Electrochromic window.

The subject of the invention is an electrochromic system, in particular glazing with transmission of the electrochromic type, or more precisely laminated glazing, the light transmission of which is modified by application across the glazing of an electrical potential. The glazings according to the invention are used to control the solar lighting in a building or in the habitat of a motor vehicle, in particular of a vehicle equipped with a glass roof.

Patent applications EP-A-253713 and EP-89400814, an electrochromic laminated glazing is known which consists of two sheets of glass coated with transparent electronic conductive layers - for example layers of indium oxide doped with tin (ITO) - successively separated by a layer of cathodic electrochromic material such as tungsten oxide (WO₃), a proton-conducting electrolyte - for example a polymer complex between polyethylene oxide (POE) and orthophosphoric acid (H₃PO₄) and a layer of an anodic electrochromic material such as iridium oxide. The two layers in contact with the electrolyte are capable of reversibly inserting protons if a suitable potential difference is applied to two opposite ends of the glazing, the insertion reaction in the tungsten oxide layer corresponding to a disinsertion reaction in the iridium oxide layer which thus plays the role of a symmetrical counter electrode of the tungsten oxide electrode. Thermodynamic equilibria can be written as follows:<maths id="math0001" num=""><math display="block"><mrow><mtext>WO₃ + xH⁺ + xe⁻ &lt;---&gt; HxW0₃</mtext></mrow></math><img file="EP0408427B1_D0001.tif" /></maths> and <maths id="math0002" num=""><math display="block"><mrow><mtext>HxIr0y &lt;---&gt; Ir0y + xH⁺ + xe⁻.</mtext></mrow></math><img file="EP0408427B1_D0002.tif" /></maths> The instantaneous measurement of the intensity I of the current flowing through the glazing is therefore a direct measurement of the number of sites of reaction of insertions / disinsertions which occur at this same instant.

The applied potential difference must be greater, in absolute value, than the thermodynamic potentials of the proton insertion or disinsertion reaction. The greater the potential difference applied, the faster the coloring - or discoloration - will be. However, beyond a certain voltage, parasites may occur, in particular the reduction in molecular hydrogen of the proton or the oxidation of oxygen in the water present in the residual state in certain layers.

Given the overvoltages at the interfaces, the limits of electrochemical stability characteristic of the system described above are between 0.6 and 1.5 Volts in the coloring phase (insertion of the protons in WO₃, disinsertion in HxIr0y) and between -0 , 6 and 0 Volt in the discoloration phase. These limits are subsequently described in this thesis as "the domain of electrochemical stability of the coloring and discoloration reaction".

The second problem which arises is the time necessary for obtaining a desired coloring or discoloration, that is to say in the hypothesis of a maximum coloring / discoloration, the time necessary for the passage of the quantity charge corresponding to all the potential reaction sites, or in other words the time necessary for the intensity I of the current to be reduced to zero - or at least to a value close to zero.

As the size of the cell increases, the amount of charge to be passed increases correspondingly; however the intensity of the current cannot increase in parallel because the theoretical relation between the difference of potential V and the current I imposes I lower than V / R where R represents the resistance of the current leads and can be confused with a good approximation with the resistance of transparent electroconductive layers. Very low for small cells, the term RI grows rapidly with the size of the cells so that the ohmic drops become a factor limiting the current and therefore the speed of staining / discoloration.

In a cell operating in transmission - which supposes transparent electroconductive layers - it is not possible to choose materials whose square resistance is less than for example 1 ohm; the most efficient materials and deposition techniques to date allowing only the production of layers of 2 to 5 Ohms of square resistance.

From document EP-A-189 601, an electrochromic device operating in transmission is known for example, comprising two glass substrates, each coated with a conductive film of tin oxide, successively separated by a layer of a material cathodic electrochromic, tungsten oxide, a liquid electrolyte and another electrochromic material such as prussian blue, auxiliary electrodes formed from a mixture of materials which are good electrical conductors such as carbon black or platinum powder being arranged along the opposite edges of the glazing and connected to a voltage generator.

With such non-punctual current leads but formed by electrically conductive strips or wires running along two opposite sides of the cell, marked by a sealing bead forming a frame around the glazing, it is thus possible to overcome some of this limit the conductivity of transparent electroconductive films. These bands or wires can be chosen from a very conductive material such as copper, so that all the points of the same band are equipotential. Consequently, if the surface of the glazing is located in a Cartesian coordinate system (x, y), where the x-axis is parallel to the current supply strips, all the points having the same ordinate are equipotential there. On the other hand, two points of the same abscissa x (and of different ordinate) are at different potentials, except to be equidistant from the median axis which is an axis of symmetry of the cell. In practice, as soon as the distance between the two electrically conductive strips exceeds for example 10 cm, the switching time of a cell is greater than one minute.

It is certainly possible to fictitiously divide this distance by multiplying the number of electrically conductive strips. Thus for a glazing of a width 1, an electrically conductive strip at y = 0 and a second strip at y = 1 is provided as before, to which are added strips at y = 1/3 and y = 21/3 - by alternating the contact faces. The cell then formed is equivalent to a set of 3 identical small cells mounted in parallel, each small cell having a resistance three times lower. However, such an arrangement leaves visible a network of electrically conductive strips which harms the general appearance of the glazing.

What is true of electrochromic glazing operating in transmission, is also true of other electrochromic systems of the display or mirror type which necessarily include at least one transparent electroconductive layer whose conductivity is relatively low in comparison, for example, with a layer thick metallic.

Furthermore, whatever the mode of operation of the electrochromic system - insertion of protons or other cations or other, for example, reduction / dissolution of a metal salt -, there are the same problems associated with these ohmic drops.

The main object of the invention is a method of using a large electrochromic system whose switching time from a colored state to a discolored state and vice versa is less than 30 seconds even if the width of the glazing is for example of the order of 50 cm, which corresponds to the dimensions of glazing for buildings or motor vehicles.

This technical problem is solved according to the invention by a method of using a system consisting of two glass sheets forming a glazing and each coated with an electroconductive layer, these electroconductive layers being successively separated by a layer of a material. electrochromic, an electrolyte and a counter electrode, said electrically conductive layers being each provided with an electrically conductive strip made of a material whose electrical conductivity is high compared to that of the electrically conductive layers, the electrically conductive strips being arranged along diagonally opposite edges of the glazing and connected to a voltage generator. According to the invention, this generator applies in the coloring phase or, respectively, in the discoloration phase, between 2 points A and B in the immediate vicinity of the electrically conductive strips, a potential difference U₁ (t) = (V_AT-V_B) (t) such that between point A and a point R of the other electrically conductive layer than that where point A is located, directly facing point A, there is a potential difference U₂ = (V_AT-V_R) (t) = U_o, where U_o is constant and chosen in the range of stability of the coloring reaction or, respectively, of discoloration.

The invention also relates to the application of such a method to known electrochromic systems and an electrochromic system adapted for the implementation of this method.

Ohmic drops being directly linked to the distance between the electrodes, it is generally operated with electrically conductive strips parallel to the length of the glazing.

In traditional operation, the potential difference between the two bands A and B is imposed, in other words between) two points of extreme ordinates; according to the invention, the potential is imposed between two points of the same abscissa, arranged on the same side of the glazing but on different electroconductive layers. In this way, the effective tension is maximum at time t = 0 and therefore the appearance of the coloration - or on the contrary its disappearance - is more quickly sensitive to an observer. It can be noted that the type of supply proposed does not really compensate for ohmic drops; so if a potential difference U_o is imposed on one side of the glazing, except at the) ends of the glazing (y = 0 or y = 1) two points facing each other always have between them a potential difference V (y) less than the imposed voltage. However, we observe experimentally that this value V (y) is always greater than the value V ′ (y) obtained when we impose Uo between two extreme strips of the glazing U₁ = U_o; consequently, the maximum coloration is reached much more quickly and it is possible to reach, for glazing units of for example (40 × 80) cm 2, overall response times of the order of 30 seconds.

Compared to electrochromic glazing known in the art, there is in fact observed with a glazing according to the invention a much more marked difference between the transient states of coloring of the marginal regions and the transient states of coloring of the central region of the glazing; the value of the effective potential difference between two points of the glazing facing each other depends much more than previously on the position of these points. However, whatever this position, the effective potential difference is higher than with glazing according to art. This results in a non-almost uniform coloring but with a very strong contrast, the edges of the glazing appearing very quickly blue-night while the coloring of the central part only appears at the end of the switching time. But of course, from this moment the shade of the glazing is perfectly uniform.

According to a first embodiment of the invention, it is determined by prior voltammetric recordings what the potential difference U₁ must be applied to time t to obtain a potential difference U une constant over time. Once these values ​​have been determined, it is sufficient to program the voltage generator accordingly.

To simplify this programming, we can approximate the curve U₁ = f (t) by an exponential function, which simplifies the electronics associated with the voltage generator but does not eliminate the need for full-scale tests, to be repeated for each model of glazing, in order to determine the parameters of the exponential function.

To overcome this last difficulty, it is preferable to use a mounting with 3 electrodes, of the potentiostat type by using for example an operational amplifier. A reference electrode is then placed at point R. For a question of balance of electrical charges, whatever the position of this reference electrode on the line y = 0, all the points on this line are equipotential. Consequently, the reference electrode can be indifferently formed by an electrically conductive strip covering the entire length of the glazing (and therefore identical to the strip forming the electrode A) or only part of it.

When the reference electrode R is constituted by an electrically conductive strip of the length of the glazing, one of the two glass sheets is advantageously provided with two electrodes mounted on two parallel edges. This arrangement can then be further exploited to remedy another handicap of electrochromic glazing, namely that the kinetics of the reactions can be very low at low temperature and in particular for temperatures below 10 ° C. In this case, the transparent electroconductive layer located between these two electrodes can be used as a heating layer, thanks to the release of heat - due to the resistance of said layer - which occurs when a potential difference is applied between these two. electrodes. Preferably, the potential difference applied for this preheating is greater than 20 volts and of the order of 24 volts, which more generally corresponds to a voltage of the order of 0.5 volts per centimeter of distance between the electrodes. This preheating phase can for example precede any coloring and be of a duration of the order of 2 minutes. Given the proximity of the second glass sheet, it has a tendency to charge during this coloring phase, which in the long term causes a bluing which can advantageously be avoided by using an alternating voltage.

Other details of advantageous characteristics of the invention appear from the description given below with reference to the appended drawings which represent:<ul id="ul0001" list-style="none"><li>. <b><u style="single">figure 1</u></b> : a block diagram of an electrochromic cell according to the invention,</li><li>. <b><u style="single">figure 2</u></b> : a sectional view of a glass roof for motor vehicles.</li></ul>

In Figure 1 is shown schematically an electrochromic cell; for the sake of clarity, the thickness ratios between the various elements of the system have not been respected. This cell is constituted by a glass sheet 1 coated with a transparent electroconductive layer 2, provided with a current supply strip 3. This strip 3 is preferably parallel to the length L of the glazing which is moreover of a width 1. The glass sheet 1 faces a second glass sheet 4 which is likewise coated with a transparent electrically conductive layer 5 provided with a current supply strip 6. Between the two transparent electrodes 2, 5, there is successively a layer 7 of an anodic electrochromic material (preferably iridium oxide), an electrolytic layer with proton conduction 8 (preferably a polymeric complex between polyoxide d ethylene and strictly anhydrous orthophosphoric acid) and a layer 9 of an electrochromic cathode material (preferably tungsten trioxide).

As an indication, it is possible to use layers having more precisely the following characteristics:<ul id="ul0002" list-style="dash"><li><b><u style="single">Substrates (1 and 4)</u></b> :    . 3 mm thick float glass sheet,</li><li><b><u style="single">Transparent electroconductive layers (2 and 5)</u></b> : <ul id="ul0003" list-style="none"><li>. indium oxide layer doped with tin, deposited by magnetron sputtering,</li><li>. thickness 400 nm,</li><li>. resistance per square 5 Ohms.</li></ul></li><li><b><u style="single">Cathode electrochromic layer (9)</u></b> : <ul id="ul0004" list-style="none"><li>. layer of tungsten oxide deposited by thermal evaporation in a molybdenum crucible under an air pressure of 5 x 10⁻⁵ torr,</li><li>. thickness 260 nm.</li></ul></li><li><b><u style="single">Electrolyte (organic polymer 8)</u></b> : <ul id="ul0005" list-style="none"><li>. Solid solution of anhydrous phosphoric acid in polyethylene oxide,</li><li>. <b><u style="single">preparation</u></b> :</li></ul></li></ul><ul id="ul0006" list-style="none"><li>. Under rigorously anhydrous conditions, phosphoric acid (17.5 g) normapur and polyethylene oxide of molecular weight equal to 5,000,000 (density 1.21, glass transition temperature -40 ° C.) are dissolved per liter of solvent. C, O / H ratio of the number of oxygen atoms of the polymer to the number of hydrogen atoms of the acid equal to 0.66).</li><li>. The common solvent is for example a 50-50 mixture of acetonitrile and tetrahydro-furan.</li><li>. The solution is poured onto a glass plate coated with a layer of tungsten oxide deposited as indicated above. The uniform thickness is obtained by the film puller method. The casting is carried out under an atmosphere with controlled humidity. After evaporation of the solvent, a film of 50 micrometers is obtained, the conductivity of which at 20 ° C. is 9.10⁻⁵ Ohm.⁻¹.cm⁻¹ and the light transmission of which is greater than 85%. The humidity level at the time of casting should preferably be between 40 and 100 ppm, which allows optimal contrast to be obtained subsequently. - <b><u style="single">Anodic electrochromic layer</u></b> : <ul id="ul0007" list-style="none"><li>. layer of iridium oxide deposited by sputtering assisted by a magnetic field, under a pressure of 6 millitorrs of a gaseous oxygen / hydrogen mixture (in an 80-20 ratio),</li><li>. thickness 55 nanometers.</li></ul></li></ul>

Preferably, the electrolytic layer is deposited on the tungsten oxide layer within a short time after the deposition thereof. The glazing is assembled in an autoclave at a temperature of 90 ° C under a pressure of 15 kg / cm².

The above data are given exclusively by way of example and should not be considered as limiting the scope of the present invention which applies to all large electrochromic cells.

Traditionally, between point A - which can be considered as a point on the electrically conductive strip 3 - and point B - which can be considered as a point on the electrically conductive strip 6 - a fixed potential difference V₁ is chosen, chosen in the stability range of the desired electrochemical reaction. Such an arrangement has been used for three homothetic cells S1, S2 and S3, the current supply strips of which are spaced 3, 4.5 and 9 centimeters apart, respectively. FIG. 3 shows the variation over time of the intensity of the coloring current. For the two small cells, the current I_o at time t = 0 is proportional to the surface and the coloring time is almost identical. In addition, after 5 seconds, most of the coloring process is completed. On the other hand, with cell S3, we see that the current I_o is not proportional to the surface and is limited by ohmic drops. In practice, this prohibits the production of a cell whose current supply strips are spaced more than 10 cm apart - unless they accept switching times greater than one minute.

Another way to analyze the problem is to look at two points M_AT and M_B which in the coordinate system (x, y, z) shown diagrammatically in Figure 1 have respectively the coordinates (x, y, a) and (x, y, b). Between these two points, there is at time t a potential difference V = VM_AT - VM_B. Furthermore, if we choose electroconductive strips 3, 6 made of copper or any other highly conductive material, we can consider that all points M_AT - and respectively M_B - of a given ordinate there are equipotential. The curve 10 representative of the different values ​​of V as a function of the ordinate of the pairs of points (M_AT, M_B), this for a cell 14 cm wide (distance AB) and a potential difference U₁ of 1.4 Volt and at time t = O. It can be seen that the effective voltage V is much less than U₁, and that this difference is further accentuated for the central area of ​​the cell.

If now we choose to operate according to the invention by maintaining a fixed potential difference U₂ between point A and point R facing it on the conductive strip 6 ′, we obtain the curve 11 established for U₂ = 1.4 Volt . We note that for any pair of points (M_AT, M_B), the observed potential difference V is always less than or equal to U₂. For the desired electrochemical reaction, it is necessary and therefore sufficient to impose a value U₂ included in the field called electrochemical stability of the invention. Furthermore, except on the edges, the effective voltage is not equal to the imposed voltage U₂; the invention therefore does not completely overcome ohmic drops. However, the comparison of curves 10 and 11 shows that the effective voltage according to the invention is approximately 3 times higher for any pair of points M_AT, M_B. This results in coloration - or discoloration - much faster. In addition we note that the effect of the edges is more marked than with a traditional assembly; this results in an almost instantaneous appearance of the color near the edges of the glazing, but later in the central region. This aspect of progressive coloring which "leaves" the edges is characteristic of the glazings according to the invention.

For terminals A and B spaced 14 cm apart, the gain in coloring time is 6 seconds, ie a time saving of 30%. For terminals even further apart the gain increases further. Thus, an electrochromic roof can be produced, the shortest length of which exceeds 30 cm and yet the switching time is less than 1 minute at 20 ° C., in this case a division by 6 of the switching time which can typically be reduced by 3 minutes to 30 seconds. .

The assembly according to the invention endows the electrically conductive layer 5 with two current supply strips 6 and 6 ′. Advantageously, the electrical resistance of this layer 5 can be used to heat the cell. For this, before coloring, a potential difference U₃ of for example 24 Volts is applied between point B and point R, which makes it possible to raise the temperature of the electrolytic layer of which it is known that the maximum performances are obtained. for a temperature between 20 and 80 ° C. The potential difference U₃ is preferably an alternating voltage in order to avoid the polarization of the layers of electrochromic materials, with in this case for example an effective voltage of 24 Volts. It should be noted that heating can be used regardless of the oxidation state of the electrochromic layers.

The invention has been described with reference to a cell whose electrolyte is proton-conducting but it should be understood that it applies mutatis mutandis to all electrochromic systems, in particular to cells whose electrolyte is ion-conducting, by lithium example. Likewise, materials other than those mentioned may be used for the production of the electrochromic layer and the counter-electrode, this in particular with a view to obtaining other colors, the values ​​of the applied voltages having to be adjusted as a function new thermodynamic balances. In addition, a 3-electrode assembly can be used more generally in any system requiring at least one transparent electrically conductive layer, whether it be systems operating by insertion / de-insertion of ions such as those mentioned in this specification, display systems for systems with an electrochromic gel or with liquid crystal.