of inert solvents selected from the group of propylene carbonate, ubutirolactone, ethylene carbonate, diethyl carbonate, dimethyl sulfoxide and acetonitrile, for the reasons listed above, can be used suitable for this purpose polyethylene glycol (PEG) with a molecular weight from 62 to 4000 g / mol, as representing a viscous gel-like thickener in this range of permissible molecular weight. Additional catalysis of the ionic conductivity of the electrolyte layer to ensure the stability of the observed electrochromic effect is achieved by adding an ionic liquid or a mixture of ionic liquids to the composition of the material forming the polymer gel layer. Suitable for use in the composition of the material of the electrolyte layer described stable multilayer electrochromic module ionic liquids are so-called. RTIL (Room Temperature Ionic Liquids) - ionic liquids, which are salts with a melting point below or equal to the values from the range of room temperatures, from the group of chlorides, tetrafluoroborates, hexafluorophosphates and alkylphosphonium perchlorates, N-alkylpyridinium, N, N'-dialkylimidazolium and N -alkylisoquinolinium. These salts, at room temperature, are ionic liquids; their addition to the material forming a layer-electrolyte polymer gel along with salts from the group of perchlorates, tetrafluoroborates, hexafluorophosphates and alkali and alkaline earth metals triphenylcyanoborates, and also tetraalkylammonium with alkyl groups with 1-4 carbon atoms, provides an increase in the ionic conductivity of the material at temperatures below the order 30-35 ° C, and also helps to minimize the effect of gradual formation of defects in the layer and on the border with the thin film layers adjacent to it. ennogo reduction electrolyte conductivity through numerous cycles electrochromic switching module between its states the optical contrast. In addition to these qualities, the polymer gel of this composition, used as the material of the electrolyte layer according to the second embodiment of the present invention, is characterized by a large number of available methods for its application, including in the framework of the industrial process, and also demonstrates a high isotropy of the distribution of individual active components , resulting in the achievement of optimal isotropy of the electrochromic effect of the described module when it is triggered.

The thickness of the electrolyte layer, according to the second embodiment of the present invention, should be from 10 to 600 microns. If the specified maximum thickness of the electrolyte layer is 600 μm, as a result of the prevailing contribution from absorption on this layer of large thickness, there is a significant decrease in the integral light transmission of the entire described multilayer stable electrochromic module to T _vis less than 62% and, as a result, loss the electrochromic optical contrast modulus at the upper limit in the range of, according to the technical result of the present invention, from 60% to 95%) to a maximum acquisitions during the recovery unit to a transparent state. At the same time, the electrolyte layer thickness of less than 10 microns, as it was empirically revealed, is insufficient both from the point of view of ensuring the principal response of the electrochromic mechanism of the described module when the voltage is applied from an external source, and from the point of view of optical maintenance of the spectral absorption maximum of the electrochromic module in the wavelength range of the electromagnetic spectrum from 400 nm to 800 nm, according to the technical result of the present invention.

In this case, all special cases of the second embodiment of the present invention are similar to the first embodiment, both in their sequence and in essence.

The table below provides an example of a specific implementation of the proposed product. In the framework of the given example, the thin-film layers of a multilayer structure of a stable multilayer electrochromic module were deposited on the surface of an optically transparent substrate from sheet silicate glass M1 by physical vapor-phase deposition of individual layers of magnetron discharge plasma. The value of the limiting residual pressure during the deposition of each of the layers of the structure ranged from 7⋅10 ^-8 to 9⋅10 ^-6 mm Hg.

The first layer of the separator adjacent to the surface of the substrate, as well as the outer layer of the separator were layers of silicon dioxide SiO ₂ deposited by sputtering silicon cathode targets in an argon-oxygen mixture of working gases in an argon / oxygen ratio of 55% / 45%. At the same time, the pressure of working gas mixtures during the deposition of both layers was maintained in the range from 1.5⋅10 ^-3 to 2⋅10 ^-3 mm Hg. The burning power of the plasma discharge in this case was 0.75 kW, with a voltage in the discharge gap of 500 V and a current on the target surface of 1.5 A.

In turn, as all the intermediate separator layers in the framework of the example given, there were layers of titanium oxide TiO _x deposited by sputtering titanium cathode targets in an argon-oxygen mixture of working gases in an argon / oxygen ratio of 55% / 45%. At the same time, the pressure of working gas mixtures during the deposition of intermediate layers-separators was also maintained in the range from 1.5⋅10 ^-3 to 210 ^-3 mm Hg for the case of deposition of each of the layers. The burning power of the plasma discharge in this case was 0.75 kW, with a voltage in the discharge gap of 500 V and a current on the target surface of 1.5 A.

In this case, ind-tin oxide In-Sn-O acted as the material of both electrically conducting layers. In the framework of the example given, the first and second electrically conductive layers were deposited by spraying preoxidized ceramic alloy targets of indium tin oxide (ITO - indium tin oxide) into an argon-oxygen mixture of working gases in an argon / oxygen ratio of 95% / 5%. At the same time, the pressure of working gas mixtures during the deposition of both layers was maintained in the range from 1.1⋅10 ^-3 to 1.4⋅10 ^-3 mm Hg. The burning power of the plasma discharge in this case was 0.5 kW, with a voltage in the discharge gap of 270 V and a current strength to the surface of the target 2 A.

As one of the two electrode layers in the framework of the example given, a layer of WO ₃ tungsten oxide was deposited by sputtering a tungsten cathode target in an argon-oxygen mixture of working gases in an argon / oxygen ratio of 50% / 50%. At the same time, the pressure of the working gas mixture was maintained in the range from 8 до10 ^-3 to 10⋅10 ^-3 mm Hg. The burning power of the plasma discharge in this case was 0.75 kW, with a voltage in the discharge gap of 500 V and a current on the target surface of 1.5 A.

In turn, the nickel hydroxide layer Ni (OH) _x , deposited by sputtering a nickel cathode target in a hydrogen-oxygen-argon mixture of working gases in a hydrogen / oxygen / argon ratio of 65% / 17%, acted as the second electrode layer in the given example. / 18%. The pressure of the mixture of working gases was also maintained in the range from 8 10 ^-3 to 10 ⋅ 10 ^-3 mm Hg. The burning power of the plasma discharge in this case was 0.6 kW, with a voltage in the discharge gap of 300 V and a current strength to the target surface of 2 A.

At the same time, the tantalum pentoxide Ta ₂ O ₅ , precipitated by spraying a tantalum cathode target in an argon-oxygen mixture of working gases in the ratio of argon / oxygen of 65% / 45%, was used as the electrolyte layer material. The pressure of the mixture of working gases was also maintained in the range from 8⋅10 ^-3 to 10⋅10 ^-3 mm Hg, and the burning power of the plasma discharge was 0.6 kW, with a voltage in the discharge gap of 300 V and amperage on the surface of the target 2 A.

As can be seen from the table, the obtained thickness of the layers satisfy the limits specified in the claims. The transmission spectrum of the product obtained in the wavelength range of electromagnetic radiation of 350-1050 nm in a bleached state is shown in FIG. 2., and in the colored state, in FIG. 3. In addition, in FIG. 4 shows the absorption spectra of the product obtained in the framework of the given example in its intercalated colored state (solid line) and the restored bleached state (intermittent dotted line) also for the range of wavelengths of electromagnetic radiation from 350 nm to 1050 nm. According to the analysis of the obtained spectra, it was found that the absolute width of the absorption line of the manufactured stable multi-layer electrochromic module is 280 nm with its actual location in the range from 405 nm to 685 nm. The maximum intensity of the absorption band of the product in the colored state falls at the wavelength of 535 nm, the absorption intensity for which is 85.33%. In turn, the transmittance intensity of the product at a given wavelength in the restored state is 79.22%, according to the corresponding spectral curve, and 8.41% in the colored intercolation state, resulting in the optical contrast value of the electrochromic module described in this example. at the maximum of its spectral absorption is 70.81%. Thus, the stable multi-layer electrochromic module obtained in the framework of the given example responds, according to the measured characteristics, with the technical result of the present invention. In addition, successive cyclic switchings of the manufactured electrochromic module between the extreme states of optical contrast did not demonstrate changes measured during comparative spectrophotometry based on the cycling results, the optical parameters of the device exceeding the limits of measurement errors, on the basis of which confirmation of the stability of the described multilayer electrochromic module in terms of resistance to cyclic switching between extreme optical contrast positions during operation.

Below is an example of a specific implementation of the proposed product according to the second embodiment. As part of it, a stable multi-layer electrochromic module was also obtained, the sheet of silicate glass M1 4 mm thick was used as an optically transparent substrate. The materials of the first adjacent to the surface of the substrate, external to the entire thin-film multilayer structure and intermediate layers-separators, the first and second electrically conductive layers and the first and second electrode layers in the framework of this example were selected to be similar to those for the respective layers of the product described in the first example. specific implementation. The application of these layers on the surface of the optically transparent substrate of the product was carried out in layers by physical vapor-phase deposition of the corresponding materials from the magnetron discharge plasma. The value of the marginal residual pressure during the deposition of each of the layers of the structure ranged from 2⋅10 ^-7 to 4⋅10 ^-6 mm Hg.

The first layer-separator, adjacent to the substrate surface, as well as the outer layer-separator, which were played by thin-film layers of silicon dioxide SiC ₂ , was deposited by sputtering silicon cathode targets into an argon-oxygen mixture of 55% / 45%). At the same time, the pressure of working gas mixtures during the deposition of both layers was maintained in the range from 1.5⋅10 ^-3 to 2⋅10 ^-3 mm Hg. The burning power of the plasma discharge in this case was 0.75 kW, with a voltage in the discharge gap of 500 V and a current on the target surface of 1.5 A.

In turn, all intermediate layer separators in the framework of the example given, which were titanium oxide layers TiO _x , were precipitated by sputtering titanium cathode targets in an argon-oxygen mixture of working gases in an argon / oxygen ratio of 55% / 45%. At the same time, the pressure of working gas mixtures during the deposition of intermediate layers-separators was also maintained in the range from 1.5⋅10 ^-3 to 210 ^-3 mm Hg for the case of deposition of each of the layers. The burning power of the plasma discharge in this case was 0.75 kW, with a voltage in the discharge gap of 500 V and a current on the target surface of 1.5 A.

The first and second electrically conductive layers, which were layers of indium tin oxide In-Sn-O, in the framework of this example were deposited by spraying preoxidized ceramic alloy targets of indium tin oxide (ITO - indium tin oxide) in an argon-oxygen mixture of working gases in an argon / oxygen constituting 95% / 5%. At the same time, the pressure of working gas mixtures during the deposition of both layers was maintained in the range from 1.1⋅10 ^-3 to 1.4⋅10 ^-3 mm Hg. The burning power of the plasma discharge in this case was 0.5 kW, with a voltage in the discharge gap of 270 V and a current strength to the surface of the target 2 A.

The first electrode layer of tungsten oxide WO _{3 was} deposited by spraying a tungsten cathode target in an argon-oxygen mixture of working gases in an argon / oxygen ratio of 50% / 50%. The pressure of the mixture of working gases was maintained in the range from 8⋅10 ^-3 to 10⋅10 ^-3 mm Hg. The burning power of the plasma discharge in this case was 0.75 kW, with a voltage in the discharge gap of 500 V and a current on the target surface of 1.5 A.

In turn, the second electrode layer of nickel hydroxide Ni (OH) _{x was} precipitated by sputtering a nickel cathode target in a hydrogen-oxygen-argon mixture of working gases in a hydrogen / oxygen / argon ratio of 65% / 17% / 18%). The pressure of the mixture of working gases was also maintained in the range from 8 в10 ^-3 to 10⋅10 ^-3 mm Hg. The burning power of the plasma discharge in this case was 0.6 kW, with a voltage in the discharge gap of 300 V and a current strength to the target surface of 2 A.

In this case, the electrolyte layer in the framework of the example cited was a polymer electrolytic gel obtained by mixing the following components at room temperature in the indicated proportion: 45% by volume of polymethyl methacrylate (PMMA), 2% by volume. % 1-butyl-3-methylimidazonium chloride (RTIL), 3% by volume PEG-600, 50% by volume % propylene carbonate (as an inert aprotic solvent), 0.6 M lithium perchlorate (salt indifferent electrolyte). At the same time, the finished unsaturated oligomerically monomeric photocurable composition, including a plasticizer, reactive oligomers and methacrylates monomers, photoinitiator - 0.005M 2,2-dimethoxy-1,2-diphenylethan-1-one, and adhesive - about 2 about % 3-methacryloxypropyltrimethoxysilane; used in the manufacture of flood-resistant high-impact triplexes for glazing of vehicles and glass for construction purposes - Akrolat 18 (according to the specifications TU 2243-069-10488057-2012). The formation of a thin film electrolyte layer was carried out by extrusion under pressure. Further stabilization of the polymer gel was provided by keeping under ultraviolet, with an irradiation intensity of 10 W / m ² in the range of 320-400 nm for 90 minutes, and then in a heat chamber at 70 ° C.

The thicknesses of the individual layers of a stable multi-layer electrochromic module, kept in the given example within the limits allowed by the formula of the present invention, are shown in the table below.

Characterization of the obtained sample was performed by spectrophotometry in the wavelength range of electromagnetic radiation from 350 to 1050 nm. The transmission spectrum of the module in a bleached state is shown in FIG. 5., in the colored state - in FIG. 6. In turn, in FIG. 7 shows the absorption spectra of the module in its intercalated colored state (solid line) and the restored bleached state (intermittent dashed line). According to the analysis of the obtained spectra, it was found that the absolute width of the absorption line of the manufactured stable multi-layer electrochromic module is 285 nm with its actual location in the range from 395 nm to 680 nm. The maximum intensity of the absorption band of the product in the colored state falls on the wavelength of 555 nm, the absorption intensity for which is 85.5%. In turn, the transmittance intensity of the product at a given wavelength in the restored state is 79.77%, according to the corresponding spectral curve), and in the painted intercollated state it is 8.15%, resulting in the optical contrast value of modulus at the maximum of its spectral absorption is 71.62%.

In addition, the connection of the optically transparent substrate of the product with a multilayer thin film coating deposited on its surface with an additional transparent substrate, which was a 4 mm thick sheet of silicate glass M1, was such that the additional optically transparent substrate was facing the outer layer-separator of the coating, containing material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, with one parties allowed to ensure an increase in the mechanical stability of a multi-layer stable electrochromic module, and on the other hand it demonstrated the preservation of the resulting characteristic values obtained during the experiments obtained by characterizing the product using optical spectrophotometry in the transmission / absorption intensity range from 0.2% to 5.8% of absolute values, above. In this case, the fixation of the connected substrates of the product was carried out by triplexing through the electrolyte layer, which is a polymer gel within the framework of this example.

Thus, based on the foregoing, the presented product demonstrates a wide absorption band with an absolute width of 250 nm to 500 nm, having a maximum in the wavelength range of the electromagnetic spectrum from 400 nm to 800 nm, and an optical contrast from 60% to 95% at the maximum absorption .

Claims (12)

1. Stable multilayer electrochromic module containing at least one optically transparent substrate and including a multilayer thin film coating on a substrate, characterized in that the multilayer coating contains directly contacting layers in the following order from the surface of the substrate: the first separator layer adjacent to the surface the substrate, and containing material selected from the group of oxides, nitrides and oxonitrides mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, M o, Hf, Ta and W, the next layer, which is the first electrically conductive layer and contains oxide of a bi-metal alloy of elements selected from the group consisting of In, Sn, F, Zn, Al, Ga, Ti, the next layer, which is intermediate layer separator and contains a material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, followed by the first electrode layer containing a material selected from the group of transition metal oxides and hydroxides of 5-10 groups of per iodic table and oxides and hydroxides of transition metal alloys of 5-10 groups of the periodic table, followed by a layer, which is an intermediate separator layer containing a material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti , Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, the subsequent layer, which is an electrolyte layer and consists of a material selected from the group of oxides, nitrides and hydrides of the elements of even rows 4- 6 periods IV and V groups of the periodic table, the next n mediocre behind the electrolyte layer, an intermediate separator layer containing a material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, the subsequent layer, which is the second electrode layer, contains material selected from the group of transition metal oxides and hydroxides of 5-10 groups of the periodic table and oxides and hydroxides of transition metal alloys of 5-10 groups of the periodic table, following him an intermediate layer separator containing material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, the subsequent layer which is the second electrically conductive layer and contains an oxide of a bi-metal alloy of elements selected from the group consisting of In, Sn, F, Zn, Al, Ga, Ti, followed by a layer-separator external to the entire thin-film multilayer structure of the electrochromic module containing material selected from the group of mono-meta oxides, nitrides and oxonitrides lv and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W; the thickness of all intermediate layers separators are in the range from 2 to 50 nm, and the thickness of the first adjacent directly to the surface of the substrate and the outer layer of separators are from 2 to 43 nm, besides the thickness of the first and second electrically conductive layers are from 40 to 210 nm, and the thickness of the first and second electrode layers are in the range from 80 to 1000 nm, while the thickness of the electrolyte layer is from 80 nm to 1200 nm. 2. Stable multi-layer electrochromic module according to claim 1, characterized in that glass, for example, fluorine-silicate, sodium-silicate or quartz glass, is used as an optically transparent substrate on which a multilayer thin-film coating is applied. 3. Stable multi-layer electrochromic module according to claim 1, characterized in that a polymer film, for example polyethylene terephthalate, polyvinyl butyral, ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polymethyl methylate, is used as an optically transparent substrate. 4. A stable multi-layer electrochromic module according to claim 1, characterized in that the optically transparent substrate coated with its multilayer thin-film coating is connected to at least one additional transparent substrate that faces the outer layer of the coating separator containing the material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, with additional transparent substrate used glass, for example fluorine-silicate, sodium silicate or quartz glass. 5. A stable multi-layer electrochromic module according to claim 1, characterized in that the optically transparent substrate coated with its multilayer thin-film coating is connected to at least one additional transparent substrate that faces the outer layer of the coating separator containing a material selected from groups of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, while as an additional transparent substrate is used olimernaya film such as polyethylene terephthalate, polyvinyl butyral, ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate or cellulose acetate. 6. The stable multi-layer electrochromic module according to claim 1, characterized in that the intermediate separator layers adjacent to the first and second electrode layers have an unequal thickness of the partial concentration of the gas component in such a way that separator from the side directly in contact with the electrode layer are sub-stoichiometric material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W. 7. Stable multilayer electrochromic module containing at least one optically transparent substrate and including a multilayer thin film coating on a substrate, characterized in that the multilayer coating contains directly contacting layers in the following order from the substrate surface: the first separator layer adjacent to the surface the substrate, and containing material selected from the group of oxides, nitrides and oxonitrides mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, M o, Hf, Ta and W, the next layer, which is the first electrically conductive layer and contains oxide of a bi-metal alloy of elements selected from the group consisting of In, Sn, F, Zn, Al, Ga, Ti, the next layer, which is intermediate layer separator and contains a material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, followed by the first electrode layer containing a material selected from the group of transition metal oxides and hydroxides of 5-10 groups of per iodic table and oxides and hydroxides of transition metal alloys of 5-10 groups of the periodic table, followed by a layer, which is an intermediate separator layer containing a material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti , Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, the next layer, which is an electrolyte layer and consists of a polymer gel, containing at least one cross-linked polymer selected from groups: polystyrene (PS), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyvinyl pyrrolidone (PVP), at least one RTIL-ionic liquid from the group of chloride, tetrafluoroborate, hexafluorophosphate, and perchlorate alkylphosphonium, N-alkylpyridinium, N, N'-dialkylimidazolium, N-alkilizohinoliniya at least one polyethylene glycol ( PEG) with a molecular weight of 62 to 4000 g / mol as well as at least one inert solvent selected from the group consisting of: propylene carbonate, γ-butyrolactone, ethylene carbonate, diethyl carbonate, dimethyl sulfoxide, acetonitrile, and at least one salt selected and From the group of perchlorates, tetrafluoroborates, hexafluorophosphates and triphenyl cyanoborates of alkali and alkaline earth metals, and also tetraalkylammonium with alkyl groups with 1-4 carbon atoms, immediately following the electrolyte layer, an intermediate separator layer containing a material selected from the group of oxides, nitrides and mononitrides - metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, the next layer, which is the second electrode layer, which contains a material selected from groups ok transition metal ides and hydroxides of 5-10 groups of the periodic table and oxides and hydroxides of transition metal alloys of 5-10 groups of the periodic table, followed by an intermediate layer separator containing a material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi- metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, the subsequent layer, which is the second electrically conductive layer and contains a bi-metal alloy oxide of elements selected from the group consisting of In, Sn, F, Zn, Al, Ga, Ti, for which This is followed by a separator layer that is external to the entire thin-film multilayer structure of the electrochromic module and contains a material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W; the thickness of all intermediate layers separators are in the range from 2 to 50 nm, and the thickness of the first adjacent directly to the surface of the substrate and the outer layer of separators are from 2 to 43 nm, besides the thickness of the first and second electrically conductive layers are from 40 to 210 nm, and the thickness of the first and second electrode layers are in the range from 80 to 1000 nm, while the thickness of the electrolyte layer is from 10 μm to 600 μm. 8. The stable multi-layer electrochromic module according to claim 7, characterized in that glass, for example fluorine-silicate, sodium silicate or quartz glass, is used as an optically transparent substrate on which a multilayer thin-film coating is applied. 9. Stable multi-layer electrochromic module according to claim 7, characterized in that a polymer film, for example polyethylene terephthalate, polyvinyl butyral, ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polymethylmethlmettept, is used as an optically transparent substrate. 10. The stable multilayer electrochromic module according to claim 7, characterized in that the optically transparent substrate coated with its multilayer thin film coating is connected to at least one additional transparent substrate that faces the outer layer of the coating separator containing a material selected from groups of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, while as an additional transparent substrate is used glass, for example fluorine-silicate, sodium silicate or quartz glass. 11. The stable multi-layer electrochromic module according to claim 7, characterized in that the optically transparent substrate, with a multi-layer thin-film coating applied to its surface, is connected to at least one additional transparent substrate that faces the outer layer of the coating separator containing the material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W, with additional transparent substrate is used polymeric film such as polyethylene terephthalate, polyvinyl butyral, ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate or cellulose acetate. 12. The stable multi-layer electrochromic module according to claim 7, characterized in that the intermediate separator layers adjacent to the first and second electrode layers have an unequal thickness of the partial concentration of the gas component in such a way that from 7% to 22% of the total layer thickness separator from the side directly in contact with the electrode layer are sub-stoichiometric material selected from the group of oxides, nitrides and oxonitrides of mono-metals and bi-metal alloys of the following elements: Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta and W.

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