EP2047326A2

EP2047326A2 - Electrochemical and/or electrocontrolable device, of the glazing type, having variable optical and/or energetic properties

Info

Publication number: EP2047326A2
Application number: EP07823645A
Authority: EP
Inventors: Emmanuel Valentin; Samuel Dubrenat
Original assignee: Saint Gobain Glass France SAS; Compagnie de Saint Gobain SA
Current assignee: Sage Electrochromics Inc
Priority date: 2006-08-04
Filing date: 2007-07-26
Publication date: 2009-04-15
Also published as: WO2008017777A3; CA2659614A1; CN101501562A; FR2904704A1; FR2904704B1; CN101501562B; JP5247695B2; KR20090034948A; WO2008017777A2; BRPI0714922A2; EA014682B1; US7894120B2; JP2009545765A; EA200970179A1; US20090323157A1

Abstract

Electrochemical/ electrocontrolable device having variable optical and/or energetic properties, comprising at least one carrier substrate with a first electroconducting layer, a first electrochemically active layer than can reversibly insert ions such as cations such as H+, Li+ or anions such as OH-, in particular in an anodic (or cathodic, respectively) electrochrome material, a layer of electrolyte, a second electrochemically active layer than can reversibly insert said ions, in particular in a cathodic (or respectively anodic) electrochrome material, a second electroconducting layer, characterized in that at least one of the electrochemically active layers that can reversibly insert said ions, in particular in an anodic or cathodic electrochrome, comprises sufficient thickness to allow insertion of all the ions without electrochemical dysfunction of said active layers.

Description

"Electrochemical device, and / or electrically controllable type glazing and optical properties and / or variable energy"

The subject of the present invention is an electro-chemical and / or electrically-controllable device of the glazing type and with variable optical and / or energy properties .There is in fact currently an increased demand for so-called "smart" glazings that are capable of adapt to the needs of users. With regard to "intelligent" ^B windows, this may be the control of the solar input through glazings mounted outdoors in buildings or vehicles of the car, train or airplane type (porthole for example). is to be able to limit an excessive heating inside the cockpits / premises, but only in case of strong sunshine.

It can also be the control of the degree of vision through glazing, especially in order to obscure them, to make them diffuse or even to prevent any vision when it is desirable. This may concern glazing mounted in interior partitions in premises, trains, planes or mounted in automotive side windows. This also applies to mirrors used as mirrors, to punctually avoid the driver to be dazzled, or signs, so that messages appear when necessary, or intermittently to better attract attention. Glazing that can be rendered at will scattering can be used when desired as projection screens.

Alternatively, it may be the generation of light through the glazing to control the level of brightness or color generated. There are various electro-controllable systems for such aspect changes / thermal properties.

In order to modulate the light transmission or the light absorption of the glazings, there are the so-called viologen systems, such as those described in the U.S. Patent Nos. 5,239,406 and 612,826.

To modulate the light transmission and / or the thermal transmission of the glazings, there are also so-called electrochromic systems.

These, in known manner, generally comprise two layers of electrochromic material separated by an electrolyte layer and framed by two electroconductive layers, the latter being associated with current leads connected to a power supply.

Each of the layers of electrochromic material can reversibly insert cations and electrons, the modification of their degree of oxidation following these insertions / désinsertions leading to a change in its optical and / or thermal properties. We can notably modulate their absorption and / or their reflection in the wavelengths of the visible and / or infra-red. It is customary to arrange the electrochromic systems in three categories:

that in which the electrolyte is in the form of a polymer or a gel; for example a proton-conductive polymer such as those described in patents EP-253 713 or EP-670 346, or a conductive polymer of lithium ions such as those described in patents EP-382 623, EP-518 754 and 532,408; the other layers of the system are generally of a mineral nature,

the one in which the electrolyte and the other layers of the stack are of a mineral nature. This category is often referred to as the "all solid" system, examples of which can be found in EP-867,752, EP-831,360, WO00-57243 and WO00-71777,

the one in which all the layers are based on polymers, a category often referred to as the "all-polymer" system.

The present invention is concerned with electrochromics "all solid" All these systems have in common the need to be equipped with current leads supplying electroconductive layers on either side of the layer or the various activated layers). system.

These current leads allow the application of a voltage and the passage of current through the stack, the passage of the current to ensure switching from a colored state to a bleached state and vice versa.

It is understood that the transition from one state to another results in either obscuration or lightening of the glazing thus controlled. The current tendency is to have systems, under the effect of a food, which produce fast, homogeneous effects and whose contrast between the 2 states (discolored / colored) is the highest possible, so as to reach a almost opaque system in the colored state, the contrast being defined as the ratio between the value of the light transmission (TL) to the faded state to the value of the light transmission in the colored state.

To do this, several solutions of the prior art are known: - increase the amount of charge or the voltage level at the terminals of the current leads, the major disadvantage of this solution lies in the fact that generally it leads to a lower robustness of the system,

- use optically more active layers broadening the ranges of light transmission achievable. The development of such layers may require considerable research work with modification or replacement of existing materials,

- Juxtapose at least 2 complete systems mounted in multiple glazing configuration (see patent US-5,076,673). This solution minimizes the chances that a defect present on ^* a system is facing a fault is present on the other system. The major disadvantage of this solution lies in the fact that it requires a power supply for each of the systems which strike the cost price; moreover, the juxtaposition of the systems results in an increase of the overall structure, considering that at least 4 substrates are necessary to the assembly. This assembly in multiple glazing, especially double glazing, necessarily increases the number of optical interfaces and therefore will lead to a lowering of the light transmission in the state discolored. This double glazing installation type "building" n ^J is not transposable in the automotive field. It can be noted that the laminated assembly, common in the automotive field, is only possible with substantially flat substrates and with a limited number of substrates (2 or 3). It is almost impossible with strongly curved substrates, especially when their number is greater than 2 or even 3 and generally leads to the risk of optical distortion.

The present invention therefore aims to overcome the solutions of the prior art by proposing a system controllable by a single power supply and whose operating performance is at least identical to that of two juxtaposed systems.

The subject of the invention is an electrochemical / electrically controllable device, with optical and / or variable energy properties of the "all solid" electrochromic type of structure TC1 / EC1 / EL / EC2 / TC2, comprising at least one carrier substrate provided with a first electroconductive layer, a first electrochemically active layer capable of reversibly inserting ions such as H +, Li + cations or anions such as OH-, in particular into an anodic (or cathodic) electrochromic material, an electrolytic layer, a second electrochemically active layer capable of reversibly inserting said ions, in particular of a cathodic (or anodic) electrochromic material, a second electroconductive layer, characterized in that at least one of the electrochemically active layers capable of inserting reversible said ions, in particular an anodic electrochromic material cathode has a sufficient thickness so as to allow insertion of all the ions without electrochemical dysfunction of said active layers, and in that the electrolyte-functional layer EL comprises at least one layer based on a material chosen from oxides, tantalum, tungsten, molybdenum, antimony, niobium, chromium, cobalt, titanium, tin, nickel, zinc optionally alloyed with aluminum, zirconium, aluminum, silicon, optionally alloyed with aluminum, silicon nitride optionally alloyed with aluminum or boron, boron nitride, aluminum nitride, vanadium oxide optionally alloyed with aluminum, tin and zinc oxide, at least one of these oxides being optionally hydrogenated, or nitride and in that each electroactive layer EC1 or EC2 comprises at least one of the following compounds: oxides of tungsten W, niobium Nb, tin Sn, bismuth Bi ₅ V vanadium, nickel Ni, iridium Ir, Sb antimony, tantalum Ta, alone or mixed, and optionally including an additional metal such as titanium, rhenium, or cobalt and in that the thickness of the EC1 layer is between 70 and 250 nm and preferably between 150 nm and 220 nm

Due to the presence of a sufficient thickness of electrochromic material, it is possible to obtain, at a lower cost, a system having a high degree of obscuration.

In preferred embodiments of the invention, it is possible further to use Tune and / or U at the other of the following provisions:

The thickness of the layer EC2 is between 400 and 150O nm and preferably between 700 nm and 1300 nm, and even more preferably between SOO and 1200 nm,

the quantity of charges exchanged during an operating cycle of said device is between 25 mC / cm. ² and 8OmC / cm ² - the electroconductive layer TC1 or TC2 is of the metallic type or of the TCO (Transparent Conductive Oxide) type in InaCtoSn (ITO), SnO2: F, ZnO: A1, or is a multi-layer of the TCO / type; metal f TCO _? this metal being chosen in particular from silver, gold, platinum, copper, or a NiCr / metal / NiCr type multi-layer, the metal being also chosen in particular from silver, gold, platinum; , the copper, the contrasts obtained are between 9 to 10,000 and preferably between 15 to 4000.

According to another aspect of the invention, it relates to electrochromic glazing, which is characterized in that it comprises the electrochemical device according to one of the preceding claims, in particular having a transmission and / or light reflection and / or variable energy, with the substrate or at least a part of the transparent (or partially transparent) substrates, made of plastic material, preferably mounted in multiple glazing and / or laminated, or in double glazing. According to yet another aspect of the invention, it relates to a method for manufacturing the electrochemical device, as previously described, in which at least one of the layers of the electrochemical device is deposited by a technique using vacuum, of the cathode sputtering type, possibly assisted. by magnetic field, by thermal evaporation or assisted by a flow of electrons, by laser ablation, by CVD, possibly assisted by plasma or by microwaves, or by a technique at atmospheric pressure, in particular by deposition of layers by solid synthesis. gel, especially of toughened type, spray-coating or laminar coating. Finally, according to yet another aspect of the invention, it relates to the use of the previously mentioned glazing as glazing for the building, glazing for the automobile, glazing of industrial vehicles or public transport, rail, sea, air, in particular portholes, mirrors, mirrors, display and display, shutter for image acquisition devices.

Within the meaning of the invention, the term "lower" electrode means the electrode which is closest to the carrier substrate taken as reference, on which at least part of the active layers (for example all the active layers in a electrochromic system "all solid") is deposited.The "upper" electrode is the one deposited on the other.

In these ranges of thickness, the electrode remains transparent, that is, it has low light absorption in the visible. However, it is not excluded to have much thicker layers (especially in the case where the electro-chromatic electroactive system operates in reflection rather than transmission), or thinner layers (especially when they are associated in the electrode to another type of conductive layer, metal for example). As mentioned above, the invention can be applied to different types of electrochemical or electro-controllable systems.

It is particularly interested in electrochromic systems, especially the "all solid"

The electrochromic systems or glazing to which the invention can be applied are described in the aforementioned patents. They may comprise at least two carrier substrates between which are included stacks of functional layers each comprising at least successively a first electroconductive layer, an electrochemically active layer capable of reversibly inserting ions such as H ^+, Li ⁺ , OH- of the type an anodic or cathodic electrochromic material, an electrolyte layer, a second electrochemically active layer capable of reversibly inserting ions such as H ⁺ , Li ⁺ , OH ^" of the cathodic or anodic electrochromic material type, and a second electroconductive layer, term "layer" is to be understood as a single layer or a superposition of several layers, continuous or discontinuous.

The invention also relates to the incorporation of the electrochemical devices described in the preamble of the present application in glazings, operating in reflection (mirror) or transmission. The term "glazing" is to be understood in the broad sense and includes any substantially transparent material, glass and / or polymeric material (such as polycarbonate PC or polymethyl methacrylate PMMA). The carrier substrates and / or counter-substrates, that is to say the substrates surrounding the active system, can be rigid, flexible or semi-flexible. This glazing can be used as glazing for the building, glazing for the automobile, glazing of industrial vehicles or public transport, railway, maritime, air, in particular porthole, mirrors, mirrors. This glazing having in particular a transmission and / or light reflection and / or variable energy, with the substrate or at least a portion of the transparent or partially transparent substrates (s), plastic material or glass, is preferably mounted in multiple glazing and / or laminated, or double glazing.

The invention also relates to the various applications that can be found in these devices, glazing or mirrors: it may be to make glazing for building, including external glazing, internal partitions or glass doors). It can also be windows, roofs or internal partitions of means of transport such as trains, planes, cars, boats. It can also be display or display screens, such as projection screens, television or computer screens, touch screens, commonly known in English.

"Display". They can also be used to make glasses or camera lenses, or to protect solar panels.

The invention will now be described in more detail using non-limiting examples and figures:

FIG. 1: a schematic view of an electrochromic cell according to the invention,

- Figure 2 shows a schematic cross section of Figure 1. Figure 2 is intentionally highly schematic and not necessarily to scale for ease of reading: it shows in section an electrochromic device "all solid ^≈ according to the teachings of the invention comprising successively:

a clear silico-sodo-calcic glass substrate Sl, 2.1 mm thick,

a lower electroconductive layer 2 comprising a stack of layers of the ITO / ZnO type: Ai / Ag / ZnO: A1 / ITO respective thicknesses 15 to 20 nm for 11TO / 60 at SO nrπ for ZnO: Al / 3 at 15 nm for silver / 60 to 80 nm for ZnO: Al / 15 at 20 nm for TITO, or di-oxide base (doped tin oxide to tin) of 500 nm, deposited hot - a first electrochromic system 3 whose structure will be described below

an upper electroconductive layer 4 based on TlO or SnOa: F or alternatively an upper electroconductive layer comprising other conductive elements: it may be more particularly to associate the electroconductive layer with a more conductive layer than , and / or a plurality of strips or conductive wires. Reference is made to the patent WO-00/57243 for the implementation of such multi-component electroconductive layers. A preferred embodiment of this type of electroconductive layer is to apply on the dlTO layer (optionally surmounted by one or more other conductive layers) a plurality of conductive strips, or a network of conductive son 6 embedded on the surface of a polymer sheet 7 as a lamination interlayer and for electrically supplying the upper electroconductive layer associated with the electrochromic stack.

a clear S2-silica-S2 glass substrate 2.1 mm thick. Electrochrome 3 comprises:

a first layer of anodic electrochromic material EC1 in iridium oxide (hydrated) of 70 nm to 250 nm or of hydrated nickel oxide of 200 to 400 nm, alloyed or not with other metals, (alternatively, layer can be replaced by a layer of anodic electrochromic material in nickel oxide of 200 to 400 nm, allied or not with other metals)

a layer of tungsten oxide of 100 nm, a second layer of hydrated tantalum oxide or of hydrated silica oxide or of hydrated zirconium oxide of 100 nm, the latter two layers forming an electrolyte-functional layer EL; a second layer of cathodic EC2 electrochromic material; The entire set of layers was deposited by magnetic field assisted sputtering using a tungsten oxide WO3 of 400 to 1200 nm. As a variant, it could be obtained, by thermal evaporation or assisted by an electron flow, by laser ablation, by CVD, optionally assisted by plasma or by microwaves, or by a technique at atmospheric pressure, in particular by deposition of layers by synthesis sol-gel, especially of toughened type, spray-coating or laminar coating.

The active stack 3 may be incised on all or part of its periphery grooves made by mechanical means or by laser radiation attack, possibly pulsed, and this, to limit peripheral electrical leakage as described in the French application FR-2 781 084.

Furthermore, the glazing shown in FIGS. 1, 2 incorporates (not shown in the figures) a first peripheral seal in contact with the faces 2 and 3 (2 and 3 being in a conventional manner the numbering of the internal faces of the substrates Sl and S2), this first seal being adapted to provide a barrier to external chemical attack. A second peripheral seal is in contact with the edge of Sl, the edge of S2 and faces 1 and 4 (1 and 4 being in a conventional manner the numbering of the external faces of substrates S1 and S2), so as to provide: a barrier, a mounting means with the means of transport, a seal between the inside and the outside, an aesthetic function, means for incorporating reinforcement elements. The electrochromic device described above constitutes Example 1.

The electrochromic device of this example 1 has been connected to a energy source so as to allow switching between a colored state and a discolored state and vice versa.

The contrast values achieved are given below for various stacking configurations. In a first exemplary configuration which constitutes an example according to the prior art to which it will be possible to compare the following,

The association, on a silico-sodo-calcic substrate coated with ITO with an overall thickness of 2.1 mm, includes an electrochromic system comprising:

a first layer of anodic electrochromic material EC1 in iridium oxide (hydrated) of 60 to 90 nm, preferably 85 nm

a layer of tungsten oxide of 100 nm,

a second layer of hydrated tantalum oxide, this layer having an electrolyte function EL

a second layer of cathodic electrochromic material EC2 based on tungsten oxide WO ₃ of 350 to 390 nm, preferably 380 nm, allows switching of the glazing between a bleached state characterized by a light transmission (TL) of 55% and a state of colored characterized by a TL of 2.5%. The contrast associated with this glazing is 22 for a quantity of exchanged charges of 25 to 30 mC / cml

For the purposes of the invention, the measurement of the quantity of charges circulating during the discoloration / discoloration cycles between the electroactive layers corresponds to a number of charges per unit of stacking surface, normalized to a given active layer thickness and increasing linearly with the thickness of said layer.

In a second configuration example,

The association, on a diO-coated silico-sodo-calcium substrate with an overall thickness of 2.1 mm, of an electrochromic system comprising:

a first layer of anodic electrochromic material EC1 in iridium oxide (hydrated) of 80 to 120 nm, preferably 105 nm a layer of tungsten oxide of 100 nm,

a second layer of hydrated tantalum oxide, this layer having an electrolyte function EL, a second layer of cathodic electro chromium material EC2 based on tungsten oxide WO3 of 400 to 600 nm, preferentially 500 nm, makes it possible to switch the glazing between a discolored state characterized by a light transmission (TL) of 50% and a colored state characterized by a TL of 1%. The contrast associated with this glazing is 50 for a quantity of exchanged charges of 33 to 40 mC / cm ² .

In a third configuration example,

The association, on a silico-sodo-caicic substrate covered diTO with a total thickness of 2.1 mm, of an electrochromic system comprising:

a first layer of anodic electrochromic material EC1 in iridium oxide (hydrated) of 150 to 300 nm, preferably 210 nm, a layer of tungsten oxide of 100 nm,

a second layer of hydrated tantalum oxide, this layer having an electrolytic function EL

a second layer of cathodic electrochromic material EC2 based on tungsten oxide WO3 of 800 to 1500 nm, preferentially 1000 nm, allows switching of the glazing between a bleached state characterized by a light transmission (TL) of 40% and a colored state characterized by a TL of 0.01%. The contrast associated with this glazing is 4000 for a quantity of exchanged charges of 66 to 80 mC / cm. ² . If we compare Examples 2 and 3 to Example 1, we can notice that as soon as the thickness of the EC2 layer is significantly increased, it is possible to obtain high contrast values, while retaining a quantity of charges exchanged substantially in the same order of magnitude.

Claims

An electrochemical / electrically controllable device, with optical and / or variable energy properties of the electrochromic "all solid" type of structure TC 1 / EC 1 / EL / EC 2 / TC 2, comprising at least one carrier substrate provided with a first electroconductive layer, a first electrochemically active layer capable of reversibly inserting ions such as ions such as H +, Li + or anions such as OH-, in particular into an anodic (or cathodic) electrochromic material, an electrolyte layer, a second electrochemically active layer capable of reversibly inserting said ions, in particular of a cathodic (or respectively anodic) electrochromic material, a second electroconductive layer, characterized in that at least one of the electrochemically active layers capable of reversibly inserting said ions, in particular of anodic or cathodic electrochromic material, comprise a the thickness is sufficient to allow insertion of all ions without electrochemical dysfunction of said active layers, and in that the EL electrσlyte function layer comprises at least one layer based on a material selected from oxides, tantalum, tungsten, molybdenum, antimony, niobium, chromium, cobalt, titanium, tin, nickel, zinc possibly alloyed with aluminum, zirconium, aluminum, silicon, possibly alloyed with aluminum, silicon oxide possibly alloyed with aluminum or boron, boron nitride, aluminum nitride, vanadium oxide, optionally alloyed with aluminum, tin oxide and zinc, at least one of these oxides being optionally hydrogenated, or nitride and in that each electroactive layer EC1 or EC2 comprises at least one of the following compounds: oxides of tungsten W, niobium Nb, tin Sn, bismuth Bi, of vanadium V, of ni ckel Ni, Ir irium, antimony Sb, tantalum Ta, alone or in mixture, and optionally comprising an additional metal such as titanium, rhenium or cobalt and in that the thickness of the ECl layer is between 70 and 250 nm and preferably between 150 nm and 220 nm.

2. Device according to claim 1, characterized in that the thickness of the EC2 layer is between 400 and 1500 nm and preferably between

700 nm and 1300 nrα, and even more preferably between 800 and 1200 nm.

3. Device according to any one of the preceding claims, characterized in that the amount of charges exchanged during an operating cycle of said device is between 25 mC / cm ² and 8OmC / cm ²

4. Device according to claim 1, characterized in that the electroconductive layer TCl or TC2 is of metallic type or of the type TCO (Transparent Conductive Oxide) in InaCtoSn (ITO), rαO ₂ : F, ZnO: Al, or be a multi TCO / metal / TCO type layer, this metal being chosen in particular from silver, gold, platinum, copper or NiCr / metal / NiCr multi-layer type, the metal being also chosen in particular from silver, gold, platinum, copper.

5. Device according to any one of the preceding claims, characterized in that the contrast values obtained are between 9 to 10,000 and preferably between 15 to 4000.

6. electrochromic glass, characterized in that it comprises the electrochemical device according to one of the preceding claims, having in particular a transmission and / or light reflection and / or variable energy, with the substrate or at least part of the transparent substrates (S) or partially tranfrpres, (s) plastic material, preferably mounted in glazing mui ple and / or laminated, or double glazing.

7. A method of manufacturing the cketrochemical device according to one of claims 1 to 5, characterized in that at least one of the layers of the electrochemical device is deposited by a technique using vacuum, sputtering type, possibly assisted by field magnetic, by thermal evaporation or assisted by an electron flow, by laser ablation, by CVD, optionally assisted by plasma or by microwaves, or by a technique at atmospheric pressure, in particular by deposition of layers by sol-gel synthesis, especially of toughened type, spray-coating or laminar coating.

S. Use of the glazing according to claim 6 as glazing for the building, glazing for the automobile, glazing of industrial vehicles or public transport, railway, maritime, air, in particular porthole, mirrors, mirrors, display and display, shutter for image acquisition devices.