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    • 专利摘要:
    transparent electrochromes system with several polarization electrodes. the present invention relates to transparent electrochromic systems (100) which each comprise a pair of supply electrodes (1,2) and at least one pair of polarization electrodes (3,4). the polarization electrodes prevent a reciprocal neutralization reaction of electroactive substances in the systems from causing useless consumption of electrical current. they also prevent the neutralization reaction from limiting a lower light transmission value of the systems. for this, the polarization electrodes produce an electric field (e) inside the systems that shoots electroactive substances that reacted on the supply electrodes in different zones.
    公开号:BR112012007612B1
    申请号:R112012007612-4
    申请日:2010-09-24
    公开日:2020-09-24
    发明作者:Samuel Archambeau；Claudine Biver；Christian Bovet；Jean-Paul Cano；Sandrine Duluard；Anthony Saugey
    申请人:Essilor International；
    IPC主号:
    专利说明:

    [0001] [0001] The present invention relates to transparent electrochromic systems with several pairs of polarization electrodes, as well as electrochromic devices that comprise these systems.
    [0002] - duas paredes externas que definem um volume fechado, o sistema sendo transparente para uma direção de olhar, atravessando as paredes externas e o volume fechado entre dois lados opostos; - um líquido ou gel que fica contido no volume fechado; - primeiras e segundas substâncias eletroativas que são repartidas no líquido ou gel, com potenciais respectivos de óxido-redução que são diferentes, as determinadas pelo menos primeiras e segundas substâncias eletroativas tendo um efeito óptico variável entre uma forma oxidada e uma forma reduzida dessas substâncias; e - um par de eletrodos de alimentação transparentes, que são destinados a serem ligados respectivamente a dois bornes de saída de uma fonte elétrica variável para alimentar o sistema com corrente elétrica, de forma a transferir elétrons para ou partir de pelo menos determinadas das substâncias eletroativas, de uma forma inversa entre as primeiras e as segundas substâncias eletroativas a um mesmo instante de um funcionamento do sistema. [0002] In an known way, an electrochromic system is a transparent element, whose optical characteristics of light transmission can vary in response to an electric current that is applied between two supply terminals of the system. For this, an electrochromic system usually comprises: - two external walls that define a closed volume, the system being transparent to a viewing direction, crossing the external walls and the closed volume between two opposite sides; - a liquid or gel that is contained in the closed volume; - first and second electroactive substances that are distributed in the liquid or gel, with respective oxide-reduction potentials that are different, those determined by at least the first and second electroactive substances having an optical effect varying between an oxidized form and a reduced form of these substances; and - a pair of transparent supply electrodes, which are intended to be connected respectively to two output terminals of a variable electrical source to supply the system with electrical current, in order to transfer electrons to or from at least certain of the electroactive substances, in an inverse way between the first and the second electroactive substances at the same instant of a system functioning.
    [0003] [0003] Within the scope of the present invention, a transparent element is understood as an optical element that allows a user, who is located on one side of the element, to see distinctly, through that element, objects that are located on the other side of and distance from the element. In other words, an image of the object is formed on the user's retina, by the light that propagates in a first non-zero distance between the object and the transparent element, then passes through the transparent element and propagates over a second non-zero distance between the transparent element and a user’s eye. For this, a diffusion and / or a light diffraction (s) that would cause the optical element must be small enough, so that the image of an object point through the transparent element is an image point and not a diffuse spot in the image that is perceived by the user.
    [0004] [0004] This electrochromic system is designed to vary the value of light transmission through this system, between a light state for which light transmission has a value that is high and a dark state for which it has a value that is low. For this, when an appropriate electrical voltage is produced between the two supply electrodes by a source, the first and second electroactive substances are oxidized to one and reduced simultaneously to the other, respectively on the supply electrode which is connected to a terminal block. positive of the voltage source, and on the electrode that is connected to a negative terminal of the same voltage source. The oxidized and reduced substances thus formed can then diffuse within the closed volume, and neutralize each other when they meet. Now, this neutralization causes a more important consumption of electric current. Simultaneously, because of this neutralization, the light transmission of the electrochromic system in the dark state can be limited to a saturation value higher than the value that would result from the concentrations of electroactive substances. In other words, the reciprocal neutralization of electroactive substances can reduce the difference between the values of the light transmission of the system between the two light and dark states, also called dynamics of the electrochromic system.
    [0005] [0005] In addition, since certain electrochemical substances reacted in contact with one of the supply electrodes, they can remain in the vicinity of that electrode and then limit the access of other electroactive substances that have not yet reacted to that same supply electrode. . This results in a reduction in the speed of the switching of the electrochromic system between its light and dark states. This decrease in speed is harmful to the function and use of the system in a large number of applications.
    [0006] [0006] Under these conditions, one of the purposes of the invention is to propose structures of electrochromic systems, whose consumption in electric current is reduced.
    [0007] [0007] Another purpose of the invention is to propose structures of electrochromic systems that allow to increase the switching dynamics.
    [0008] [0008] Yet another purpose of the invention is to propose structures of electrochromic systems that have higher switching speeds.
    [0009] [0009] Another purpose of the invention is to propose structures of electrochromic systems that are simple to manufacture.
    [0010] [00010] The present invention then proposes two electrochromic systems that each constitute a solution to these technical problems. Each electrochromic system of the invention is of the type that has been described previously. In particular, it is transparent to allow a different view through the system.
    [0011] [00011] Furthermore, in the systems of the invention, the two supply electrodes are carried together by the same of the two external walls of each of these systems.
    [0012] [00012] A first electrochromic system that is proposed by the present invention comprises, in addition, a pair of first transparent polarization electrodes, which are carried together by the other of the two external walls than the one that carries the supply electrodes, without contact with these feeding electrodes inside the system. In addition, these first polarization electrodes are located one by one in front of the supply electrodes, on both sides of the closed volume in a direction perpendicular to the external walls.
    [0013] [00013] In this first system, each first polarization electrode and the supply electrode that is located face to face are intended to be connected, in addition, respectively to two output terminals of a second variable electrical source, with respective polarities that are identical at least in certain moments of the system's operation, for the output terminals of the first and second electrical sources that are connected to the same of the supply electrodes, these polarities being considered respectively in relation to the other output terminal of the corresponding electrical source .
    [0014] [00014] A second electrochromic system that is proposed by the present invention likewise comprises the pair of the first polarization electrodes, with an arrangement of those first polarization electrodes that is identical to that of the first system of the above invention. But the second electrochromic system comprises, in addition, a pair of second transparent polarization electrodes, which are located between the supply electrodes, on the one hand, and the outer wall that carries these supply electrodes, on the other hand. In addition, the second polarization electrodes are located one by one vertically in the supply electrodes, in the direction perpendicular to the external walls, without contact with these supply electrodes inside the system.
    [0015] [00015] In this second system, each of the first polarization electrodes and that of the second polarization electrodes that is located in the vertical of that first polarization electrode, according to the direction perpendicular to the external walls, are intended to be connected to two terminals respectively. output from a second variable electrical source. In addition, the output terminals of the first and second electrical sources that are connected respectively to one of the supply electrodes and one of the second polarization electrodes that are located vertically in each other, have respective polarities that are identical at least in certain when the system is in operation, these polarities are considered respectively in relation to the other output terminal of the corresponding electrical source.
    [0016] [00016] In general, all polarization electrodes that are introduced by the invention are electrically isolated from each other within the electrochromic system and insulated in relation to each supply electrode.
    [0017] [00017] However, the first electrochromic system that is proposed by the invention can be deduced from the second, joining each supply electrode with that of the second polarization electrodes that is aligned with it, in the direction perpendicular to the external walls. For this reason, the two systems solve in the same way the same technical problems that were indicated above.
    [0018] [00018] In the two electrochromic systems of the invention, an additional electrical source is provided to connect each first polarization electrode. Each system is therefore electrically connected, in general, to one or two electrical source (s) which is (are) dedicated to its polarization, in addition to the first one dedicated to supplying the system with electric current. In contrast to this first source, each electrical source that is dedicated to polarization applies an electrical voltage between two of the electrodes in the electrochromic system, but without releasing electrical current to these electrodes.
    [0019] [00019] In both cases, each second electrical source produces an electric field in the closed volume of the system that contains the electroactive substances. This electric field throws substances that have been oxidized or reduced on one of the supply electrodes, to the opposite side of the closed volume, more than the same substances, before they have reacted on the same supply electrode. In this way, access to the supply electrodes by electroactive substances that are to be oxidized or reduced is improved, which increases the switching speed of the system.
    [0020] [00020] In addition, the first electroactive substances that have been oxidized and the second electroactive substances that have been reduced, or vice versa depending on the direction of the current switching of the electrochromic system, can be thrown towards the first polarization electrodes that are many different. They can thus be kept at a distance from each other, which limits their reciprocal neutralization. The electrical consumption of the system and the saturation of its colored state that would result from this neutralization are thus avoided, or in part suppressed. In particular, the switching dynamics of electrochromic systems are thus increased.
    [0021] [00021] This separation of the oxidized and reduced forms of the electroactive substances that are formed, when switching the electrochromic system can be all the more effective as these forms have respective electrical charges that are different and notably that the oxidized form of each electroactive substance has an electrical charge that is higher than that of the reduced form of the other electroactive substance. In other words, the first electro-active substances in their oxidized form, preferably, each have an electrical charge that is greater than or equal to the electrical charge of each second electroactive substance in its reduced form. Symmetrically, each second electroactive substance in its oxidized form preferably has an electrical charge that is greater than or equal to that of each first reduced electroactive substance. For these comparisons the electrical charges of the substances are considered in algebraic values to be compared between them. In this case, the two switching, from the light state to the dark state and inversely, are favored by the invention. If the electrical charge of the oxidized form of one of the two electroactive substances is greater than that of the reduced form of the other electroactive substance, for only one of the two states of the electrochromic system, this state is improved by the invention.
    [0022] [00022] However, the attraction of certain forms of electroactive substances to one of the polarization electrodes, in relation to other electroactive substances in the opposite form, may result from the respective mobilities of these substances, when they have equal electrical charges.
    [0023] [00023] However, the effect of the invention is all the more important that the electric charge of the oxidized form of one of the electroactive substances is strictly higher than the electric charge of the reduced form of the other substance that is formed, when switching over.
    [0024] [00024] On the other hand, considering that all electrodes, supply and polarization, are carried by the external walls of the system, it is simple to manufacture. In effect, each electrode can be made in the form of a thin layer that is deposited on the corresponding external wall, without the need for additional support elements inside the electrochromic system. In addition, the electrodes of the same pair can have identical motifs each on the corresponding external wall, so that the same mask can be used for each pair of electrodes, to define these motifs.
    [0025] [00025] In different ways of making electrochromic systems, according to the invention, the closed volume containing the liquid or gel in which the electroactive substances are distributed, can be divided into cells juxtaposed parallel to the external walls. In this case, each cell contains a part of the liquid or gel that is subjected to the electrical effects, inside that cell, of a single or two electrodes of each pair.
    [0026] [00026] An electrochromic system, according to the invention, can form at least a part of numerous optical components, such as a spectacle glass, a mask glass, an optical lens, a helmet visor, an airplane window, a pane, etc.
    [0027] - o primeiro ou o segundo sistema eletrodos transparente, tal como descrito anteriormente; - a primeira fonte elétrica variável, com os dois bornes de saída dessa primeira fonte elétrica que são ligados respectivamente aos eletrodos de alimentação, e que é adaptado para alimentar o sistema com corrente elétrica, aplicando-se entre seus dois eletrodos de alimentação uma tensão elétrica superior à diferença entre os potenciais respectivos de óxido- redução das primeiras e segundas eletroa-tivas; e - pelo menos uma segunda fonte elétrica variável, com um primeiro borne de saída dessa segunda fonte elétrica que é ligada a pelo menos um dos primeiros eletrodos de polarização. [00027] Finally, the invention also proposes electrochromic devices that comprise: - the first or the second transparent electrode system, as described above; - the first variable electrical source, with the two output terminals of that first electrical source that are connected respectively to the supply electrodes, and which is adapted to supply the system with electrical current, applying an electrical voltage between its two supply electrodes greater than the difference between the respective oxide-reduction potentials of the first and second electro-active ones; and - at least a second variable electrical source, with a first output terminal of that second electrical source that is connected to at least one of the first polarization electrodes.
    [0028] [00028] When the first electrochromic system proposed by the invention is used, a second output terminal of the second electrical source can be connected to the supply electrode which is located in front of the first polarization electrode to which the first output terminal of the same is connected. second electrical source. In this case, the first output terminal of the second electrical source can, in addition, be connected to another supply electrode than the one to which the second output terminal of that second electrical source is connected. At the same time, the second output terminal of the second electrical source can, in addition, be connected to the other first polarization electrodes than the one to which the first output terminal of the second electrical source is connected. The output terminals of the first and second electrical sources that are connected to the same of the supply electrodes then have respective polarities that are identical at certain times of the system functioning, these polarities being considered respectively in relation to the other terminal output from the corresponding electrical source. An electrochromic device that works with two electrical sources is only obtained in this way.
    [0029] [00029] A device with three electrical sources can also be formed with the first electrochromic system of the invention. For this, a second output terminal of the second electrical source is connected to the supply electrode which is located in front of the first polarization electrode to which the first output terminal of that second electrical source is connected. The device then also comprises a third variable electrical source, which has a first output terminal connected to another supply electrode than the one to which the second output terminal of the second electrical source is connected, and a second output terminal. connected to the other first polarization electrode than the one to which the first output terminal of the second electrical source is connected. In this case, the output terminals of the first and the second or third electrical sources that are connected to the same supply electrodes have respective polarities that are identical at certain moments at least when the system is functioning, these polarities being considered respectively in relation to to the other output terminal of the corresponding electrical source.
    [0030] [00030] Similarly, devices with two or three electrical sources can be formed, using the second electro-chromic system proposed by the invention. For the connections of the second and / or the third electrical source (s), each supply electrode is replaced, in relation to the connections that were described above, for the first system of the invention, by the second polarization electrode which is aligned with it, in the direction perpendicular to the outer walls.
    [0031] - as figuras 1a e 1b representam vistas em corte de dois sistemas eletrocrômicos, de acordo com a invenção; - as figuras 2a e 2b representam dispositivos eletrocrômi-cos, compreendendo primeiros sistemas, de acordo com as figuras 2a e 2b, respectivamente com duas ou três fontes elétricas; - as figuras 3a e 3b correspondem respectivamente às figuras 1a e 1b para dois segundos sistemas eletrocrômicos, de acordo com a invenção; e - as figuras 4a e 4b correspondem, respectivamente, às figuras 2a e 2b, para os segundos sistemas das figuras 3a e 3b. [00031] Other particularities and advantages of the present invention will appear in the following description of non-limiting realization examples, with reference to the attached drawings, in which: figures 1a and 1b represent sectional views of two electrochromic systems, according to the invention; figures 2a and 2b represent electrochromic devices, comprising first systems, according to figures 2a and 2b, respectively with two or three electrical sources; figures 3a and 3b correspond to figures 1a and 1b respectively for two second electrochromic systems, according to the invention; and figures 4a and 4b correspond to figures 2a and 2b, respectively, for the second systems of figures 3a and 3b.
    [0032] [00032] For the sake of clarity, the dimensions of the elements that are represented in these figures correspond neither to real dimensions nor to relations of real dimensions. In addition, identical references that are indicated in different figures designate identical elements or that have identical functions.
    [0033] [00033] However, the internal walls 12 were not represented in figures 2a, 2b, 4a and 4b, of course they are optional for the entire invention, and may be in accordance with figures 1a and 3a, or figures 1b and 3b, notably .
    [0034] [00034] In addition, by way of illustration, the systems that are described below are intended to form glasses glasses, but of course they can form other transparent elements, notably adapting properly to the external walls of these systems.
    [0035] [00035] According to figures 1a, 1b, and 3a, 3b, an ele-trochromic system 100 comprises two external walls 10 and 11 which are parallel, and which delimit an internal volume V. Volume V is closed, so watertight, for example, using a peripheral joint not shown. The outer walls 10 and 11 can be a flexible film, such as a polyethylene terephthalate (PET) film, a polycarbonate film (PC) or a polyimide film. This film can have an e11 thickness of 50mm (micrometer), in particular. The outer wall 10 can also be a glass of glasses, in mineral, organic, or hybrid material commonly used in the ophthalmic domain.
    [0036] [00036] All the supply and polarization electrodes that are listed in the sequence are electrically isolated from each other within the system 100. They can be in tin-doped indium oxide (ITO for "indium-tin oxide" in English) or in fluorine-doped tin oxide (SnO2: F). These electrodes can be deposited on the inner face of the corresponding wall 10, 11 in the form of thin layers with motifs, with a layer thickness that can be comprised between 0.1 μm and 3 μm, for example.
    [0037] [00037] The external wall 10 holds two supply electrodes that are referenced with 1 and 2. These electrodes 1 and 2 are in contact with a liquid or gel that is contained in volume V. They can have any respective complementary reasons, remaining separate from each other by a gap I parallel to the outer wall 10. This gap I can ensure that electrodes 1 and 2 are electrically isolated between them. In particular, electrodes 1 and 2 may have comb motifs, with comb teeth that are interwoven in an alternating step that can be between 50 μm and 1.5 mm (millimeter), for example. The I interval can be 18 μm wide, for example.
    [0038] [00038] The outer wall 11 holds the first two polarization electrodes that are referenced with 3 and 4. These electrodes 3 and 4 are located one by one in front of electrodes 1 and 2, on both sides of volume V, in a direction D which is perpendicular to the outer walls 10 and 11. Thus, electrode 3 is aligned with electrode 1, in the direction D, and electrode 4 is aligned with electrode 2.
    [0039] [00039] In all electrochromic systems 100 according to the invention, each polarization electrode 3, 4 can be in contact with the liquid or gel that is contained in volume V. Alternatively, at least one electrically insulating film can be disposed on polarization electrodes 3 and 4, between these and volume V, to suppress the contact between each of these polarization electrodes 3,4 and the liquid or gel. In all figures, this insulating film is referenced with 5 and is represented only on part of the corresponding systems 100, to show that this insulating film is not systematically present. When used, film 5 can be made of silica (SiO2) with a thickness e5 that is less than 0.1 μm, for example.
    [0040] [00040] The thickness d of volume V, according to direction D, can be 20 μm, for example.
    [0041] [00041] The external walls 10 and 11, as well as electrodes 1 to 4, are transparent to light rays that pass through the system 100 between two opposite sides of it, notably parallel to the D direction.
    [0042] [00042] The fluid medium that is contained in volume V is a liquid or a gel, depending on its composition. It contains electrostatic substances that are intended to be oxidized or reduced on supply electrodes 1 and 2, when system 100 is in operation. It may also contain other additives, such as a solvent common to electroactive substances, anti-oxidants UV, fluidizers, etc.
    [0043] - a N,N,N',N' tetrametil- fenileno diamina, que possui um valor de aproximadamente 0,2 V (volt) de potencial de óxido- redução em relação a um eletrodo de referência ao calomel saturado. Ela é incolor e neutra eletricamente em sua forma reduzida e azul com uma carga elétrica positiva em sua forma oxidada; e - a etil-antraquinona, que possui um valor de aproximadamente -1,5 V do potencial de óxido-redução em relação ao eletrodo ao calomel saturado. Ela é incolor em sua forma oxidada e vermelha em sua forma oxidada, e carregada negativamente em sua forma reduzida. [00043] The electroactive substances that are contained in volume V can be, by way of illustrative example: - at N, N, N ', N' tetramethyl-phenylene diamine, which has a value of approximately 0.2 V (volt) of oxide-reduction potential in relation to a saturated calomel reference electrode. It is colorless and electrically neutral in its reduced form and blue with a positive electrical charge in its oxidized form; and - ethyl anthraquinone, which has a value of approximately -1.5 V of the oxide-reduction potential in relation to the electrode to the saturated calomel. It is colorless in its oxidized form and red in its oxidized form, and negatively charged in its reduced form.
    [0044] [00044] When the voltage is zero between the two supply electrodes 1 and 2 of the same pair, the first of these substances is in its reduced form, and the second in its oxidized form, because of their respective values of the potential of oxide -reduction. The electrochromic system is then in its clear state, with a high light transmission value, for example, above 70% and, preferably, above 80%. When the voltage that is applied between the two supply electrodes 1 and 2 is more than approximately 1.7 V, N, N, N ', N'tetramethyl phenylene diamine is oxidized in contact with that of those electrodes 1 and 2 which is connected to the positive output terminal of the corresponding electrical supply of the electrochromic system, and the ethyl anthraquinone is reduced in contact with another supply electrode that is connected to the positive output terminal of the same electrical source. The electrochromic system 100 then becomes absorbent with a blue color. Its light transmission can then be less than 20%, for example, even less than 10%, depending on the concentrations of the electroactive species, notably.
    [0045] [00045] These two electroactive substances can be introduced into volume V, each with a concentration between 0.001 and 1.mol.l-1. (mol per liter), depending on the level of luminous absorption that is sought for the absorbing state of the electro-chromic system 100. For example, the concentrations of the two electroactive species mentioned above can be equal to 0.2 mol.l-1 .
    [0046] [00046] In particular embodiments of the invention, and optionally, the system 100 may further comprise a network of internal walls 12, which forms a division of volume V into cells 13 juxtaposed parallel to the external walls 10 and 11 The inner walls 12 are perpendicular to the outer walls 10 and 11, and they divide the liquid or gel that are respectively contained in cells 13. The composition and embodiment of the walls 12 are assumed to be known to the skilled person and are not repeated here. For example, the walls 12 can each have a thickness that is greater than 0.1 μm, preferably between 0.5 and 8 μm, and each cell 13 can have a dimension that is between 50 μm and 1.5 mm, for example, parallel to the outer walls 10 and 11. The cells 13 then form a floor of the electrochromic system 100, parallel to the walls 10 and 11, whose motive can be any, regular, for example, hexagonal or pseudo-random.
    [0047] [00047] According to a first way of dividing volume V which is illustrated by figure 1a, the two feeding electrodes 1 and 2 are each in contact with the liquid or gel which, contained in each cell 13, and the liquid or gel that is contained in each cell contains both the first and the second electroactive substances. Thus, the two electrodes 1 and 2 are in contact with the liquid or gel parts of all cells 13. According to an advantageous embodiment, certain internal walls 12 can extend between electrodes 1 and 3, and others inner walls 12 between electrodes 2 and 4, with extensions of the electrodes on both sides of each corresponding inner wall 12, parallel to the outer walls 10 and 11. Thus, each of the electrodes 1 to 4 extends continuously between adjacent cells 13, and each cell 13 can be powered by the two electrodes 1 and 2, by their respective extensions within that cell.
    [0048] [00048] According to a second mode of dividing the volume V which is illustrated by figure 1b, for at least certain cells 13, a single of the two electrodes 1 and 2, is in contact with the liquid or gel that is contained in each cell. In that case, a first cell 13 that is fed by one of the electrodes 1 and 2 is adjacent to a second cell 13 that is fed by the other electrode 1 or 2. According to a possible embodiment, certain of the inner walls 12 can be extend between the outer walls 10 and 11 in the vertical of the inter-electrode I separation intervals in the D direction. Within the system 100, ionic bridges 14 electrically connect cells 13 that are neighboring and fed separately by electrode 1 and electrode 2. These ionic bridges can be made in one of the ways commonly used in electrochemistry. For example, ionic bridges 14 can be located at the ends of the inner walls 12, for example, on the side of the outer wall 11. They can also be made on the inner walls 12, notably when these are permeable to small ions that are contained in liquid or gel with electroactive substances. These ionic bridges 14 ensure an electrical neutrality of the content of each cell 13 at each instant of the operation of the system 100. They thus allow to keep the system 100 in any state in a stationary manner.
    [0049] [00049] When a single of the two feeding electrodes 1 or 2 feeds each cell 13 of the system 100, the liquid or gel may contain first electroactive substances without second electro-active substances inside the cells 13 that are fed by one of these two electrodes , and second electroactive substances without first electroactive substances inside the cells 13 which are fed by the other feeding electrode. For example, for the volume V division mode of figure 1b, those of cells 13 that are fed by electrode 1 may contain only molecules of tetramethyl-phenylene diamine, and those of cells 13 that are fed by electrode 2 may contain only molecules of ethyl anthraquinone. In this case, the first switching of the system 100, after its manufacture is done, connecting electrode 1 to the positive output terminal of an electrical source and electrode 2 to the negative output terminal of that source.
    [0050] [00050] For the use of all systems 100 that are described, a first variable electric source 20 is connected electrically, through two current output terminals of that first source, to the supply electrodes 1 and 2. The source 20 is adapted for produce, between its output terminals, an electrical voltage that is greater than or equal to the difference between the respective oxide-reduction potentials of the first and second electroactive substances. It then produces an electrical current that passes through the system 100 between electrodes 1 and 2. When the system 100 is switched from the light state to the dark state, molecules of tetramethylphenylene diamine are oxidized in contact with that of the electrodes of supply 1 and 2 which is connected to the positive output terminal of the source 20, and molecules of ethyl anthraquinone are reduced in contact with the other electrode 1 or 2 which is connected to the negative output terminal of the source 20. From the connection of the source 2- which is represented in figures 2a, 2b, 4a and 4b, the tetramethyl - phenylene diamine molecules are thus oxidized on electrode 1 and the ethyl anthraquinone molecules are reduced to electrode 2. To return to the clear state, the polarity of source 20 is reversed with respect to feed electrodes 1 and 2. The tetramethyl-phenylene diamine molecules that had been oxidized are then reduced to electrode 1, and the previously reduced ethyl anthraquinone molecules are re-oxidized on electrode 2.
    [0051] [00051] The source 20 can be of the type of direct current source or impulse source.
    [0052] [00052] According to figure 2a, a second variable electrical source 21 can be connected electrically between the supply electrode 1 and the polarization electrode 3. Simultaneously, a third variable electrical source 22 can be connected electrically between the supply electrode. 2 and the polarization electrode 4. Each source 21 or 22 is adapted to produce an electrical voltage between the two electrodes of the system 100 to which it is connected, without releasing electrical current. For this reason, sources 21 and 22 are called polarization sources. They therefore produce an electric field in volume V, between one of the supply electrodes 1 or 2 and the polarization electrode 3 or 4 that is located in front of that supply electrode.
    [0053] [00053] When switching the system 100, the respective polarities of the polarization sources 21 and 22 are subject to the polarity of the power supply 20. Thus, when switching from the light state to the dark state, the supply electrodes 1 is connected to the positive output terminal of the source 21, in addition to the positive output terminal of the source 20. The polarization electrode 3 is then connected to the negative output terminal of the source 21. At the same time, the supply electrode 2 is connected to the negative output terminal of source 22, in addition to the negative output terminal of source 20, and the polarization electrode 4 is connected to the positive output terminal of source 22. Under the effect of the electric field that is produced by source 21 between the electrodes 1 and 3, the oxidized tetramethyl - phenylene diamine molecules, which are positively charged, migrate from electrode 1 to electrode 3. This migration ensures better access from feed electrode 1 to the tetramethyl - phenylene diamine molecules q u have not reacted yet.
    [0054] [00054] Likewise, the ethyl anthraquinone molecules that are reduced on the feeding electrode 2, when coloring the system 100, with a negatively charged reduced shape, then migrate to the polarization electrode 4. Thus, the oxidized and reduced forms of all electroactive substances, which are produced simultaneously on the supply electrodes 1 and 2, when the system is switched, remain apart from each other. Those that are oxidized remain in the vicinity of that of polarization electrodes 3 or 4 that is connected to the negative output terminal of one of the sources 21 or 22, and the electroactive substances that are reduced remain in the vicinity of the other polarization electrodes 3 or 4, connected to the positive output terminal of the other source 21 or 22. Being thus spatially separated in zones other than volume V, their mutual neutralization is prevented. In all figures, the arrows that are marked with E inside volume V represent the orientations of the electric fields that have just been described.
    [0055] - uma atração para os eletrodos de alimentação com corrente elétrica do sistema eletrocrômico, para aquelas das substâncias eletroativas que são carregadas eletricamente e destinadas a reagir sobre esses eletrodos, quando de uma comutação do sistema; - um afastamento em relação aos eletrodos de alimentação, para aquelas das substâncias eletroativas que reagiram sobre os eletrodos de alimentação, a fim de melhorar o acesso a esses eletrodos às substâncias eletroativas que não reagiram ainda; e - uma separação em zonas diferentes do volume interno dos sistemas eletrocrômicos, das substâncias eletroativas que reagiram sobre os eletrodos de alimentação. [00055] Thus, depending on the electrical charge of the oxidized and reduced forms of electroactive substances, the use of polarization electrodes, according to the invention, offers the following beneficial effects: - an attraction for the electrodes of electric current supply of the electrochromic system, for those of the electroactive substances that are electrically charged and destined to react on these electrodes, when a system switching; - a departure from the supply electrodes, for those of the electroactive substances that reacted on the supply electrodes, in order to improve access to those electrodes to the electroactive substances that have not yet reacted; and - a separation in different zones of the internal volume of the electrochromic systems, of the electroactive substances that reacted on the supply electrodes.
    [0056] [00056] Higher switching speed of the electrochromic systems results from the first two effects. In addition, the latter effect prevents the electroactive substances from mutually neutralizing each other after having been oxidized or reduced on the supply electrodes. Thus, the consumption of supplementary electric current that would cause this reciprocal neutralization is avoided. The saturation of the light transmission of the system in the dark state, with a value higher than that corresponding to the concentrations of the electroactive substances, and which would also be due to the reciprocal neutralization of the electroactive substances, is also avoided.
    [0057] [00057] The improvement that is then described allows to totally avoid any reciprocal neutralization of the electroactive species. It applies when volume V is divided into cells 13 which are each fed by a single of the two electrodes 1 or 2. In this configuration of system 100, at least certain of the inner walls 12 can extend towards the outer wall 11 which carries polarization electrodes 3 and 4, in the D direction, until closing cells 13 on the side of the outer wall 11. This closing of cells 13 is adapted so that electroactive substances that are in the vicinity of polarization electrodes 3 and 4 cannot move from cell 13 to a neighboring cell. However, it is possible simultaneously for ions of smaller sizes to pass through these walls 12 in the vicinity of electrodes 3 and 4, notably when an ionic bridge 14 is predicted in that location of volume V.
    [0058] [00058] Although the advantages of the invention have been described for switching the electrochromic system in the direction of its coloring, the technician will know, based on this description, to transpose them in the case of the reverse switching of the system, from its dark state to its state clear. The same advantages are provided by the invention to switching in both directions.
    [0059] [00059] From the function of the polarization electrodes introduced by the invention, the electroactive substances are not oxidized, nor reduced on that electrodes. The use of insulating film 5 ensures that no oxide-reduction reaction can occur on polarization electrodes 3 and 4. Another method for this is to limit electrical voltages that are produced by the polarization sources 21 and 22, so that they are lower than the difference between the respective oxide-reduction potentials of the first and second electroactive substances, in absolute values.
    [0060] [00060] According to a further improvement of the devices, according to figure 2a, the electrochromic systems used may comprise, in addition, an additional transparent polarization electrode 9, which is located between the supply electrodes 1 and 2, for a side, and the outer wall 10, on the other. This supplementary polarization electrode 9 has no contact either with supply electrodes 1 and 2, nor with the liquid or gel that is contained in volume V, nor with polarization electrodes 3 and 4. For example, an intermediate layer 8 An insulating material can be inserted between electrode 9 and electrodes 1 and 2. Supplementary electrode 9 is intended to be connected to an electrical potential reference terminal. In particular, at least one of the sources 21 and 22 may have a potential reference terminal. This and preferably the respective potential reference terminals of the two sources 21 and 22, can then be electrically connected to the additional polarization electrode 9 via an additional connection 23. If necessary, the power supply may also have a potential reference electrode that is connected by connection 23. Electrode 9 ensures better control of the distribution of electrical potential within the volume V assembly, notably in the vertical of the inter-electrode I separation intervals.
    [0061] [00061] The device of figure 2b corresponds to that of figure 2a, with a single electrical source of polarization that fills the functions of the two sources 21 and 22 of figure 2a. Thus, in an instant of operation of the device in which the supply electrode 1 is connected to the positive output terminal of the source 20 and the supply electrode 2 to the negative output terminal of the source 20, the only source of polarization, which is still referenced 21, is connected by its positive output terminal to electrodes 1 and 4, and by its negative output terminal to electrodes 2 and 3. The operation of the device is then identical to that described in relation to figure 2a.
    [0062] [00062] The electrochromic systems 100 of figures 3a and 3b comprise all elements of the systems of figures 1a and 1b. In particular, they comprise electrodes 3 and 4 which form a pair of first polarization electrodes. But they also comprise a pair of second polarization electrodes, which are referenced 6 and 7. Electrodes 6 and 7 are carried by the outer wall 10, like the supply electrodes 1 and 2, between these and the wall 10. The electrodes 6 and 7 can be electrically isolated from electrodes 1 and 2 by an intermediate layer 8 of an insulating material. The second polarization electrodes 6 and 7 are, moreover, located one by one in the vertical of the supply electrodes 1 and 2, possibly with the same motifs on the outer wall 10. Thus, the polarization electrode 6 is located under the electrode supply line 1, in the oriented direction D, and the polarization electrode 7 is located under the supply electrode 2, in the same direction D. Figure 3a illustrates this system 100 with a division of volume V in juxtaposed cells such that each cell 13 is fed simultaneously by the two electrodes 1 and 2. In the division of figure 3b, each cell 13 is fed by a single of the two electrodes 1 and 2, with an alternation between these two supply electrodes between neighboring cells 13.
    [0063] [00063] The device of figure 4a is formed, associating one of the electrochromic systems 100 of figures 3a and 3b to three variable electrical sources. These sources are identical to those 20-22 that were introduced previously with reference to figure 2a, with the exception of the connections of the polarization sources 21 and 22. the output terminals of the polarization source 21 are then connected to the polarization electrodes 3 and 6. The one of the output terminals of the source 21 that is positive is connected to the electrode 6 in an instant of operation of the device in which the supply electrode 1 is itself connected to the positive output terminal of the source 20. The negative output terminal of the source 21 is then connected to electrode 3. Simultaneously, the negative output terminal of the polarization source 22 is connected to the polarization electrode 7, and the positive output terminal of the source 22 is connected to electrode 4. The polarities of the two polarization sources 21 and 22 are still inverted, following the polarity changes of the power supply 20. A decoupling is thus obtained, between the supply electrodes 1 and 2, on the one hand, and the polarization electrodes 6 and 7, on the other hand The. However, the operation of the device is identical to that described in relation to figure 2a. The use of internal walls 12 that are watertight to electroactive substances, when each cell 13 is powered only by a single electrode 1 and 2, the use of insulating film 5, as well as the connection of respective potential reference terminals of the sources 20 , 21 and 22 are still identical to those previously described.
    [0064] [00064] Finally, figure 4b illustrates the use of a system 100, according to figures 3a and 3b with two electrical sources: source 20 to supply the system with electrical current and a single source of polarization 21. This use can be deduced from that of figure 4a, in the same way as for figures 2a and 2b.
    [0065] [00065] Naturally, the invention can be reproduced, adapting characteristics that were mentioned by way of example, preserving at least certain of the mentioned advantages. In particular, the values of concentrations and / or dimensions of the elements of the electrochromic system can be modified for each application that is considered. Supplementary ionic substances can also be added to the composition of the liquid or gel, notably to increase its ionic conduction.
    权利要求:
    Claims (13)
    [0001]
    Electrochromic device, comprising: - a transparent electrochromic system (100), allowing a different view through this system, and comprising: - two walls (10, 11) that define a closed volume (V), the system being transparent to a viewing direction, crossing the walls and the closed volume between two opposite sides; - a liquid or gel that is contained in the closed volume (V); - first and second electroactive substances that are distributed in the liquid or gel, with respective oxide-reduction potentials that are different, those determined by at least the first and second electroactive substances having an optical effect varying between an oxidized form and a reduced form of these substances; and - a pair of transparent feeding electrodes (1, 2), carried together by the same (10) of the two walls; and - a first variable electrical source (20), with two output terminals, the two output terminals of that first electrical source (20) connected respectively to the supply electrodes (1, 2) and adapted to supply the system (100) with current electrical voltage between these supply electrodes greater than the difference between the respective oxide-reduction potentials of the first and second electroactive substances, in order to transfer electrons to or from at least certain of the electroactive substances, in an inverse way between the first and second elective substances at the same moment of a system functioning; characterized by the fact that the device comprises at least a second variable electrical source (21, 22) and the system further comprises: - a pair of first transparent polarization electrodes (3, 4), these first polarization electrodes (3, 4) are held together by the other (11) of the two walls than the one (10) that carries the supply electrodes ( 1, 2) and not having contact with these supply electrodes (1, 2) inside the system, and these first polarization electrodes (3, 4) being located one by one in front of the supply electrodes (1, 2) of both sides of the closed volume in a direction (D) perpendicular to the walls (10, 11), and - at least one electrically insulating film (5) arranged to prevent contact between each first polarization electrode (3, 4) and the liquid or gel contained in the closed volume (V), so that the electroactive substances are neither oxidized nor reduced in the first polarization electrodes, each of the first polarization electrodes (3, 4) and that of the supply electrodes (1, 2) which is located in front of that first polarization electrode and are intended to be connected, in addition, respectively to two output terminals of a second variable electrical source (21, 22) with respective polarities that are identical at certain times at least when the system is operating, to the output terminals of this first (20) and second (21) electrical sources that are connected to the same electrodes power supply (1, 2), these polarities being defined respectively in relation to the other output terminal of the corresponding electrical source.
    [0002]
    Electrochromic device according to claim 1, characterized by the fact that at least one second electrical source (21, 22) comprises only a single second variable electrical source (21), and in which: a first output terminal of the second electrical source (21) is connected to one of the first polarization electrodes (3); a second output terminal of the second electrical source (21) is connected to the supply electrode (1) which is located in front of the first polarization electrode (3) to which this first output terminal of that second electrical source is connected; the first output terminal of the second electrical source (21) being, in addition, connected to another supply electrode (2) than the one to which this second output terminal of that second electrical source is connected; and the second output terminal of the second electrical source (21) being, in addition, connected to the other first polarization electrode (4) than the one to which this first output terminal of that second electrical source is connected.
    [0003]
    Electrochromic device according to claim 1, characterized by the fact that said at least one second variable electrical source comprises a second variable electrical source (21) and a third variable electrical source (22), a second output terminal of the second electrical source (21) is connected to the supply electrode (1) which is located in front of the first polarization electrode (3) to which this first output terminal of this second electrical source, the third variable electrical source (22), is connected having a first output terminal connected to the other supply electrode (2) than the one to which it is connected to that second output terminal of this second electrical source (21) and a second output terminal connected to the other first polarization electrode (4) which the one to which this first output terminal of this second electrical source (21) is connected, with respective polarities that are identical to the output terminals of said first (20) and second (21) or third (22) electrical sources that are connected to one of the supply electrodes (1, 2), these polarities being defined respectively in relation to the other output terminal of the corresponding electrical source.
    [0004]
    Device according to any one of claims 1 to 3, characterized by the fact that the electrochromic system (100) further comprises an additional transparent polarization electrode (9) located between the supply electrodes (1,2), on the one hand, and the external wall (10) that holds these supply electrodes, on the other hand, this supplementary polarization electrode having neither contact with these supply electrodes nor with the liquid or gel contained in the closed volume (V) , nor with these first polarization electrodes (3, 4), and in which at least one of the electrical sources (20, 21, 22) has a good electrical potential reference distinct from the output terminals of that electrical source, that electrical potential reference terminal being connected to the supplementary polarization electrode (9).
    [0005]
    Electrochromic device comprising: - a transparent electrochromic system (100), allowing a different view through this system, and comprising: - two walls (10, 11) that define a closed volume (V), the system being transparent to a viewing direction, crossing the walls and the closed volume between two opposite sides; - a liquid or gel that is contained in the closed volume (V); - first and second electroactive substances that are distributed in the liquid or gel, with respective oxide-reduction potentials that are different, determined at least from the first and second electroactive substances having an optical effect varying between an oxidized form and a reduced form of these substances; and - a pair of transparent feeding electrodes (1, 2), carried together by the same (10) of the two walls; and - a first variable electrical source (20), with two output terminals, the two output terminals of that first electrical source (20) connected respectively to the supply electrodes (1, 2) and adapted to supply the system (100) with current electrical voltage applying between these supply electrodes an electrical voltage higher than the difference between the respective oxide-reduction potentials of the first and second electroactive substances, in order to transfer electrons to or from at least certain of the electroactive substances, in an inverse way between the first and the second elective substances at the same moment of a functioning system; characterized by the fact that the device comprises at least a second variable electrical source (21, 22) and said system further comprises: - a pair of first transparent polarization electrodes (3, 4), these first polarization electrodes are carried together by the other (11) of the two walls than the one (10) that carries the supply electrodes (1, 2) and not having contact with these supply electrodes (1,2) inside the system, and these first polarization electrodes (3, 4) being located one by one in front of the supply electrodes (1, 2) on both sides of the closed volume according to a direction (D) perpendicular to the walls (10, 11); - at least one electrically insulating film (5) arranged to prevent contact between each first polarization electrode (3, 4) and the liquid or gel contained in the closed volume (V), the electroactive substances being neither oxidized nor reduced in the first polarization electrodes; and - a pair of second transparent polarization electrodes (6, 7) located between the supply electrodes (1, 2), on the one hand, and the external wall (10) that carries these supply electrodes, on the other, and these second electrodes polarization (6, 7) being located one by one in the vertical of these supply electrodes (1, 2) in a direction (D) perpendicular to the walls (10, 11), without contact with these supply electrodes inside the system; each of the first polarization electrodes (3, 4) and that of the second polarization electrodes (6, 7) which is located in front of that first polarization electrode (1, 2) which is located directly opposite to said polarization electrode (3 , 4) in the direction (D) perpendicular to the walls (10, 11), being connected, respectively, to two output terminals of at least one second variable electrical source (21, 22) with respective polarities that are identical for each terminal of the output of the first electrical source (20) which is connected to one of the supply electrodes (1, 2) and to the output terminals of at least a second electrical source (21, 22) which is connected to that of the second electrodes polarization (6, 7) which is located in front of said supply electrode, said polarities being defined respectively in relation to the other output terminal of the corresponding electrical source.
    [0006]
    Electrochromic device according to claim 5, characterized by the fact that said at least one second electrical source comprises only a single second variable electrical source (21) and in which: a first output terminal of the second electrical source (21) is connected to one of the first polarization electrodes (3); a second output terminal of the second electrical source (21) is connected to the second polarization electrode (6) which is located in front of the first polarization electrode (3) to which the first output terminal of said second electrical source is connected, the first output terminal of the second electrical source (21) being, in addition, connected to the other second polarization electrode (7) than the one to which the second output terminal of said second electrical source is connected, and the second output terminal of the second electrical source (21) being, in addition, connected to the other first polarization electrode (4) than the one to which the first output terminal of said second electrical source is connected.
    [0007]
    Electrochromic device according to claim 5, characterized by the fact that said at least one second variable electrical source comprises a second variable electrical source (21) and a third variable electrical source (22), a second output terminal of the second electrical source (21) is connected to the second polarization electrode (6) which is located in front of the first polarization electrode (3) to which this first output terminal of this second electrical source, the third variable electrical source (22) is connected ) having a first output terminal connected to the other second polarization electrode (7) than the one to which the second output terminal of that second electrical source (21) is connected and having a second output terminal connected to the other first polarization electrode (4) that the one to which the said first output terminal of that second electrical source is connected (21).
    [0008]
    Electrochromic device according to any one of the preceding claims, characterized by the fact that the first electroactive substances in the oxidized form of said first electroactive substances each have an electrical charge greater than an electrical charge of each second electroactive substance in reduced form of these second electroactive substances.
    [0009]
    Electrochromic device according to any one of the preceding claims, characterized by the fact that it forms at least part of a spectacle glass, a mask glass, an optical lens, a helmet visor, an airplane window or a pane.
    [0010]
    Electrochromic device according to any one of claims 1 to 9, characterized in that it also comprises a network of internal walls (12), forming a division of the closed volume (V) in cells (13) juxtaposed parallel to the walls (10, 11) that limit said closed volume, said internal walls being perpendicular to said walls that limit said closed volume, and in which the two supply electrodes (1, 2) are each in contact with the liquid or gel contained in each cell, and the liquid or gel contained in that cell containing both the first and second electroactive substances.
    [0011]
    Electrochromic device according to any one of claims 1 to 10, characterized in that it also comprises a network of internal walls (12) forming a division of the closed volume (V) into cells (13) juxtaposed parallel to the walls (10, 11) that limit said closed volume, said internal walls being perpendicular to said walls that limit the internal volume and in which, for at least certain of the cells, a single of the two supply electrodes (1, 2) is in contact with the liquid or gel contained in each cell, a first of said cells that is fed by one of the feeding electrodes (1) being adjacent to a second of said cells that is fed by the other feeding electrode (2) with a ionic bridge (14) between said first and second cells.
    [0012]
    Electrochromic device according to claim 11, characterized by the fact that at least certain of the inner walls (12) extend in the direction of that of the walls (11) that carry the first polarization electrodes (3, 4) in one direction ( D) perpendicular to the walls (10, 11) that limit the closed volume, until closing these cells on the side of the said wall that holds the first polarization electrodes avoiding the passage of electroactive substances that are in the vicinity of these first polarization electrodes of a cell (13) to a neighboring cell.
    [0013]
    Electrochromic device according to claim 11 or 12, characterized in that the liquid or gel contains first electroactive substances without second electroactive substances inside the cells (13) fed by one of the supply electrodes (1), and second substances electroactive, without first electroactive substances inside the cells (13) fed by the other feeding electrode (2).
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    同族专利:
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    FR2950710B1|2012-03-16|
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    KR101713812B1|2017-03-09|
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    法律状态:
    2018-08-14| B25A| Requested transfer of rights approved|Owner name: ESSILOR INTERNATIONAL (FR) |
    2019-01-08| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-16| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-11-12| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2020-07-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-09-24| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 24/09/2020, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    FR0956707A|FR2950710B1|2009-09-28|2009-09-28|TRANSPARENT ELECTROCHROMIC SYSTEMS WITH MULTIPLE POLARIZATION ELECTRODES|
    FR0956707|2009-09-28|
    PCT/FR2010/052013|WO2011036420A1|2009-09-28|2010-09-24|Transparent electrochromic systems with a plurality of polarisation electrodes|
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