CA1256187A - Electrochromic devices using proton-conducting acid- polymer blends as the solid electrolyte - Google Patents
Electrochromic devices using proton-conducting acid- polymer blends as the solid electrolyteInfo
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- CA1256187A CA1256187A CA000499837A CA499837A CA1256187A CA 1256187 A CA1256187 A CA 1256187A CA 000499837 A CA000499837 A CA 000499837A CA 499837 A CA499837 A CA 499837A CA 1256187 A CA1256187 A CA 1256187A
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- electrochromic device
- solid electrolyte
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Abstract
"ELECTROCHROMIC DEVICES USING PROTON-CONDUCTING
ACID-POLYMER BLENDS AS THE SOLID ELECTROLYTE"
ABSTRACT
Electrochromic display devices which maintain coloration after an electric current has been removed comprise an electronic conductor consisting of a support which may be electrically conductive per se or contain an electronic conductor thereon, an electrochromic material in contact with said conductor, a solid electrolyte comprising a blend of an organic polymer and a heteropoly acid or salt thereof disposed on said electrochromic material and a counter-electrode in con-tact with the solid electrolyte. By utilizing this type of solid elec-trolyte, it is possible to obtain a display device which may range from about 5 to about 100 microns in thickness.
ACID-POLYMER BLENDS AS THE SOLID ELECTROLYTE"
ABSTRACT
Electrochromic display devices which maintain coloration after an electric current has been removed comprise an electronic conductor consisting of a support which may be electrically conductive per se or contain an electronic conductor thereon, an electrochromic material in contact with said conductor, a solid electrolyte comprising a blend of an organic polymer and a heteropoly acid or salt thereof disposed on said electrochromic material and a counter-electrode in con-tact with the solid electrolyte. By utilizing this type of solid elec-trolyte, it is possible to obtain a display device which may range from about 5 to about 100 microns in thickness.
Description
12S~37 ACID-POLYMER BLENDS AS THE SOLID ELECTROLYT~"
BACKGROUND OF ~HE INVENTION
Electrochromism is the change in light-absorbing properties of a material under the influence of an applied voltage. The induced coloration will remain even after the voltage is removed. An electro-chromic material has the property of changing color when the voltage i5 applied across the material or, alternatively, if a current is passed through it. The electrochromic material can be made to return to its original light absorbing state or color by reversing the polarity of the voltage or current. By changing the polarity of the applied voltage or current, known electrochromic materials which may be both organic and inorganic in nature can be cycled in such a manner so that the color change may be made from clear or transparent to colored, or from one color state to another color state, the last case being characteristic but not exclusive of organic materials. For example, electrochromic d-isplays may go from clear to blue, from yellow to blue, from red to blue, from green to blue/black, etc., and the reverse. This is in contradistinction to other displays such as light-emitting diode displays which may go from off to red or liquid crystal displays which may go from clear to blue and reverse. Once an electrochromic display is in either its color or trans-parent state, it will remain in such a state for a considerable lengthy period of time, even though the power has been turned off. This is also in contradistinction to light-emitting diode displays and liquid crystal disDlavs which require continuous power in order to be seen. The beneficial char-acteristics which are possessed by electrochromic displays include a low voltage operation, low power requirements, storage of the display with-out the dissipation of power, potentially low cost as well as a relatively simple construction. ~hey also will provide a pleasina display in that -the color will be present in a relatively good contrast compared to the background while providing a wide angle of viewing.
The electrochromic material which is utilized in electro-chromic displays must possess a color center or other color absorbing structure having some optical absorption in the visible light range plus the presence of both electronic and ionic conduction. One class of electrochromic materials of the type hereinafter set forth in greater detail will possess high ion mobilities and the ability to produce a strong optical absorption in the visible light range upon injection of electrons. The protons which are present in the electrolyte which is in contact with the electrochromic material will contact said electro-chromic material and provide a means of maintaining charge neutrality in the electrochromic material. An example of this color change occurs when an electrochromic material such as tungsten trioxide is subjected to the action of an applied voltage through an electrolyte to form what is called tungsten bronze, said tungsten bronze producing a blue color from the colorless tungsten trioxide. To reverse the coloration process and bleach out the blue color produced by the tungsten bronze, the polar-ity is reversed so that the electrons and protons leave the electro-chromic material, said polarity reversal being effected until the entire tungsten bronze has been reconverted to the tungsten trioxide and the latter is restored to its original colorless state.
In the past, there have been electrochromic devices utilizing this phenomena. For example, U.S. Patent 4,306,773 discloses an electro-chromic display device utilizing a tungsten trioxide film and an aque-ous acidic electrolyte in contact with the surface of said film. Like-wise, U.S. Patent 3,843,232 also discloses an electrochromic device utilizing an electrochromic material and an ion-conductive medium between
BACKGROUND OF ~HE INVENTION
Electrochromism is the change in light-absorbing properties of a material under the influence of an applied voltage. The induced coloration will remain even after the voltage is removed. An electro-chromic material has the property of changing color when the voltage i5 applied across the material or, alternatively, if a current is passed through it. The electrochromic material can be made to return to its original light absorbing state or color by reversing the polarity of the voltage or current. By changing the polarity of the applied voltage or current, known electrochromic materials which may be both organic and inorganic in nature can be cycled in such a manner so that the color change may be made from clear or transparent to colored, or from one color state to another color state, the last case being characteristic but not exclusive of organic materials. For example, electrochromic d-isplays may go from clear to blue, from yellow to blue, from red to blue, from green to blue/black, etc., and the reverse. This is in contradistinction to other displays such as light-emitting diode displays which may go from off to red or liquid crystal displays which may go from clear to blue and reverse. Once an electrochromic display is in either its color or trans-parent state, it will remain in such a state for a considerable lengthy period of time, even though the power has been turned off. This is also in contradistinction to light-emitting diode displays and liquid crystal disDlavs which require continuous power in order to be seen. The beneficial char-acteristics which are possessed by electrochromic displays include a low voltage operation, low power requirements, storage of the display with-out the dissipation of power, potentially low cost as well as a relatively simple construction. ~hey also will provide a pleasina display in that -the color will be present in a relatively good contrast compared to the background while providing a wide angle of viewing.
The electrochromic material which is utilized in electro-chromic displays must possess a color center or other color absorbing structure having some optical absorption in the visible light range plus the presence of both electronic and ionic conduction. One class of electrochromic materials of the type hereinafter set forth in greater detail will possess high ion mobilities and the ability to produce a strong optical absorption in the visible light range upon injection of electrons. The protons which are present in the electrolyte which is in contact with the electrochromic material will contact said electro-chromic material and provide a means of maintaining charge neutrality in the electrochromic material. An example of this color change occurs when an electrochromic material such as tungsten trioxide is subjected to the action of an applied voltage through an electrolyte to form what is called tungsten bronze, said tungsten bronze producing a blue color from the colorless tungsten trioxide. To reverse the coloration process and bleach out the blue color produced by the tungsten bronze, the polar-ity is reversed so that the electrons and protons leave the electro-chromic material, said polarity reversal being effected until the entire tungsten bronze has been reconverted to the tungsten trioxide and the latter is restored to its original colorless state.
In the past, there have been electrochromic devices utilizing this phenomena. For example, U.S. Patent 4,306,773 discloses an electro-chromic display device utilizing a tungsten trioxide film and an aque-ous acidic electrolyte in contact with the surface of said film. Like-wise, U.S. Patent 3,843,232 also discloses an electrochromic device utilizing an electrochromic material and an ion-conductive medium between
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the electrochromic material such as tungsten trioxide and a counter-electrode such as palladium, said ion-conductive medium being liquid in nature such as a strong sulfuric acid solution. It is to be noted that both of these patents disclose the use of a liquid electrolyte such as sulfuric acid. The use of liquid electrolytes possess certain disad-vantages. For example, the display cell utilizing a liquid electrolyte requires a relatively complicated construction inasmuch as care must be taken to insure a permanent seal of the electrolyte within the cell in-asmuch as any leakage of the electrolyte will result in a breakdown of the display device. The care and means which are undertaken to insure the permanent seal of the electrolyte will, of necessity, add to the ex-pense in manufacturing such a device. Likewise, the acid may have a tendency to attack the electrochromic material, thus leading to a fail-ure of the device after a period of time.
In addition to the aforementioned U.S. patents, other U.S. pat-ents disclose solid electrochromic display devices. In this respect, U.S. Patent 3,995,943 shows a display device utilizing as an electro-chromic material an oxide of tungsten or vanadium and a solid electro-lyte comprising a mixed inorganic silver salt, one salt being silver io-dide. U.S. Patent 4,306,774 utilizes, as the electrochromic material a layer of material being selected from the group consisting of a diphthalo-cyanine of a rare earth element, yttrium and scandium. The solid electro-lyte which is employed is selected from the group consisting of a hetero-poly acid and hydrogen uranyl phosphate. Another solid state electro-chromic device is shown in U.S. Patent 4,350,414 which comprises a pair of electrodes, an oxidizable film and a reducible film capable of a redox reaction as well as an insulating film positioned between the oxidizable film and the insulating film. U.S. Patent 4,184,751 discloses an electro-' ~256~8~
chromic display utilizing a metal diphthalocyanine complex and as the electrolyte a porous solid which has been saturated with an inert electrolyte such as an aqueous solution of potass;um chloride. The por-ous solid which is illustrated in this patent comprises calcium sulfate dihydride, commonly known as plaster of paris which is white in nature and is preferred in order that the plaster will not adversely affect the colors which are generated during the display. However, such a system will sti11 involve the use of a wet electrolyte with the attendant costs and disadvantages previously discussed with reference to the use of liquid electrolytes.
In contrast to these prior art electrochromic devices, we have now discovered that an electrochromic device may be prepared in a solid state utilizing, as a solid electrolyte, a blend of an organic polymer and a heteropoly acid or salt thereof. This solid electrolyte will pro-lS vide the advantage of being an excellent proton-conducting material whereby the disassociated molecular hydrogen will migrate through the polymer as a proton and provide the impetus necessary to effect the de-sired color change. In addition, the polymer blend electrolyte will also possess other advantages over the electrolytes of prior use, said advantages being subsequently more fully discussed.
BRIEF SUMMARY OF THE INVENTION
This invention relates to an electrochromic display device which utilizes, as a solid electrolyte, a polymeric blend of an organic com-pound and a heteropoly acid or salt thereof, said solid electrolyte being a proton-conducting substrate whereby disassociated hydrogen will migrate through the electrolyte and activate the electrochromic material, thus 1 ~25 ~i3L8'~
providing the necessary change in color essential for the operation of the device.
Electrochromic devices in which a chemical change is produced in response to an electrical potential applied to the material will pro-vide changes in color in electrochromic materials which are a part of the device. This change in color of the material will enable the device to be used in any circumstances involving a color display. For example, the electrochromic display devices may be used for watches, calculators, computers, radio, television, etc. The electrochromic devices possess many advantages over other electrically controllable display devices such as liquid crystal displays, light-emitting diode displays, plasma dis-plays, etc. The power requirements for the electrochromic display de-vices (ECD) will be approximately the same as the liquid crystal displays (LCD) and less than that required to activate light-emitting diode dis-plays (LED). Other advantages have also been previously discussed and, in addition, the ECD can be viewed in a bright light with no restriction on the viewing angle as distinguished by the disadvantage possessed by the LED which cannot be viewed in a bright light and possesses a re-stricted viewing angle. Likewise, LCD devices are only operative over a limited temperature range and, like the LED, possess no memory, but must be refreshed. This is in contrast to the ECD which has a nonvolatile memory and will retain the color despite the absence of any power. Like-wise, ECD's may also be made in a relatively large assortment of colors in contrast to the LCD or LED devices which possess only one color.
By utilizing a blend of an organic polymer and a heteropoly acid or salt thereof of the type hereinafter set forth in greater detail as the solid electrolyte, it is possible to obtain several advantages over an electrochromic display device which utilizes other types of - ~25~i18~
solid electrolytes. For example, the use of a polymer blend as an electrolyte will render the device easier to manufacture inasmuch as the polymer blend will not require pressing and, in addition, will maintain its physical integrity due to its durability and elasticity. This is in contradistinction to other types of solid electrolytes which, in the pressed state, are very brittle, thus being readily subject to disinte-gration, and therefore are hard to work into a display device. Another advantage which is possessed by the polymer blend which comprises the electrolyte of the present device is that the polymer may be fabricated to form an electrolyte which is relatively thin in nature, thus requir-ing less material with a concurrent reduction in cost, in contrast to a pressed solid electrolyte which is thicker in nature. The electro-; chromic display device utilizing such a polymer blend as the electrolyte will also require a lower voltage for a successful operation, for exam-ple, requiring a voltage of about O.S volts as compared to a voltage of about 1 volt for a pressed electrolyte.
It is therefore an object of this invention to provide an electro-chromic display device which utilizes as a solid electrolyte a polymer blend of the type hereinafter set forth in greater detail.
In one aspect, an embodiment of this invention resides in an electrochromic device comprising in combination an electronic conductor, ~n electrochromic material in contact with said conductor, a solid electrolyte comprising a blend of an organic polymer and a heteropoly acid or salt thereof disposed on said electrochrom~v material and a counter-electrode in contact with said solid electrolyte.
,, A specific embodiment of this invention is found in an electro-~ ~2561~3 ~
chromic device comprising in combination an electrically conductive support comprising glass coated with tin oxide, an electrochromic material comprising tungsten trioxide in contact with said support, a solid electrolyte comprising a blend of poly(vinyl alcohol) and dodecamolybdo-phosphoric acid disposed on said tungsten trioxide, and a counter-electrode comprising platinum, the thickness of said device being in a range of from about 5 to about 100 microns.
Other objects and embodiments will be found in the following further detailed description of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The preferred embodiments of the inve~tion will be described with reference to the accompanying drawings, wherein:
Figure 1 is a schematic cross-sectional view of one embodiment of an electrochromic display device of the present invention; and Figure 2 is a schematic cross-sectional view of another embodiment of the present invention.
It is to be noted that variations may be made without departing from the general scope of the invention.
DETAILED DESCRIPTION OF THE INVENTION
As hereinbefore set forth, the present invention is concerned with an electrochromic device in which the electrolyte which is employed in combination with other components of the device comprises a blend of an organic polymer and a heteropoly acid or salt thereof. The elec-trochromic display device will comprise a combination of an electronic conductor, an electrochromic material, and ,~ ~
~ -7-~:25618~
electrolyte of the type hereinafter set forth in greater detail, and a counter-electrode. The electronic conductor will comprise an electrically conductive support. This electrically conductive support may be either transparent of reflective in nature, and may be electrically conductive per se or coated with an electronic conductive material.
For example, when the support is transparent in nature, it may consist of glass, quartz, transparent polymers, etc.
Conversely, when the support is re~lective in nature, it may be formed from a metal which is electrically conductive per se such as aluminum, nickel, platinum, palladium, tin, gold , silver, etc. or may be formed of a nonconductive material, non-transparent material such as wood, plastic, rubber, etc. which themselves are coated with an elec--7a-1256i87 tronic conductive material. It is also contemplated within the scope of this invention that supports which are transparent in nature may also be formed from transparent polymers which possess electrically conductive properties or which may be doped to possess the desired property. When the sùpport comprises glass, quartz, or a nonconductive polymer, the sup-port may be coated with a material which will provide the desired con-ductivity. For example, glass may be coated with electronically con-ductive materials such as tin oxide, antimony tin oxide, indium tin oxide, etc. to provide the desired electronic conductor.
The electrochromic material which is in contact with the elec-tronic conductor will comprise those materials which are capable of mani-festing a change in color when subjected to the action of protons due to the application of an electrical voltage. The electrochromic materials will comprise, in general, the oxides of metals which possess multiple oxidation states, some representative samples of these metal oxides will include tungsten oxide, molybdenum oxide, chromium oxide, niobium oxide, vanadium oxide, titanium oxide, manganese oxide, iridium oxide, rhodium oxide, ruthenium oxide, nickel oxide, osmium oxide, rhenium oxide, co-balt oxide, etc. In addition, it is also contemplated within the scope ~0 of this invention that the electrochromic materials which fonm one com-ponent of the electrochromic device of the present invention may also comprise polymeric redox dyes. Some examples of these dyes which may be employed will include the alkyl or aromatic-substituted viologens, or other ionenes, phenazines, phthalocyanines, metalloporphyrins, etc.
The solid electrolyte, which is used as a protonic conductor to enable the disassociated hydrogen to contact the electrochromic mate-rial, comprises a blend of an organic polymer and a heteropoly acid or salt thereof. Examples of organic polymers which may be employed as one ~256~8~7 component of the blend of the present invention include poly(vinyl alco-hol), poly(acrylic acid), polyethylene oxide, polyethyleneimine, poly-acrylic acid, polyethylene glycol, cellulose acetate, polyvinylmethyl-ethyl ether, phenol formaldehyde resins, etc.
Examples of heteropoly acids or salts thereof which may be em-ployed as the second component of the organic-inorganic blend which may be used to form a membrane will possess the generic formula:
Am[XxYyoz]-n H20 in which X and Y may be selected from the group consisting of boron, alu-minum, gallium, silicon, germanium, tin, phosphorus, arsenic, antimony, bismuth, selenium, tellurium, iodine, and the first, second, third and fourth transitional metal series, said series including scandium, yttrium, lanthanum, actinium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten, X and Y being dissimilar in nature, Y being at least one metal selected from the first, second, third or fourth transition metal series above named, A is selected from the group consisting of hydrogen, ammonium, sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium, m is an integer of from 1 to 10, y is an integer of from 6 to 12 based on x taken as 1, z is an integer of from 30 to 80 and n is an integer of from 3 to 100.
Specific examples of these compounds will include dodecamolybdo-phosphoric acid, ammonium molybdophosphate, sodium molybdophosphate, po-: tassium molybdophosphate, lithium molybdophosphate, calcium molybdophos-phate, magnesium molybdophosphate, dodecatungstophosphoric acid, ammonium tungstophosphate, sodium tungstophosphate, potassium tungstophosphate, lithium tungstophosphate, calcium tungstophosphate, magnesium tungstophos-~25618'7 phate, dodeca~olybdosilicic acid, ammonium molybdosilicate, sodium molyb-dosilicate, potassium molybdosilicate, lithium molybdosilicate, calcium molybdosilicate, magnesium molybdosilicate, dodecamolybdogermanic acid, ammonium molybdogermanate, sodium molybdogermanate, potassium molybdo-germanate, lithium molybdogermanate, calcium molybdogermanate, magnesium S molybdogermanate, hexamolybdotelluric acid, ammonium molybdotellurate,sodium molybdotellurate, potassium molybdotellurate, lithium molybdotel-lurate, calcium molybdotellurate, magnesium molybdotellurate, dodeca-tungstosilicic acid, ammonium tungstosilicate, sodium tungstosilicate, potassium tungstosilicate, lithium tungstosilicate, calcium tungstosil-icate, magnesium tungstosilicate, etc. It is also contemplated within the scope of this invention that some uranyl compounds may also be em-ployed as the heteropoly acid or salt thereof. These uranyl compounds will possess the generic formula:
A[U02] X04.n H20 in which A is selected from the group consisting of hydrogen, lithium, sodium, potassium, ammonium, copper, magnesium, calcium, barium, stron-tium, lead, iron, cobalt, nickel, manganese and aluminum, X is selected from the group consisting of phosphorus and arsenic and n is an integer of from 1 to 4. Some specific examples of these uranyl compounds will include uranyl orthophosphate, uranyl orthoarsenate, lithium uranyl-phosphate, lithium uranylarsenate, sodium uranylphosphate, sodium uranyl-arsenate, potassium uranylphosphate, potassium uranylarsenate, ammonium uranylphosphate, ammonium uranylarsenate, calcium uranylphosphate, cal-cium uranyiarsenate, birium uranylphosphate, bari~m uranylarsenate, copper uranylphosphate, copper uranylarsenate, iron uranylphosphate, iron uranylarsenate, cobalt uranylphosphate, cobalt uranylarsenate, nickel uranylphosphate, nickel uranylarsenate, etc.
l2s6~a!7 It is to be understood that the aforementioned listin~ of organic polymeric compounds, heteropoly acids or sa1ts thereof are only representative of the class of compounds which may be employed in for-mulating the organic-inorganic blends of the present invention, and that this invention is not necessarily limited thereto.
Some representative examples of organic-inorganic polymer blends which may be used to provide the solid electrolyte in the form of a thin film which acts as a proton conductor in the electrochromic de-vice of the present invention will include poly(vinyl alcohol)-dodeca-molybdophosphoric acid, cellulose acetate-dodecamolybdophosphoric acid, polyethylene oxide-dodecamolybdophosphoric acid, polyethylene glycol-do-decamolybdophosphoric acid, poly(vinyl alcohol)-dodecatungstophosphoric acid, cellulose acetate-dodecatungstophosphoric acid, polyethylene oxide-dodecatungstophosphoric acid, polyethylene glycol-dodecatungsto-lS phosphoric acid, poly(vinyl alcohol)-dodecamolybdosilicic acid, cellulose acetate-dodecamolybdosilicic acid, polyethylene oxide-dodecamolybdosilic-ic acid, polyethylene glycol-dodecamolybdosilicic acid, poly(vinyl alco-h`ol)-ammonium molybdophosphate, cellulose acetate-ammonium molybdophos-phate, polyethylene oxide-ammonium molybdophosphate, polyethylene glycol-ammonium molybdophosphate, poly(vinyl alcohol)-uranyl orthophosphate, poly(acrylic acid)-dodecamolybdophosphoric acid, poly(acrylic acid)-do-; decatungstophosphoric acid, poly(acrylic acid)-uranyl orthophosphate,cellulose acetate-uranyl orthophosphate, polyethylene oxide-uranyl ortho-phosphate, polyethylene glycol-uranyl orthophosphate, etc. It is to be understood that the aforementioned list of polymer blends is only repre-sentative of the class of blends which may be employed as solid electro-lytes in the electrochromic display device of the present invention and that the type of blend is not necessarily limited thereto.
:
The amount of heteropoly acid or salts thereof used in formulatin~ ~he blend is typical~ly expressed as a percent by weight of the organic polymer compounds used therein and tt ts tntended to cover any amount which will be operative in the contemplated device wtth satisfactory results obtained in the range 0.5 to 100 wt. X and best results are t~ypically obtained at 50 wt. X.
125618~
Referring now to the drawing, in Figure 1 which is one embodi-ment of the display device of the present invention, the electrochromic display device comprises a support 1 which, as hereinbefore set forth, may be either transparent or reflective in nature such as glass, metal, plastic, etc. The support will be thick enough to provide structural strength and support for the remaining elements or components of the de-vice. In one embodiment the electronic conductor 2 is deposited on the support, said electronic conductor comprising a conductive material such as tin oxide. An electrochromic material 3 is in contact with the con-ductive material and support in a relatively thin layer, the thicknessof which is hereinafter set forth in greater detail. The solid electro-lyte 4 is disposed on the electrochromic material in contact therewith, the solid electrolyte comprising a blend of an organic polymer and a heteropoly acid or salt thereof. In contact with the electrolyte is counter-electrode 5, the counter-electrode comprising a conductive metal deposited on the electrolytic membrane. The device is then connected by contacts 6 and 7 to an electric source 8 which may comprise a battery or an electric circuit. While the above description of the drawing shows separate support 1 and electronic conductor ~, it is contemplated within the scope of this invention that the electrically conductive material such as tin oxide may be incorporated into the support such as ,.
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~25618r~'' a transparent polymer so that the support and electronic conductor may comprise only one layer, this variation being within the intention or parameters of the invention.
Figure 2 represents another embodiment of the invention in which support 21, comprising glass or a transparent polymer which is thick enough to provide structural strength and support, has deposited thereon an electronic conductor 22 of the type similar in nature to that hereinbefore set forth in the description of Figure 1. It is also contemplated that, as in the prior description of Figure 1, the elec-tronic conductor may be incorporated into the support. An electro-chromic material 23 such as tungsten trioxide, molybdenum trioxide, etc.
of the type hereinbefore set forth in greater detail is in contact with ~ the electronic conductor 22 in the form of a relatively thin layer.
; Solid electrolyte 24 is disposed on the electrochromic material and in contact therewith, said solid electrolyte also comprising a blend of an organic polymer and a heteropoly acid or salt thereof. The electrolyte will contain an inert compound which is capable of effecting a diffuse scattering of light, thus rendering the electrolyte nontransparent in nature. The counter-electrode will comprise a combination of electro-chromic material 25 similar in nature to electrochromic material 23 in contact with electrolyte 24. Also, in contact with electrochromic material 25 is an electronic conductor 26, said electronic conductor 26 also being similar in nature to electronic conductor 22. Support mem-ber 27 will contact the side of electronic conductor 26 which is not in contact with electrochromic material 25. The device, which repre-sents a solid electrolyte 27 sandwiched between the electronic conductor and support will be connected by means of contacts 28 and 29 to an electric source 30 which, as in the case of the other embodiment of the 125~;~8 ~
invention, comprises a battery or an electric circuit.
In one embodiment the electrochromic display device may be prepared by depositing the electronically conductive material on the sur-face of a solid support such as glass in any manner known in the art.
For example, a compound such as tin chloride may be deposited on the sur-face of the support in a vapor state in an oxygen atmosphere at a tem-perature which may range from about 300 to about 400C to provide a layer of tin oxide on the glass. Alternatively, the tin oxide may be sputter deposited on the support, either method of deposition being sufficient to form a film of electrically conductive material on the support having a thickness of from about 100 to about 1000 Angstroms. Following the deposition of the electrically conductive material on the support, the electrochromic material is then applied to the electronic conductor by any manner so selected, the various methods of deposition includina sputter deposition, electrodeposition, evaporation, or solution deposi-tion in an amount sufficient to impart a layer of electrochromic mate-rial in contact with the electronic conductor which will have a thick-ness in the range of from about 1,000 to about 10,000 Angstroms. When employing these methods of depositing the electrochromic material on the surface of the electronic conductor, deposition conditions which are em-ployed will include temperatures ranging from about 4 to about 80C
and atmospheric pressure.
Following the deposition of the electrochromic material on the electronic conductor, the solid electrolyte is then applied to the surface of the electrochromic material. The solid electrolyte which comprises a blend of an organic polymer and a heteropoly acid or salt thereof of the type hereinbefore set forth in greater detail is pre-pared by admixing the two components of the blend in a mutually miscible ~256~a~
solvent under solution conditions for a period of time sufficient to form the desired blend. The mutually miscible solvent which is gener-ally employed to dissolve the components comprises water, although it is also contemplated that other mutually miscible solvents, either in-organic or organic in nature, may also be employed. The solution con-ditions will usually include a temperature in the range of from about ambient up to the boiling point of the mutually miscible solvent for a period of time necessary to form the blend. This time will vary with the particular components of the blend as well as the solvent and may range for a period of time from about 0.5 up to about 10 hours or more in duration. Upon completion of the solution period, the blend is then cast upon the surface of the electrochromic material in such an amount as to form a relatively thin film of a solid electrolyte layer having a thickness of from about 4 to about 99 microns. After casting the sol-ution upon the surface of the electrochromic material, the solvent is removed by any conventional means including natural evaporation or forced evaporation by the application of elevated temperatures whereby the solvent is evaporated and the desired film of the polymeric blend is formed. The last component of the electrochromic display device is applied to the surface of the electrolyte which is not in contact with the electrochromic material also by any means convenient to employ.
For example, in one embodiment of the invention, the counter-electrode comprising a conductive material such as platinum, palladium, etc. may be sputter deposited on the electrolyte in such an amount so as to pro-vide an electrode having a thickness of from about 200 to about 1000 Angstroms. In addition, the surface area of the counter-electrode will vary in size, the size of the electrode being sufficient to provide a good contact with the electrical system.
l2s6~ar~
When preparing an electrochromic display device as illustrated by Figure 2 of the drawing, the electronic conductive material is de-posited on the surface of a transparent support such as glass, polymer, etc. in a manner similar to that hereinbefore described. Alternatively, the transparent support may comprise an electrically conductive trans-parent material such as an electrically conductive polymer in which the presence of the electronic conductor may be omitted. Following the de-position of the electrically conductive material to the support, the electrochromic material is then deposited on the surface of the elec-tronic conductor also in a manner similar to that hereinbefore set forth.The solid electrolyte comprising a blend of an organic polymer and a heteropoly acid or salt thereof may then be cast on the surface of the electronic conductor in the form of a thin film membrane. The counter-electrode, which, in this instance comprises a combination of the sup-port, electronic conductor and electrochromic material in the form oflayers is then placed on the upper surface of the electrolyte so that the electrochromic material is in contact with the electrolyte and there-after pressed to insure a permanent and intimate contact between the counter-electrode and the electrolyte. The solid electrolyte compris-ing the polymeric blend will also contain an inert compound such as ti-tanium dioxide, zinc oxide, aluminum oxide, etc. which will produce the diffused scattering of light and thus render the electrolyte nontrans-parent in nature. The electrochromic display device which now comprises `~ a symmetrical device in which the electrolyte is sandwiched between two layers of the electrochromic material which itself is in contact with a transparent electronic conductor, the latter comprising an electrically conductive support, is then fitted with electrical contacts which are, in turn, connected to a source of electricity.
' ~2S618P~
As hereinbefore set forth, the power which is required to operate the electrochromic display will be greater than the power which is required to operate a liquid crystal display but less than that which is required to operate a light-emitting diode display. Generally speaking, the vol~age required to operate an electrochromic display de-vice may range from about 0.4 to about 1.5 volts with a change in color being effected for a period which may range from about 25 to about 500 milliseconds. In the range of response time to ~he electric current, it is to be noted that the response time of the electrochromic display is greater than the response time for a liquid crystal display, but less than that of the light-emitting display. Again, the power may come from any source such as a battery or electric current, either direct current or countercurrent in nature.
The following examples are given to illustrate a process for preparing an electrochromic device of the present invention. However, it is to be understood that these examples are given merely for purposes of illustration and that the present process is not necessarily limited thereto.
EXAMPLE I
In this example, a conductive glass substrate having a layer of tin oxide deposited thereon was placed in a sputter deposition cham-ber. The sputter deposition of tungsten trioxide on the tin oxide was effected at a pressure of about 100 torr (13;33 kPa ~abs)) for a period of 20 minutes using a combination of air and argon as the sputter gas, utilizing a tungsten target. J
A solution of a polymeric blend was prepared by admixing poly-(vinyl alcohol) and dodecamolybdophosphoric acid in a 50/50~ by weight 1256~3r~
amount with a sufficient amount of water to obtain a 2% solution of the blend. The polymeric blend was then cast on the tin oxide/tungsten tri-oxide coated glass and allowed to dry at ambient temperature to give a thin membrane f;lm which was approximately 5 microns in thickness.
Thereafter, the device in which the polymeric blend membrane acts as a solid electrolyte, was placed in a sputter deposition chamber and subjected to the sputter deposition of platinum thereon until a thickness of about 200 Angstroms of platinum was deposited on the sur-face of the membrane. Electrical contacts were then added to the plati-num which acted as a counter-electrode and to the glass containing the tin oxide deposited thereon which acted as the electronic conductor. An electric charge of 10 millicoulombs per square cm was charged to the de-vice and the tungsten oxide changed from transparent to blue.
EXAMPLE II
In a manner similar to that set forth in Example I above, an electrochromic display device was prepared by sputter-depositing tung-sten trioxide on the surface of a tin oxide glass-coated substrate.
The polymeric blend which formed a membrane, the latter acting as a solid electrolyte, was prepared by dissolving equal proportions by weight of poly(vinyl alcohol) and dodecatungstophosphoric acid. The polymer was cast on the surface of the electrochromic material and, after being al-lowed to dry, had platinum sputter-deposited thereon to form a counter-electrode. The tungsten oxide had a thickness of about 1000 Angstroms, the membrane a thickness of about 5 microns and the platinum a thickness of about 200 Angstroms. When an electric current ~as charged to the de-vice, the tungsten trioxide changed from transparent to a blue color.
~,256~8 ~
EXAMPLE III
To illustrate an electrochromic display device as shown in Figure 2 of the drawing, two pieces of conductive glass substrates hav-ing a layer of tin oxide deposited thereon were treated in a manner sim-ilar to that set forth in Example I above, that is, by being placed in a sputter depos;tion chamber. The pressure in the cylinder was reduced to approximately lO0 torr (13.33 kPa (abs)) and tungsten trioxide was sputter-deposited on the tin oxide surface utilizing a combination of air and argon as the sputter gas.
Thereafter, a solution of a polymeric blend was prepared by admixing equal amounts by weight of poly~acrylic acid) and dodecatungsto-phosphoric acid, plus a sufficient amount of titanium dioxide to impart an opaqueness or milk-like appearance to the polymeric solution, with water to obtain a 2% solution of the blend. The polymeric blend solu-tion was then cast on one of the tungsten trioxide-treated tin oxide-coated glass supports to obtain a thin film. Thereafter, the second tungsten trioxide-treated tin oxide-coated glass support was placed on the surface of the polymer, the tin oxide contacting the polymer. The device was allowed to dry at ambient temperature, electrical contacts were added to the conductive supports and a charge of lO millicoulombs/
square cm was charged to the device. The tungsten trioxide changed from transparent to a blue color, said blue color remaining after the charge had been discontinued.
the electrochromic material such as tungsten trioxide and a counter-electrode such as palladium, said ion-conductive medium being liquid in nature such as a strong sulfuric acid solution. It is to be noted that both of these patents disclose the use of a liquid electrolyte such as sulfuric acid. The use of liquid electrolytes possess certain disad-vantages. For example, the display cell utilizing a liquid electrolyte requires a relatively complicated construction inasmuch as care must be taken to insure a permanent seal of the electrolyte within the cell in-asmuch as any leakage of the electrolyte will result in a breakdown of the display device. The care and means which are undertaken to insure the permanent seal of the electrolyte will, of necessity, add to the ex-pense in manufacturing such a device. Likewise, the acid may have a tendency to attack the electrochromic material, thus leading to a fail-ure of the device after a period of time.
In addition to the aforementioned U.S. patents, other U.S. pat-ents disclose solid electrochromic display devices. In this respect, U.S. Patent 3,995,943 shows a display device utilizing as an electro-chromic material an oxide of tungsten or vanadium and a solid electro-lyte comprising a mixed inorganic silver salt, one salt being silver io-dide. U.S. Patent 4,306,774 utilizes, as the electrochromic material a layer of material being selected from the group consisting of a diphthalo-cyanine of a rare earth element, yttrium and scandium. The solid electro-lyte which is employed is selected from the group consisting of a hetero-poly acid and hydrogen uranyl phosphate. Another solid state electro-chromic device is shown in U.S. Patent 4,350,414 which comprises a pair of electrodes, an oxidizable film and a reducible film capable of a redox reaction as well as an insulating film positioned between the oxidizable film and the insulating film. U.S. Patent 4,184,751 discloses an electro-' ~256~8~
chromic display utilizing a metal diphthalocyanine complex and as the electrolyte a porous solid which has been saturated with an inert electrolyte such as an aqueous solution of potass;um chloride. The por-ous solid which is illustrated in this patent comprises calcium sulfate dihydride, commonly known as plaster of paris which is white in nature and is preferred in order that the plaster will not adversely affect the colors which are generated during the display. However, such a system will sti11 involve the use of a wet electrolyte with the attendant costs and disadvantages previously discussed with reference to the use of liquid electrolytes.
In contrast to these prior art electrochromic devices, we have now discovered that an electrochromic device may be prepared in a solid state utilizing, as a solid electrolyte, a blend of an organic polymer and a heteropoly acid or salt thereof. This solid electrolyte will pro-lS vide the advantage of being an excellent proton-conducting material whereby the disassociated molecular hydrogen will migrate through the polymer as a proton and provide the impetus necessary to effect the de-sired color change. In addition, the polymer blend electrolyte will also possess other advantages over the electrolytes of prior use, said advantages being subsequently more fully discussed.
BRIEF SUMMARY OF THE INVENTION
This invention relates to an electrochromic display device which utilizes, as a solid electrolyte, a polymeric blend of an organic com-pound and a heteropoly acid or salt thereof, said solid electrolyte being a proton-conducting substrate whereby disassociated hydrogen will migrate through the electrolyte and activate the electrochromic material, thus 1 ~25 ~i3L8'~
providing the necessary change in color essential for the operation of the device.
Electrochromic devices in which a chemical change is produced in response to an electrical potential applied to the material will pro-vide changes in color in electrochromic materials which are a part of the device. This change in color of the material will enable the device to be used in any circumstances involving a color display. For example, the electrochromic display devices may be used for watches, calculators, computers, radio, television, etc. The electrochromic devices possess many advantages over other electrically controllable display devices such as liquid crystal displays, light-emitting diode displays, plasma dis-plays, etc. The power requirements for the electrochromic display de-vices (ECD) will be approximately the same as the liquid crystal displays (LCD) and less than that required to activate light-emitting diode dis-plays (LED). Other advantages have also been previously discussed and, in addition, the ECD can be viewed in a bright light with no restriction on the viewing angle as distinguished by the disadvantage possessed by the LED which cannot be viewed in a bright light and possesses a re-stricted viewing angle. Likewise, LCD devices are only operative over a limited temperature range and, like the LED, possess no memory, but must be refreshed. This is in contrast to the ECD which has a nonvolatile memory and will retain the color despite the absence of any power. Like-wise, ECD's may also be made in a relatively large assortment of colors in contrast to the LCD or LED devices which possess only one color.
By utilizing a blend of an organic polymer and a heteropoly acid or salt thereof of the type hereinafter set forth in greater detail as the solid electrolyte, it is possible to obtain several advantages over an electrochromic display device which utilizes other types of - ~25~i18~
solid electrolytes. For example, the use of a polymer blend as an electrolyte will render the device easier to manufacture inasmuch as the polymer blend will not require pressing and, in addition, will maintain its physical integrity due to its durability and elasticity. This is in contradistinction to other types of solid electrolytes which, in the pressed state, are very brittle, thus being readily subject to disinte-gration, and therefore are hard to work into a display device. Another advantage which is possessed by the polymer blend which comprises the electrolyte of the present device is that the polymer may be fabricated to form an electrolyte which is relatively thin in nature, thus requir-ing less material with a concurrent reduction in cost, in contrast to a pressed solid electrolyte which is thicker in nature. The electro-; chromic display device utilizing such a polymer blend as the electrolyte will also require a lower voltage for a successful operation, for exam-ple, requiring a voltage of about O.S volts as compared to a voltage of about 1 volt for a pressed electrolyte.
It is therefore an object of this invention to provide an electro-chromic display device which utilizes as a solid electrolyte a polymer blend of the type hereinafter set forth in greater detail.
In one aspect, an embodiment of this invention resides in an electrochromic device comprising in combination an electronic conductor, ~n electrochromic material in contact with said conductor, a solid electrolyte comprising a blend of an organic polymer and a heteropoly acid or salt thereof disposed on said electrochrom~v material and a counter-electrode in contact with said solid electrolyte.
,, A specific embodiment of this invention is found in an electro-~ ~2561~3 ~
chromic device comprising in combination an electrically conductive support comprising glass coated with tin oxide, an electrochromic material comprising tungsten trioxide in contact with said support, a solid electrolyte comprising a blend of poly(vinyl alcohol) and dodecamolybdo-phosphoric acid disposed on said tungsten trioxide, and a counter-electrode comprising platinum, the thickness of said device being in a range of from about 5 to about 100 microns.
Other objects and embodiments will be found in the following further detailed description of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The preferred embodiments of the inve~tion will be described with reference to the accompanying drawings, wherein:
Figure 1 is a schematic cross-sectional view of one embodiment of an electrochromic display device of the present invention; and Figure 2 is a schematic cross-sectional view of another embodiment of the present invention.
It is to be noted that variations may be made without departing from the general scope of the invention.
DETAILED DESCRIPTION OF THE INVENTION
As hereinbefore set forth, the present invention is concerned with an electrochromic device in which the electrolyte which is employed in combination with other components of the device comprises a blend of an organic polymer and a heteropoly acid or salt thereof. The elec-trochromic display device will comprise a combination of an electronic conductor, an electrochromic material, and ,~ ~
~ -7-~:25618~
electrolyte of the type hereinafter set forth in greater detail, and a counter-electrode. The electronic conductor will comprise an electrically conductive support. This electrically conductive support may be either transparent of reflective in nature, and may be electrically conductive per se or coated with an electronic conductive material.
For example, when the support is transparent in nature, it may consist of glass, quartz, transparent polymers, etc.
Conversely, when the support is re~lective in nature, it may be formed from a metal which is electrically conductive per se such as aluminum, nickel, platinum, palladium, tin, gold , silver, etc. or may be formed of a nonconductive material, non-transparent material such as wood, plastic, rubber, etc. which themselves are coated with an elec--7a-1256i87 tronic conductive material. It is also contemplated within the scope of this invention that supports which are transparent in nature may also be formed from transparent polymers which possess electrically conductive properties or which may be doped to possess the desired property. When the sùpport comprises glass, quartz, or a nonconductive polymer, the sup-port may be coated with a material which will provide the desired con-ductivity. For example, glass may be coated with electronically con-ductive materials such as tin oxide, antimony tin oxide, indium tin oxide, etc. to provide the desired electronic conductor.
The electrochromic material which is in contact with the elec-tronic conductor will comprise those materials which are capable of mani-festing a change in color when subjected to the action of protons due to the application of an electrical voltage. The electrochromic materials will comprise, in general, the oxides of metals which possess multiple oxidation states, some representative samples of these metal oxides will include tungsten oxide, molybdenum oxide, chromium oxide, niobium oxide, vanadium oxide, titanium oxide, manganese oxide, iridium oxide, rhodium oxide, ruthenium oxide, nickel oxide, osmium oxide, rhenium oxide, co-balt oxide, etc. In addition, it is also contemplated within the scope ~0 of this invention that the electrochromic materials which fonm one com-ponent of the electrochromic device of the present invention may also comprise polymeric redox dyes. Some examples of these dyes which may be employed will include the alkyl or aromatic-substituted viologens, or other ionenes, phenazines, phthalocyanines, metalloporphyrins, etc.
The solid electrolyte, which is used as a protonic conductor to enable the disassociated hydrogen to contact the electrochromic mate-rial, comprises a blend of an organic polymer and a heteropoly acid or salt thereof. Examples of organic polymers which may be employed as one ~256~8~7 component of the blend of the present invention include poly(vinyl alco-hol), poly(acrylic acid), polyethylene oxide, polyethyleneimine, poly-acrylic acid, polyethylene glycol, cellulose acetate, polyvinylmethyl-ethyl ether, phenol formaldehyde resins, etc.
Examples of heteropoly acids or salts thereof which may be em-ployed as the second component of the organic-inorganic blend which may be used to form a membrane will possess the generic formula:
Am[XxYyoz]-n H20 in which X and Y may be selected from the group consisting of boron, alu-minum, gallium, silicon, germanium, tin, phosphorus, arsenic, antimony, bismuth, selenium, tellurium, iodine, and the first, second, third and fourth transitional metal series, said series including scandium, yttrium, lanthanum, actinium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten, X and Y being dissimilar in nature, Y being at least one metal selected from the first, second, third or fourth transition metal series above named, A is selected from the group consisting of hydrogen, ammonium, sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium, m is an integer of from 1 to 10, y is an integer of from 6 to 12 based on x taken as 1, z is an integer of from 30 to 80 and n is an integer of from 3 to 100.
Specific examples of these compounds will include dodecamolybdo-phosphoric acid, ammonium molybdophosphate, sodium molybdophosphate, po-: tassium molybdophosphate, lithium molybdophosphate, calcium molybdophos-phate, magnesium molybdophosphate, dodecatungstophosphoric acid, ammonium tungstophosphate, sodium tungstophosphate, potassium tungstophosphate, lithium tungstophosphate, calcium tungstophosphate, magnesium tungstophos-~25618'7 phate, dodeca~olybdosilicic acid, ammonium molybdosilicate, sodium molyb-dosilicate, potassium molybdosilicate, lithium molybdosilicate, calcium molybdosilicate, magnesium molybdosilicate, dodecamolybdogermanic acid, ammonium molybdogermanate, sodium molybdogermanate, potassium molybdo-germanate, lithium molybdogermanate, calcium molybdogermanate, magnesium S molybdogermanate, hexamolybdotelluric acid, ammonium molybdotellurate,sodium molybdotellurate, potassium molybdotellurate, lithium molybdotel-lurate, calcium molybdotellurate, magnesium molybdotellurate, dodeca-tungstosilicic acid, ammonium tungstosilicate, sodium tungstosilicate, potassium tungstosilicate, lithium tungstosilicate, calcium tungstosil-icate, magnesium tungstosilicate, etc. It is also contemplated within the scope of this invention that some uranyl compounds may also be em-ployed as the heteropoly acid or salt thereof. These uranyl compounds will possess the generic formula:
A[U02] X04.n H20 in which A is selected from the group consisting of hydrogen, lithium, sodium, potassium, ammonium, copper, magnesium, calcium, barium, stron-tium, lead, iron, cobalt, nickel, manganese and aluminum, X is selected from the group consisting of phosphorus and arsenic and n is an integer of from 1 to 4. Some specific examples of these uranyl compounds will include uranyl orthophosphate, uranyl orthoarsenate, lithium uranyl-phosphate, lithium uranylarsenate, sodium uranylphosphate, sodium uranyl-arsenate, potassium uranylphosphate, potassium uranylarsenate, ammonium uranylphosphate, ammonium uranylarsenate, calcium uranylphosphate, cal-cium uranyiarsenate, birium uranylphosphate, bari~m uranylarsenate, copper uranylphosphate, copper uranylarsenate, iron uranylphosphate, iron uranylarsenate, cobalt uranylphosphate, cobalt uranylarsenate, nickel uranylphosphate, nickel uranylarsenate, etc.
l2s6~a!7 It is to be understood that the aforementioned listin~ of organic polymeric compounds, heteropoly acids or sa1ts thereof are only representative of the class of compounds which may be employed in for-mulating the organic-inorganic blends of the present invention, and that this invention is not necessarily limited thereto.
Some representative examples of organic-inorganic polymer blends which may be used to provide the solid electrolyte in the form of a thin film which acts as a proton conductor in the electrochromic de-vice of the present invention will include poly(vinyl alcohol)-dodeca-molybdophosphoric acid, cellulose acetate-dodecamolybdophosphoric acid, polyethylene oxide-dodecamolybdophosphoric acid, polyethylene glycol-do-decamolybdophosphoric acid, poly(vinyl alcohol)-dodecatungstophosphoric acid, cellulose acetate-dodecatungstophosphoric acid, polyethylene oxide-dodecatungstophosphoric acid, polyethylene glycol-dodecatungsto-lS phosphoric acid, poly(vinyl alcohol)-dodecamolybdosilicic acid, cellulose acetate-dodecamolybdosilicic acid, polyethylene oxide-dodecamolybdosilic-ic acid, polyethylene glycol-dodecamolybdosilicic acid, poly(vinyl alco-h`ol)-ammonium molybdophosphate, cellulose acetate-ammonium molybdophos-phate, polyethylene oxide-ammonium molybdophosphate, polyethylene glycol-ammonium molybdophosphate, poly(vinyl alcohol)-uranyl orthophosphate, poly(acrylic acid)-dodecamolybdophosphoric acid, poly(acrylic acid)-do-; decatungstophosphoric acid, poly(acrylic acid)-uranyl orthophosphate,cellulose acetate-uranyl orthophosphate, polyethylene oxide-uranyl ortho-phosphate, polyethylene glycol-uranyl orthophosphate, etc. It is to be understood that the aforementioned list of polymer blends is only repre-sentative of the class of blends which may be employed as solid electro-lytes in the electrochromic display device of the present invention and that the type of blend is not necessarily limited thereto.
:
The amount of heteropoly acid or salts thereof used in formulatin~ ~he blend is typical~ly expressed as a percent by weight of the organic polymer compounds used therein and tt ts tntended to cover any amount which will be operative in the contemplated device wtth satisfactory results obtained in the range 0.5 to 100 wt. X and best results are t~ypically obtained at 50 wt. X.
125618~
Referring now to the drawing, in Figure 1 which is one embodi-ment of the display device of the present invention, the electrochromic display device comprises a support 1 which, as hereinbefore set forth, may be either transparent or reflective in nature such as glass, metal, plastic, etc. The support will be thick enough to provide structural strength and support for the remaining elements or components of the de-vice. In one embodiment the electronic conductor 2 is deposited on the support, said electronic conductor comprising a conductive material such as tin oxide. An electrochromic material 3 is in contact with the con-ductive material and support in a relatively thin layer, the thicknessof which is hereinafter set forth in greater detail. The solid electro-lyte 4 is disposed on the electrochromic material in contact therewith, the solid electrolyte comprising a blend of an organic polymer and a heteropoly acid or salt thereof. In contact with the electrolyte is counter-electrode 5, the counter-electrode comprising a conductive metal deposited on the electrolytic membrane. The device is then connected by contacts 6 and 7 to an electric source 8 which may comprise a battery or an electric circuit. While the above description of the drawing shows separate support 1 and electronic conductor ~, it is contemplated within the scope of this invention that the electrically conductive material such as tin oxide may be incorporated into the support such as ,.
`' P~
~25618r~'' a transparent polymer so that the support and electronic conductor may comprise only one layer, this variation being within the intention or parameters of the invention.
Figure 2 represents another embodiment of the invention in which support 21, comprising glass or a transparent polymer which is thick enough to provide structural strength and support, has deposited thereon an electronic conductor 22 of the type similar in nature to that hereinbefore set forth in the description of Figure 1. It is also contemplated that, as in the prior description of Figure 1, the elec-tronic conductor may be incorporated into the support. An electro-chromic material 23 such as tungsten trioxide, molybdenum trioxide, etc.
of the type hereinbefore set forth in greater detail is in contact with ~ the electronic conductor 22 in the form of a relatively thin layer.
; Solid electrolyte 24 is disposed on the electrochromic material and in contact therewith, said solid electrolyte also comprising a blend of an organic polymer and a heteropoly acid or salt thereof. The electrolyte will contain an inert compound which is capable of effecting a diffuse scattering of light, thus rendering the electrolyte nontransparent in nature. The counter-electrode will comprise a combination of electro-chromic material 25 similar in nature to electrochromic material 23 in contact with electrolyte 24. Also, in contact with electrochromic material 25 is an electronic conductor 26, said electronic conductor 26 also being similar in nature to electronic conductor 22. Support mem-ber 27 will contact the side of electronic conductor 26 which is not in contact with electrochromic material 25. The device, which repre-sents a solid electrolyte 27 sandwiched between the electronic conductor and support will be connected by means of contacts 28 and 29 to an electric source 30 which, as in the case of the other embodiment of the 125~;~8 ~
invention, comprises a battery or an electric circuit.
In one embodiment the electrochromic display device may be prepared by depositing the electronically conductive material on the sur-face of a solid support such as glass in any manner known in the art.
For example, a compound such as tin chloride may be deposited on the sur-face of the support in a vapor state in an oxygen atmosphere at a tem-perature which may range from about 300 to about 400C to provide a layer of tin oxide on the glass. Alternatively, the tin oxide may be sputter deposited on the support, either method of deposition being sufficient to form a film of electrically conductive material on the support having a thickness of from about 100 to about 1000 Angstroms. Following the deposition of the electrically conductive material on the support, the electrochromic material is then applied to the electronic conductor by any manner so selected, the various methods of deposition includina sputter deposition, electrodeposition, evaporation, or solution deposi-tion in an amount sufficient to impart a layer of electrochromic mate-rial in contact with the electronic conductor which will have a thick-ness in the range of from about 1,000 to about 10,000 Angstroms. When employing these methods of depositing the electrochromic material on the surface of the electronic conductor, deposition conditions which are em-ployed will include temperatures ranging from about 4 to about 80C
and atmospheric pressure.
Following the deposition of the electrochromic material on the electronic conductor, the solid electrolyte is then applied to the surface of the electrochromic material. The solid electrolyte which comprises a blend of an organic polymer and a heteropoly acid or salt thereof of the type hereinbefore set forth in greater detail is pre-pared by admixing the two components of the blend in a mutually miscible ~256~a~
solvent under solution conditions for a period of time sufficient to form the desired blend. The mutually miscible solvent which is gener-ally employed to dissolve the components comprises water, although it is also contemplated that other mutually miscible solvents, either in-organic or organic in nature, may also be employed. The solution con-ditions will usually include a temperature in the range of from about ambient up to the boiling point of the mutually miscible solvent for a period of time necessary to form the blend. This time will vary with the particular components of the blend as well as the solvent and may range for a period of time from about 0.5 up to about 10 hours or more in duration. Upon completion of the solution period, the blend is then cast upon the surface of the electrochromic material in such an amount as to form a relatively thin film of a solid electrolyte layer having a thickness of from about 4 to about 99 microns. After casting the sol-ution upon the surface of the electrochromic material, the solvent is removed by any conventional means including natural evaporation or forced evaporation by the application of elevated temperatures whereby the solvent is evaporated and the desired film of the polymeric blend is formed. The last component of the electrochromic display device is applied to the surface of the electrolyte which is not in contact with the electrochromic material also by any means convenient to employ.
For example, in one embodiment of the invention, the counter-electrode comprising a conductive material such as platinum, palladium, etc. may be sputter deposited on the electrolyte in such an amount so as to pro-vide an electrode having a thickness of from about 200 to about 1000 Angstroms. In addition, the surface area of the counter-electrode will vary in size, the size of the electrode being sufficient to provide a good contact with the electrical system.
l2s6~ar~
When preparing an electrochromic display device as illustrated by Figure 2 of the drawing, the electronic conductive material is de-posited on the surface of a transparent support such as glass, polymer, etc. in a manner similar to that hereinbefore described. Alternatively, the transparent support may comprise an electrically conductive trans-parent material such as an electrically conductive polymer in which the presence of the electronic conductor may be omitted. Following the de-position of the electrically conductive material to the support, the electrochromic material is then deposited on the surface of the elec-tronic conductor also in a manner similar to that hereinbefore set forth.The solid electrolyte comprising a blend of an organic polymer and a heteropoly acid or salt thereof may then be cast on the surface of the electronic conductor in the form of a thin film membrane. The counter-electrode, which, in this instance comprises a combination of the sup-port, electronic conductor and electrochromic material in the form oflayers is then placed on the upper surface of the electrolyte so that the electrochromic material is in contact with the electrolyte and there-after pressed to insure a permanent and intimate contact between the counter-electrode and the electrolyte. The solid electrolyte compris-ing the polymeric blend will also contain an inert compound such as ti-tanium dioxide, zinc oxide, aluminum oxide, etc. which will produce the diffused scattering of light and thus render the electrolyte nontrans-parent in nature. The electrochromic display device which now comprises `~ a symmetrical device in which the electrolyte is sandwiched between two layers of the electrochromic material which itself is in contact with a transparent electronic conductor, the latter comprising an electrically conductive support, is then fitted with electrical contacts which are, in turn, connected to a source of electricity.
' ~2S618P~
As hereinbefore set forth, the power which is required to operate the electrochromic display will be greater than the power which is required to operate a liquid crystal display but less than that which is required to operate a light-emitting diode display. Generally speaking, the vol~age required to operate an electrochromic display de-vice may range from about 0.4 to about 1.5 volts with a change in color being effected for a period which may range from about 25 to about 500 milliseconds. In the range of response time to ~he electric current, it is to be noted that the response time of the electrochromic display is greater than the response time for a liquid crystal display, but less than that of the light-emitting display. Again, the power may come from any source such as a battery or electric current, either direct current or countercurrent in nature.
The following examples are given to illustrate a process for preparing an electrochromic device of the present invention. However, it is to be understood that these examples are given merely for purposes of illustration and that the present process is not necessarily limited thereto.
EXAMPLE I
In this example, a conductive glass substrate having a layer of tin oxide deposited thereon was placed in a sputter deposition cham-ber. The sputter deposition of tungsten trioxide on the tin oxide was effected at a pressure of about 100 torr (13;33 kPa ~abs)) for a period of 20 minutes using a combination of air and argon as the sputter gas, utilizing a tungsten target. J
A solution of a polymeric blend was prepared by admixing poly-(vinyl alcohol) and dodecamolybdophosphoric acid in a 50/50~ by weight 1256~3r~
amount with a sufficient amount of water to obtain a 2% solution of the blend. The polymeric blend was then cast on the tin oxide/tungsten tri-oxide coated glass and allowed to dry at ambient temperature to give a thin membrane f;lm which was approximately 5 microns in thickness.
Thereafter, the device in which the polymeric blend membrane acts as a solid electrolyte, was placed in a sputter deposition chamber and subjected to the sputter deposition of platinum thereon until a thickness of about 200 Angstroms of platinum was deposited on the sur-face of the membrane. Electrical contacts were then added to the plati-num which acted as a counter-electrode and to the glass containing the tin oxide deposited thereon which acted as the electronic conductor. An electric charge of 10 millicoulombs per square cm was charged to the de-vice and the tungsten oxide changed from transparent to blue.
EXAMPLE II
In a manner similar to that set forth in Example I above, an electrochromic display device was prepared by sputter-depositing tung-sten trioxide on the surface of a tin oxide glass-coated substrate.
The polymeric blend which formed a membrane, the latter acting as a solid electrolyte, was prepared by dissolving equal proportions by weight of poly(vinyl alcohol) and dodecatungstophosphoric acid. The polymer was cast on the surface of the electrochromic material and, after being al-lowed to dry, had platinum sputter-deposited thereon to form a counter-electrode. The tungsten oxide had a thickness of about 1000 Angstroms, the membrane a thickness of about 5 microns and the platinum a thickness of about 200 Angstroms. When an electric current ~as charged to the de-vice, the tungsten trioxide changed from transparent to a blue color.
~,256~8 ~
EXAMPLE III
To illustrate an electrochromic display device as shown in Figure 2 of the drawing, two pieces of conductive glass substrates hav-ing a layer of tin oxide deposited thereon were treated in a manner sim-ilar to that set forth in Example I above, that is, by being placed in a sputter depos;tion chamber. The pressure in the cylinder was reduced to approximately lO0 torr (13.33 kPa (abs)) and tungsten trioxide was sputter-deposited on the tin oxide surface utilizing a combination of air and argon as the sputter gas.
Thereafter, a solution of a polymeric blend was prepared by admixing equal amounts by weight of poly~acrylic acid) and dodecatungsto-phosphoric acid, plus a sufficient amount of titanium dioxide to impart an opaqueness or milk-like appearance to the polymeric solution, with water to obtain a 2% solution of the blend. The polymeric blend solu-tion was then cast on one of the tungsten trioxide-treated tin oxide-coated glass supports to obtain a thin film. Thereafter, the second tungsten trioxide-treated tin oxide-coated glass support was placed on the surface of the polymer, the tin oxide contacting the polymer. The device was allowed to dry at ambient temperature, electrical contacts were added to the conductive supports and a charge of lO millicoulombs/
square cm was charged to the device. The tungsten trioxide changed from transparent to a blue color, said blue color remaining after the charge had been discontinued.
Claims (11)
1. An electrochromic device comprising in combination an electronic conductor, an electrochromic material in contact with said conductor, a solid electrolyte comprising a blend of an organic polymer and a heteropoly acid or salt thereof disposed on said electrochromic material and a counter-electrode in contact with said solid electrolyte.
2. The electrochromic device as set forth in Claim 1 in which said electronic conductor comprises glass coated with an electrically conductive material.
3. The electrochromic device as set forth in Claim 2 in which said electrically conductive material comprises tin oxide or antimony tin oxide or indium tin oxide.
4. The electrochromic device as set forth in Claim 1 in which said electronic conductor comprises an electrically conductive polymer.
5. The electrochromic device as set forth in Claim 1 in which said electrochromic material comprises an oxide of a metal which possesses multiple oxidation states.
6. The electrochromic device as set forth in Claim 5 in which said electrochromic material comprises tungsten trioxide or molybdenum trioxide or vanadium trioxide or niobium trioxide or titanium trioxide.
7. The electrochromic device as set forth in Claim 1 in which said solid electrolyte comprises poly(vinyl alcohol)-dodecamolyb-dophosphoric acid or poly(acrylic acid)-dodecatungstophosphoric acid or poly(vinyl alcohol)-dodecatungstophosphoric acid or poly(vinyl alcohol)-ammonium molybdophosphoric acid or poly(acrylic acid)-uranyl orthophosphate.
8. The electrochromic device as set forth in Claim 1 in which said counter-electrode comprises palladium or platinum or nickel.
9. The electrochromic device as set forth in Claim 1 in which said counter-electrode comprises an electronic conductor and an electrochromic material in contact with said electrolyte.
10. The electrochromic device as set forth in Claim 10 in which said electrolyte contains an inert compound which will produce diffuse scattering of light.
11. The electrochromic device as set forth in Claim 11 in which said inert compound comprises titanium dioxide or zinc oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000499837A CA1256187A (en) | 1986-01-17 | 1986-01-17 | Electrochromic devices using proton-conducting acid- polymer blends as the solid electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000499837A CA1256187A (en) | 1986-01-17 | 1986-01-17 | Electrochromic devices using proton-conducting acid- polymer blends as the solid electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1256187A true CA1256187A (en) | 1989-06-20 |
Family
ID=4132300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000499837A Expired CA1256187A (en) | 1986-01-17 | 1986-01-17 | Electrochromic devices using proton-conducting acid- polymer blends as the solid electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1256187A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114149797A (en) * | 2021-12-06 | 2022-03-08 | 哈尔滨商业大学 | Dual-regulation multicolor composite material, preparation method thereof and electrochromic device |
-
1986
- 1986-01-17 CA CA000499837A patent/CA1256187A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114149797A (en) * | 2021-12-06 | 2022-03-08 | 哈尔滨商业大学 | Dual-regulation multicolor composite material, preparation method thereof and electrochromic device |
| CN114149797B (en) * | 2021-12-06 | 2023-10-27 | 哈尔滨商业大学 | Dual-regulation multi-color composite material, preparation method thereof and electrochromic device |
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