WO2010039141A1 - Flexible panel based on electrochromic polymers - Google Patents

Flexible panel based on electrochromic polymers Download PDF

Info

Publication number
WO2010039141A1
WO2010039141A1 PCT/US2008/078599 US2008078599W WO2010039141A1 WO 2010039141 A1 WO2010039141 A1 WO 2010039141A1 US 2008078599 W US2008078599 W US 2008078599W WO 2010039141 A1 WO2010039141 A1 WO 2010039141A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
flexible
electrochromic
working
panel
Prior art date
Application number
PCT/US2008/078599
Other languages
French (fr)
Inventor
Chunye Xu
Chao Ma
Minoru Taya
Original Assignee
University Of Washington
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University Of Washington filed Critical University Of Washington
Priority to PCT/US2008/078599 priority Critical patent/WO2010039141A1/en
Publication of WO2010039141A1 publication Critical patent/WO2010039141A1/en

Links

Classifications

    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153Constructional details
    • G02F1/161Gaskets; Spacers; Sealing of cells; Filling or closing of cells
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/133305Flexible substrates, e.g. plastics, organic film
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1516Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
    • G02F1/15165Polymers

Definitions

  • Electrochromic (EC) materials are a subset of the family of chromogenic materials, which includes photochromic materials, and thermochromic materials. These materials change their tinting level or opacity when exposed to light (p/zotochromic), heat (thermochromic), or an electric potential (electrochromic). Chromogenic materials have attracted widespread interest in applications relating to the transmission of light.
  • chromogenic materials An early application for chromogenic materials was in sunglasses or prescription eyeglasses that darken when exposed to the sun. Such photochromic materials were first developed by researchers at Corning Incorporated in the late 1960s. Since that time, it has been recognized that chromogenic materials could potentially be used to produce window glass that can vary the amount of light transmitted, although the use of such materials is clearly not limited to that prospective application. Another likely application will be in the production of display devices. Indeed, EC technology is already employed in the displays of digital watches.
  • the EC layer is typically tungsten oxide (WO 3 ).
  • WO 3 tungsten oxide
  • U.S. Patent Nos. 5,598,293; 6,005,705; and 6,136,161 describe an inorganic thin film EC device based on a tungsten oxide EC layer.
  • Other inorganic EC materials such as molybdenum oxide, are also known. While many inorganic materials have been used as EC materials, difficulties in processing and a slow response time that is associated with many inorganic EC materials have created the need to develop different types of EC materials.
  • Conjugated, redox-active polymers represent one different type of EC material. These polymers (cathodic or anodic polymers) are inherently electrochromic and can be switched electrochemically (or chemically) between different color states.
  • a family of redox-active copolymers are described in U.S. Patent No. 5,883,220.
  • Another family of nitrogen-based heterocyclic organic EC materials is described in U.S. Patent No. 6,197,923.
  • Research into still other types of organic film EC materials continues, in hopes of identifying or developing EC materials that will be useful in commercial applications such as EC windows. There still exists room for improvement and development of new types of EC organic polymer films, and methods of making EC organic polymer films.
  • the EC devices that have thus far been constructed employ relatively rigid substrates. Polymer films are readily deposited on glass, and it is typically employed for this purpose when fabricating EC devices. However, for certain applications, it would be preferable to produce an ECD that is entirely flexible. Since a flexible ECD that is actuated with an applied electrical potential must retain the spacing between the working and counter electrodes comprising the device, it is not trivial to construct such a device. A flexible ECD must be capable of retaining the seal that keeps an electrolyte between the two electrodes, even when the device is repeatedly flexed. The configuration must enable bending of the device without sustaining damage.
  • flexible ECD clearly indicates an electrochromic display that is flexible and can be bent without being damaged.
  • the present novel approach is intended to produce a flexible EC panel and is not limited specifically to the use of a flexible panel only as a display device.
  • a flexible EC panel might be included in sunglasses.
  • the lens portion of the glasses comprising the flexible EC panel would be more readily fabricated as a planar multilayer configuration, but when mounted in the frames, would have the capability of being readily bent or flexed to conform to a frame that is designed to curve around a user's eyes. Accordingly, it will be understood that discussion of a "flexible ECD" is not intended to be limited only to a display device, but instead, is intended to more broadly apply to a flexible EC panel.
  • one aspect of this novel technology is directed to an exemplary method for producing a flexible electrochromic panel.
  • the method includes the steps of depositing a working electrochromic film on a first flexible polymer substrate.
  • the working electrochromic film is selected for its ability to repetitively change between at least a first state in which the working electrochromic film exhibits a first transmittance characteristic, and a second state in which the working electrochromic film exhibits a second, substantially different transmittance characteristic.
  • the term substantially different should be understood to mean that the different transmittance characteristics can be differentiated by the naked eye.
  • the working electrochromic film in the first state the working electrochromic film is generally an opaque color, and in the second state the working electrochromic film is substantially transparent. The change between states occurs as a result of the working electrochromic film undergoing a redox process.
  • the transmittance characteristics of some electrochromic polymers in the different states is a function of the applied voltage, such that one can vary the voltage applied to the EC polymer to selectively vary its transmittance (i.e., the EC polymer is oxidized or reduced, depending on the applied voltage, and different voltages can be applied to vary the degree of oxidation or reduction, resulting in changing the relative transmittance of the EC polymer).
  • an ion storage film is deposited on a second flexible polymer substrate.
  • the ion storage film chemically interacts with the working electrochromic film during the redox process.
  • the first and the second flexible polymer substrates are selected for a characteristic flexibility that enables them to be readily bent in an arc.
  • the first and the second flexible polymer substrates are then coupled together with a film sealant that is disposed between them.
  • the film sealant serves as a spacer and defines a volume that is disposed between the working electrochromic film and the ion storage film.
  • An electrolyte solution is injected into the volume defined by the film sealant.
  • the flexible electrochromic panel is then sealed to exclude moisture and oxygen, and to maintain the electrolyte solution within the volume.
  • the flexible electrochromic panel that is thus produced is capable of being bent in a substantial curve without experiencing damage.
  • the step of sealing the flexible electrochromic panel can include the step of curing the film sealant with ultraviolet light.
  • the film sealant can also define an inlet port in fluid communication with the volume.
  • the step of injecting the electrolyte solution into the volume can then include the step of injecting the electrolyte solution through the inlet port.
  • the step of sealing can include the step of sealing the inlet port with a sealant material after the electrolyte has been injected into the volume.
  • Another step of the method is providing terminals on the flexible electrochromic panel to enable a voltage to be applied to the working electrochromic film and to the ion storage film for selectively changing the working electrochromic film between the first state and the second state.
  • the method further includes the step of coating the first and the second flexible polymer substrates with an indium tin oxide (ITO) coating before depositing the working electrochromic film and the ion storage film on the flexible substrates.
  • ITO indium tin oxide
  • the method further includes the step of coating the first and the second flexible polymer substrates with an indium tin oxide (ITO) coating before depositing the working electrochromic film and the ion storage film on the flexible substrates.
  • ITO indium tin oxide
  • An exemplary embodiment employs a polyethylene terephthalate
  • PET polyethylene terephthalate
  • the method can then include the step of baking the ion storage film deposited on the second flexible polymer substrate at a sufficiently elevated temperature so as to evaporate a liquid from the vanadium oxide-titanium oxide composite that is deposited on the second flexible polymer substrate, while avoiding thermal damage to the second flexible polymer substrate.
  • At least one exemplary embodiment uses dimethyl substituted poly(3,4-propylenedioxythiophene) for the working electrochromic film, although it is contemplated that many other types of polymers might instead be used for this purpose.
  • Dimethyl substituted poly(3,4-propylenedioxythiophene) is also known as poly(3 ,4-(2,2-dimethylpropylene-dioxy)thiophene) and poly[3,3-dimethyl-3,4-dihydro- 2H-thieno[3,4-b][l,4] dioxepine]; and is referred to in abbreviated format as PPrODOT-Me 2 .
  • Another aspect of the novel technology is directed to a flexible electrochromic panel that is configured generally as discussed above in regard to the method for making such a device.
  • FIGURE 1 is a schematic diagram illustrating the layers of an exemplary flexible ECD configured in accord with the present novel approach
  • FIGURE 2 illustrates a schematic plan view and an isometric view of the exemplary flexible ECD that is being fabricated, showing the patterned inlet port of a film sealant layer that is adherently disposed between the counter layer and the working layer;
  • FIGURE 3 illustrates exemplary fabrication steps and components used for making a flexible ECD in accord with the present novel approach
  • FIGURE 4 is a graph showing an exemplary cyclic voltammetry (CV) curve of the electrochromic (EC) film on the flexible substrate for a potential range from about -1.5 V to about +1.5 V;
  • FIGURE 5 is a graph showing an exemplary CV curve of the counter film, which requires a potential of about 0.8 V to about 1.0 V;
  • FIGURE 6 is a graph illustrating the typical transmittance as a function of wavelength for both the transparent and opaque states, for a plurality of flexible ECDs configured according to the present novel approach;
  • FIGURES 7A-7D are graphs illustrating the response time for switching states as the applied potential is alternately stepped between -1.2 V and +1.2 V for each of four different flexible ECDs configured according to the present novel approach;
  • FIGURES 8A and 8B respectively illustrate an exemplary flexible
  • ECD in its transparent state and its colored (opaque) state as the appropriate potential is applied to switch to each of these states by leads attached to terminals on the device;
  • FIGURES 9A and 9B respectively illustrate an exemplary flexible
  • ECD in its normal flat state, and in its flexed or bent state that is achieved when opposed forces are applied to opposite ends of the device;
  • FIGURE 10 is a flowchart illustrating steps that are carried out to fabricate the exemplary flexible ECD.
  • electrochromic polymer materials have been developed that are blue, red, or green in color and which can be employed to produce a full color display.
  • An initial exemplary embodiment of the present novel approach employs a cathodic EC polymer material, poly [3,3 -dimethyl-3, 4-dihydra2H- thieno[3,4-b][l,4]dioxepine] (PPrODOT-Me 2 ), as a working material on which to fabricate a flexible electrochromic display (ECD) that can be controllably changed from a transparent state to a blue colored (opaque) state by applying an appropriate potential across the counter and working electrodes of the device.
  • ECD flexible electrochromic display
  • the PProDOT- Me 2 EC film exhibits a high transmittance contrast ratio (having 0% transmittance in its colored state) between a blue color and a transparent state, operates at low potentials, has high conductivity, and exhibits excellent thermal stability.
  • a plurality of different colors can be selectively provided by fabricating a flexible ECD with a plurality of different EC films, to produce a multicolor display or panel.
  • the flexibility of this ECD device makes it useful in many applications in which a rigid ECD fabricated using glass substrates would be unacceptable and readily broken, if the display or panel were flexed or bent while in use or during construction of the product that includes the EC device.
  • An exemplary flexible ECD 20 comprises a multilayer electrochromic polymer configuration, as illustrated in FIGURE 1.
  • ITO indium tin oxide
  • PET polyethylene terephthalate
  • the PProDOT- Me 2 polymer film was deposited from a 0.01 M monomer in a 0.1 M LiCKVAcetonitrile (ACN) solution on ITO coated PET substrate 22 (obtained from Sheldahl, Inc. of Minnesota), which has a surface resistance of about 20 ⁇ .
  • ACN LiCKVAcetonitrile
  • An oxidative electrochemical polymerization method was used to deposit polymer films onto the ITO PET substrate in this exemplary embodiment.
  • the monomer is oxidized and forms a radical cation, which undergoes a further coupling reaction with other monomers or radical cations, forming insoluble polymer chains on the electrode surface of the ITO PET substrate.
  • the applied potential during the deposition is 1.5-2.5 V, and the deposition time is from about 1 s to about 15 s. Due to the relatively low quality and conductivity of the ITO coating on the PET substrate, a copper tape can be applied to minimize the potential drop through the substrate surface.
  • a counter layer 26 of the flexible ECD is a vanadium oxide-titanium oxide (V 2 Os-TiO 2 ) composite film, which is also deposited on an ITO PET substrate 24 that is substantially identical to ITO coated substrate 22.
  • V 2 Os-TiO 2 vanadium oxide-titanium oxide
  • ITO coated substrate 22 an applied potential controlled to be about 3.5 V was used, resulting in a deposition time of about 10 s to about 20 s.
  • excess liquid needs to be evaporated from the deposited V 2 Os- TiO 2 composite film, which can be accomplished by baking the assembly in an oven at over 100 0 C.
  • the PET plastic comprising this substrate can experience a damaging deformation during heating at such an elevated temperature, it is necessary to carefully control the baking time and temperature.
  • the PET substrate After being coated with the V 2 Os-TiO 2 composite film, the PET substrate is placed on a flat glass substrate support and heated to about 104 0 C for 4 h.
  • This exemplary embodiment also includes a transparent electrolyte layer 30, which is a good conductor for small ions, such as ClO 4 " and Li + , and an insulator for electrons.
  • the transparent liquid electrolyte layer is sandwiched between the working and counter layers.
  • This transparent liquid electrolyte layer serves as an ion transport layer, and ions move quickly inside the transparent electrolyte layer during switching of the display device between states.
  • a gel or solid electrolyte can also be used, although empirical studies have suggested that liquid electrolytes offer enhanced performance.
  • the V 2 Os-TiO 2 composite film serves as an ion storage layer (i.e., an ion attracting layer) and works with the PProDOT-Me 2 film - each forming one part of a pair.
  • the V 2 Os-TiO 2 film When the EC film is reduced with an applied potential and changes color to blue (attracting positively charged lithium (Li) ions), the V 2 Os-TiO 2 film simultaneously attracts negatively charged perchlorate (ClO 4 ) ions.
  • the V 2 Os-TiO 2 film attracts positively charged Li + ions.
  • the V 2 Os-TiO 2 film While switching between these two states, the V 2 Os-TiO 2 film maintains a light green color.
  • the relatively light tint provided by the V 2 Os-TiO 2 film is acceptable for most applications. If a more optically transparent counter layer is desired, (i.e., a counter layer without the green tint), other counter layers, such as patterned gold or graphite layers, can also be employed.
  • an ultraviolet (UV) light cured film sealant 36 (FIGURE 2) was adopted to seal the flexible ECD.
  • This cured film sealant serves as spacer 32 (see FIGURE 1) that is sized to maintain about a 30 ⁇ m gap between the working and counter electrodes, while also serving as a barrier (in addition to barrier 34) to prevent moisture and oxygen absorption by the display device.
  • the cured film sealant thus maintains the separation between the two electrodes, while sealing the flexible ECD, and is patterned to provide an inlet port 40 into a relatively thin volume 42 for holding liquid electrolyte 30 (FIGURE 1), as shown in FIGURE 2.
  • liquid transparent electrolyte solution is injected through the inlet port of the film sealant, and inlet port 40 is then sealed with a glue or other suitable adhesive/sealant.
  • a glue or other suitable adhesive/sealant it should be recognized that the concepts disclosed herein encompass embodiments in which the cured film sealant also functions as barrier 34 (such that separate barrier and spacer elements are not required, with the cured film sealant simultaneously implementing both elements).
  • FIGURE 2 note that while substrate 22 and 24 overlap in a center portion of the device (i.e., proximate thin volume 42), a right edge 24a (relative to the drawing figure) of substrate 24 extends beyond the center portion, and a left edge 22a (relative to the drawing figure) of substrate 22 extends beyond the center portion.
  • the substrates do not overlap at these edge portions.
  • the specific dimensions of the edge portions are not critical, but these edge portions do provide a functional role, in that electrical connections can be made relatively easily at these edge portions.
  • FIGURE 8A and 8B schematically illustrate such connections.
  • the edges act as terminals for electrical connections.
  • FIGURE 3 The components that are assembled to produce a flexible ECD 50 are shown in FIGURE 3.
  • the steps used for fabricating flexible ECD 50 are illustrated in FIGURE 10, and the following discussion is directed to both FIGURES 3 and 10.
  • steps 132 and 134 working layer 28 comprising the EC film, and counter layer 26 comprising the V 2 Os-TiO 2 composite film are respectively deposited on ITO PET substrates 22 and 24.
  • Film sealant 36 is patterned and applied between the working and counter substrates in a step 136.
  • the liquid electrolyte solution is then injected through inlet port 40 provided in the patterned film sealant.
  • a step 140 the open inlet port is sealed using a UV curable glue or other suitable adhesive or sealant, and the entire device is then irradiated with UV light for about 10 minutes, which causes the sealant to fully bond between the two substrate layers and to become impermeable to moisture and oxygen.
  • the flexible ECD, barriers 34 can be provided to more fully seal the ends of the layers comprising the flexible ECD, but are not shown in FIGURE 3, and this aspect is not included as a step shown in FIGURE 10.
  • FIGURE 4 illustrates an exemplary cyclic voltammetry (CV) curve 60 of the EC film for the flexible substrate, which ranges from about -1.5 V to about +1.5 V in potential.
  • CV cyclic voltammetry
  • T% light transmittance
  • Several flexible devices were fabricated and a typical (average) T% for visible light wavelengths was measured, yielding the results shown in FIGURE 6.
  • a flat line curve 80 at the top of the graph in this Figure represents T% in the transparent state of the devices, and indicates that the device provides high transmittance in the visible light range.
  • a "U" shaped curve 82 at the bottom of the graph is the T% in the opaque state and has a minimum transmittance in the range of 550 nm-600 nm, which is the most sensitive portion of the visible light spectrum, to human eyes.
  • the contrast ratio of light transmittance at a certain wavelength is defined as the difference between T% for the transparent and the opaque states at that wavelength.
  • the highest contrast ratio, ⁇ T% max , for these exemplary display devices appears at a wavelength of about 580 nm, as indicated by the double arrowhead line in FIGURE 6.
  • FIGURES 7A-7D illustrate the measured results of reversing the potential applied to four devices, in regard to the cyclic light transmittance. This technique is used to test the response time and repeatability of the display devices. In this test, the potential was stepped between -1.2 V and ⁇ 1.2 V, with a delay time of about 2 seconds between each stepped change in the potential polarity.
  • the light transmittance was measured at 580 nm wavelength.
  • T% max , T% n , and AT% were measured.
  • a curve 92 indicates that the range was from 62% to 5%, with ⁇ T% ⁇ 57%.
  • a curve 94 indicates that the range was from 57% to 3%, with ⁇ T% ⁇ 54%.
  • the range of these parameters is controlled by the thickness of the EC polymer film, i.e., the thicker the EC polymer film, the darker will be the film; and conversely, the thinner the EC polymer film, the lighter will be the film.
  • the thickness of the EC polymer film can be controlled during film deposition by adjusting parameters such as deposition potential and charging time.
  • the response time of the flexible devices is relatively fast, since they can be switched from a completely transparent state to a completely opaque state (and vice versa) in about 1 second.
  • FIGURES 8 A and 8B A test setup 100 for the flexible ECDs is illustrated in FIGURES 8 A and 8B.
  • the flexible ECD was changed from a colored or opaque state 102 as shown in FIGURE 8 A to a transparent state 102', as shown in FIGURE 8B, by applying the appropriate potential through leads 104 and 106, which are clipped to terminals 108 and 110, respectively.
  • the light transmittance for the colored state displayed almost no change.
  • the light transmittance of the transparent state decreased slightly during the first 5,000 cycles, but became stable after that. At the beginning of this test, the light transmittance was about 55.2% ⁇ 2.4%, and after 40,000 cycles, it had decreased to about 52.1% ⁇ 2.6%.
  • FIGURES 9A and 9B respectively illustrate a device made in accord with the novel approach described above in a normal flat state 120, and in a flexed or bent state 120', which is achieved when a force F is applied to opposite edges of the flexible ECD causing the edges to move toward each other and the center of the flexible ECD to bend outwardly.
  • the capability of the flexible ECD to bend without being damaged enables it to be used in any application where such bending of the device may occur.
  • prior art rigid ECDs would be damaged if an attempt were made to flex them in this manner.

Abstract

A flexible electrochromic (EC) panel that is usable for a display device or for other applications in which at least a region of the panel is selectively caused to change opacity. An exemplary panel includes an EC working layer or electrode formed of a PProDOT-Me2 polymer film that is deposited on an indium tin oxide (ITO)-coated polyethylene terephthalate (PET) flexible substrate. Similarly, a counter electrode is formed by depositing a vanadium oxide-titanium oxide (V2O5-TiO2) composite film on another ITO PET coated flexible substrate. An ultraviolet light-cured film sealant is employed to seal the flexible panel and also serves as a spacer between the electrodes. The film sealant is patterned to define a volume for injecting an electrolyte solution through an inlet port provided in the film sealant. The inlet port is then closed. The EC panel can readily be flexed without damage.

Description

FLEXIBLE PANEL BASED ON ELECTROCHROMIC POLYMERS
Background
[0001] Electrochromic (EC) materials are a subset of the family of chromogenic materials, which includes photochromic materials, and thermochromic materials. These materials change their tinting level or opacity when exposed to light (p/zotochromic), heat (thermochromic), or an electric potential (electrochromic). Chromogenic materials have attracted widespread interest in applications relating to the transmission of light.
[0002] An early application for chromogenic materials was in sunglasses or prescription eyeglasses that darken when exposed to the sun. Such photochromic materials were first developed by researchers at Corning Incorporated in the late 1960s. Since that time, it has been recognized that chromogenic materials could potentially be used to produce window glass that can vary the amount of light transmitted, although the use of such materials is clearly not limited to that prospective application. Another likely application will be in the production of display devices. Indeed, EC technology is already employed in the displays of digital watches.
[0003] Several different distinct types of EC materials are known. Three primary types are: inorganic thin films, organic polymer films, and organic solutions. For many applications, the use of a liquid EC material is inconvenient, and as a result, inorganic thin films and organic polymer films appear to have more industrial applications.
[0004] For inorganic thin film-based EC devices, the EC layer is typically tungsten oxide (WO3). U.S. Patent Nos. 5,598,293; 6,005,705; and 6,136,161 describe an inorganic thin film EC device based on a tungsten oxide EC layer. Other inorganic EC materials, such as molybdenum oxide, are also known. While many inorganic materials have been used as EC materials, difficulties in processing and a slow response time that is associated with many inorganic EC materials have created the need to develop different types of EC materials.
[0005] Conjugated, redox-active polymers represent one different type of EC material. These polymers (cathodic or anodic polymers) are inherently electrochromic and can be switched electrochemically (or chemically) between different color states. A family of redox-active copolymers are described in U.S. Patent No. 5,883,220. Another family of nitrogen-based heterocyclic organic EC materials is described in U.S. Patent No. 6,197,923. Research into still other types of organic film EC materials continues, in hopes of identifying or developing EC materials that will be useful in commercial applications such as EC windows. There still exists room for improvement and development of new types of EC organic polymer films, and methods of making EC organic polymer films.
[0006] The EC devices that have thus far been constructed employ relatively rigid substrates. Polymer films are readily deposited on glass, and it is typically employed for this purpose when fabricating EC devices. However, for certain applications, it would be preferable to produce an ECD that is entirely flexible. Since a flexible ECD that is actuated with an applied electrical potential must retain the spacing between the working and counter electrodes comprising the device, it is not trivial to construct such a device. A flexible ECD must be capable of retaining the seal that keeps an electrolyte between the two electrodes, even when the device is repeatedly flexed. The configuration must enable bending of the device without sustaining damage.
Summary
[0007] As used herein the term flexible ECD clearly indicates an electrochromic display that is flexible and can be bent without being damaged. An initial effort was made to create such a display, and much of the following discussion is directed to the procedure for fabricating the device. However, it should be understood that in a broader sense, the present novel approach is intended to produce a flexible EC panel and is not limited specifically to the use of a flexible panel only as a display device. For example, instead of being used for a display, a flexible EC panel might be included in sunglasses. The lens portion of the glasses comprising the flexible EC panel would be more readily fabricated as a planar multilayer configuration, but when mounted in the frames, would have the capability of being readily bent or flexed to conform to a frame that is designed to curve around a user's eyes. Accordingly, it will be understood that discussion of a "flexible ECD" is not intended to be limited only to a display device, but instead, is intended to more broadly apply to a flexible EC panel.
[0008] More specifically, one aspect of this novel technology is directed to an exemplary method for producing a flexible electrochromic panel. The method includes the steps of depositing a working electrochromic film on a first flexible polymer substrate. The working electrochromic film is selected for its ability to repetitively change between at least a first state in which the working electrochromic film exhibits a first transmittance characteristic, and a second state in which the working electrochromic film exhibits a second, substantially different transmittance characteristic. The term substantially different should be understood to mean that the different transmittance characteristics can be differentiated by the naked eye. In an exemplary embodiment, in the first state the working electrochromic film is generally an opaque color, and in the second state the working electrochromic film is substantially transparent. The change between states occurs as a result of the working electrochromic film undergoing a redox process.
[0009] The specific use of the flexible electrochromic panel will generally determine how different the first and second transmittance characteristics will be. Furthermore, it should be recognized that the transmittance characteristics of some electrochromic polymers in the different states is a function of the applied voltage, such that one can vary the voltage applied to the EC polymer to selectively vary its transmittance (i.e., the EC polymer is oxidized or reduced, depending on the applied voltage, and different voltages can be applied to vary the degree of oxidation or reduction, resulting in changing the relative transmittance of the EC polymer).
[0010] Referring once again to the deposition of the ITO conductive layer on a first flexible polymer substrate; similarly, an ion storage film is deposited on a second flexible polymer substrate. The ion storage film chemically interacts with the working electrochromic film during the redox process. The first and the second flexible polymer substrates are selected for a characteristic flexibility that enables them to be readily bent in an arc. The first and the second flexible polymer substrates are then coupled together with a film sealant that is disposed between them. The film sealant serves as a spacer and defines a volume that is disposed between the working electrochromic film and the ion storage film. An electrolyte solution is injected into the volume defined by the film sealant. The flexible electrochromic panel is then sealed to exclude moisture and oxygen, and to maintain the electrolyte solution within the volume. The flexible electrochromic panel that is thus produced is capable of being bent in a substantial curve without experiencing damage.
[0011] The step of sealing the flexible electrochromic panel can include the step of curing the film sealant with ultraviolet light.
[0012] The film sealant can also define an inlet port in fluid communication with the volume. The step of injecting the electrolyte solution into the volume can then include the step of injecting the electrolyte solution through the inlet port. In this case, the step of sealing can include the step of sealing the inlet port with a sealant material after the electrolyte has been injected into the volume.
[0013] Another step of the method is providing terminals on the flexible electrochromic panel to enable a voltage to be applied to the working electrochromic film and to the ion storage film for selectively changing the working electrochromic film between the first state and the second state.
[0014] In at least one exemplary embodiment, the method further includes the step of coating the first and the second flexible polymer substrates with an indium tin oxide (ITO) coating before depositing the working electrochromic film and the ion storage film on the flexible substrates. While ITO represents an exemplary conductive coating, it should be recognized that other conductive coatings can be employed. In many embodiments generally transparent coatings are preferred, however, it should be understood that in some embodiments a tinted coating may be acceptable, or even preferred.
[0015] An exemplary embodiment employs a polyethylene terephthalate
(PET) material for the first and the second flexible polymer substrates and a vanadium oxide-titanium oxide composite for the ion storage film. While PET represents an exemplary flexible polymer substrate, it should be recognized that other flexible polymer substrates can be employed. The method can then include the step of baking the ion storage film deposited on the second flexible polymer substrate at a sufficiently elevated temperature so as to evaporate a liquid from the vanadium oxide-titanium oxide composite that is deposited on the second flexible polymer substrate, while avoiding thermal damage to the second flexible polymer substrate. At least one exemplary embodiment uses dimethyl substituted poly(3,4-propylenedioxythiophene) for the working electrochromic film, although it is contemplated that many other types of polymers might instead be used for this purpose. Dimethyl substituted poly(3,4-propylenedioxythiophene) is also known as poly(3 ,4-(2,2-dimethylpropylene-dioxy)thiophene) and poly[3,3-dimethyl-3,4-dihydro- 2H-thieno[3,4-b][l,4] dioxepine]; and is referred to in abbreviated format as PPrODOT-Me2.
[0016] Another aspect of the novel technology is directed to a flexible electrochromic panel that is configured generally as discussed above in regard to the method for making such a device.
[0017] This application specifically incorporates by reference the disclosures and drawings of each patent application and issued patent identified above as a related application.
[0018] This Summary has been provided to introduce a few concepts in a simplified form that are further described in detail below in the Description. However, this Summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
Drawings
[0019] Various aspects and attendant advantages of one or more exemplary embodiments and modifications thereto will become more readily appreciated as the same becomes better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein:
[0020] FIGURE 1 is a schematic diagram illustrating the layers of an exemplary flexible ECD configured in accord with the present novel approach;
[0021] FIGURE 2 illustrates a schematic plan view and an isometric view of the exemplary flexible ECD that is being fabricated, showing the patterned inlet port of a film sealant layer that is adherently disposed between the counter layer and the working layer;
[0022] FIGURE 3 illustrates exemplary fabrication steps and components used for making a flexible ECD in accord with the present novel approach;
[0023] FIGURE 4 is a graph showing an exemplary cyclic voltammetry (CV) curve of the electrochromic (EC) film on the flexible substrate for a potential range from about -1.5 V to about +1.5 V; [0024] FIGURE 5 is a graph showing an exemplary CV curve of the counter film, which requires a potential of about 0.8 V to about 1.0 V;
[0025] FIGURE 6 is a graph illustrating the typical transmittance as a function of wavelength for both the transparent and opaque states, for a plurality of flexible ECDs configured according to the present novel approach;
[0026] FIGURES 7A-7D are graphs illustrating the response time for switching states as the applied potential is alternately stepped between -1.2 V and +1.2 V for each of four different flexible ECDs configured according to the present novel approach;
[0027] FIGURES 8A and 8B respectively illustrate an exemplary flexible
ECD in its transparent state and its colored (opaque) state as the appropriate potential is applied to switch to each of these states by leads attached to terminals on the device;
[0028] FIGURES 9A and 9B respectively illustrate an exemplary flexible
ECD in its normal flat state, and in its flexed or bent state that is achieved when opposed forces are applied to opposite ends of the device; and
[0029] FIGURE 10 is a flowchart illustrating steps that are carried out to fabricate the exemplary flexible ECD.
Description Figures and Disclosed Embodiments Are Not Limiting
[0030] One or more exemplary embodiments are illustrated in referenced
Figures of the drawings. It is intended that each embodiment and the Figures disclosed herein are to be considered illustrative rather than restrictive. No limitation on the scope of the technology and of the claims that follow is to be imputed to the examples shown in the drawings and discussed herein.
[0031] Several new kinds of electrochromic polymer materials have been developed that are blue, red, or green in color and which can be employed to produce a full color display. An initial exemplary embodiment of the present novel approach employs a cathodic EC polymer material, poly [3,3 -dimethyl-3, 4-dihydra2H- thieno[3,4-b][l,4]dioxepine] (PPrODOT-Me2), as a working material on which to fabricate a flexible electrochromic display (ECD) that can be controllably changed from a transparent state to a blue colored (opaque) state by applying an appropriate potential across the counter and working electrodes of the device. The PProDOT- Me2 EC film exhibits a high transmittance contrast ratio (having 0% transmittance in its colored state) between a blue color and a transparent state, operates at low potentials, has high conductivity, and exhibits excellent thermal stability. It will be understood that other EC films having different colors can alternatively be employed in the flexible ECD, and it is contemplated that a plurality of different colors can be selectively provided by fabricating a flexible ECD with a plurality of different EC films, to produce a multicolor display or panel. The flexibility of this ECD device makes it useful in many applications in which a rigid ECD fabricated using glass substrates would be unacceptable and readily broken, if the display or panel were flexed or bent while in use or during construction of the product that includes the EC device.
[0032] An exemplary flexible ECD 20 comprises a multilayer electrochromic polymer configuration, as illustrated in FIGURE 1. An electrochromic working layer 28, i.e., the PPrODOT-Me2 polymer film, is deposited on an indium tin oxide (ITO)-coated polyethylene terephthalate (PET) substrate 22, which is relatively flexible, in contrast to the rigid glass or the non-flexible polymer substrates used in prior electrochromic devices. In making this exemplary embodiment, the PProDOT- Me2 polymer film was deposited from a 0.01 M monomer in a 0.1 M LiCKVAcetonitrile (ACN) solution on ITO coated PET substrate 22 (obtained from Sheldahl, Inc. of Minnesota), which has a surface resistance of about 20 Ω.
[0033] An oxidative electrochemical polymerization method was used to deposit polymer films onto the ITO PET substrate in this exemplary embodiment. The monomer is oxidized and forms a radical cation, which undergoes a further coupling reaction with other monomers or radical cations, forming insoluble polymer chains on the electrode surface of the ITO PET substrate. The applied potential during the deposition is 1.5-2.5 V, and the deposition time is from about 1 s to about 15 s. Due to the relatively low quality and conductivity of the ITO coating on the PET substrate, a copper tape can be applied to minimize the potential drop through the substrate surface.
[0034] A counter layer 26 of the flexible ECD is a vanadium oxide-titanium oxide (V2Os-TiO2) composite film, which is also deposited on an ITO PET substrate 24 that is substantially identical to ITO coated substrate 22. To deposit the V2Os-TiO2 composite film onto the ITO PET substrate, an applied potential controlled to be about 3.5 V was used, resulting in a deposition time of about 10 s to about 20 s. However, excess liquid needs to be evaporated from the deposited V2Os- TiO2 composite film, which can be accomplished by baking the assembly in an oven at over 1000C. Since the PET plastic comprising this substrate can experience a damaging deformation during heating at such an elevated temperature, it is necessary to carefully control the baking time and temperature. After being coated with the V2Os-TiO2 composite film, the PET substrate is placed on a flat glass substrate support and heated to about 1040C for 4 h.
[0035] This exemplary embodiment also includes a transparent electrolyte layer 30, which is a good conductor for small ions, such as ClO4 " and Li+, and an insulator for electrons. The transparent liquid electrolyte layer is sandwiched between the working and counter layers. This transparent liquid electrolyte layer serves as an ion transport layer, and ions move quickly inside the transparent electrolyte layer during switching of the display device between states. Note that a gel or solid electrolyte can also be used, although empirical studies have suggested that liquid electrolytes offer enhanced performance. The V2Os-TiO2 composite film serves as an ion storage layer (i.e., an ion attracting layer) and works with the PProDOT-Me2 film - each forming one part of a pair. When the EC film is reduced with an applied potential and changes color to blue (attracting positively charged lithium (Li) ions), the V2Os-TiO2 film simultaneously attracts negatively charged perchlorate (ClO4) ions. When the EC film is oxidized with an opposite potential and changes to its transparent state (attracting negatively charged perchlorate (ClO4) ions), the V2Os-TiO2 film attracts positively charged Li+ ions. While switching between these two states, the V2Os-TiO2 film maintains a light green color. The relatively light tint provided by the V2Os-TiO2 film is acceptable for most applications. If a more optically transparent counter layer is desired, (i.e., a counter layer without the green tint), other counter layers, such as patterned gold or graphite layers, can also be employed.
[0036] For this exemplary embodiment of the flexible substrate device, an ultraviolet (UV) light cured film sealant 36 (FIGURE 2) was adopted to seal the flexible ECD. This cured film sealant serves as spacer 32 (see FIGURE 1) that is sized to maintain about a 30 μm gap between the working and counter electrodes, while also serving as a barrier (in addition to barrier 34) to prevent moisture and oxygen absorption by the display device. The cured film sealant thus maintains the separation between the two electrodes, while sealing the flexible ECD, and is patterned to provide an inlet port 40 into a relatively thin volume 42 for holding liquid electrolyte 30 (FIGURE 1), as shown in FIGURE 2. The liquid transparent electrolyte solution is injected through the inlet port of the film sealant, and inlet port 40 is then sealed with a glue or other suitable adhesive/sealant. It should be recognized that the concepts disclosed herein encompass embodiments in which the cured film sealant also functions as barrier 34 (such that separate barrier and spacer elements are not required, with the cured film sealant simultaneously implementing both elements).
[0037] Referring to FIGURE 2, note that while substrate 22 and 24 overlap in a center portion of the device (i.e., proximate thin volume 42), a right edge 24a (relative to the drawing figure) of substrate 24 extends beyond the center portion, and a left edge 22a (relative to the drawing figure) of substrate 22 extends beyond the center portion. Significantly, the substrates do not overlap at these edge portions. The specific dimensions of the edge portions are not critical, but these edge portions do provide a functional role, in that electrical connections can be made relatively easily at these edge portions. FIGURE 8A and 8B schematically illustrate such connections. Thus, the edges act as terminals for electrical connections.
[0038] The components that are assembled to produce a flexible ECD 50 are shown in FIGURE 3. The steps used for fabricating flexible ECD 50 are illustrated in FIGURE 10, and the following discussion is directed to both FIGURES 3 and 10. In a flowchart 130, in steps 132 and 134, working layer 28 comprising the EC film, and counter layer 26 comprising the V2Os-TiO2 composite film are respectively deposited on ITO PET substrates 22 and 24. Film sealant 36 is patterned and applied between the working and counter substrates in a step 136. In a step 138, the liquid electrolyte solution is then injected through inlet port 40 provided in the patterned film sealant. After this electrolyte injection is completed, in a step 140, the open inlet port is sealed using a UV curable glue or other suitable adhesive or sealant, and the entire device is then irradiated with UV light for about 10 minutes, which causes the sealant to fully bond between the two substrate layers and to become impermeable to moisture and oxygen. Before the UV light is used for curing the sealant, the flexible ECD, barriers 34 (see FIGURE 1) can be provided to more fully seal the ends of the layers comprising the flexible ECD, but are not shown in FIGURE 3, and this aspect is not included as a step shown in FIGURE 10.
[0039] FIGURE 4 illustrates an exemplary cyclic voltammetry (CV) curve 60 of the EC film for the flexible substrate, which ranges from about -1.5 V to about +1.5 V in potential. Two peaks (positive and negative), which indicate the reduction and oxidation of the EC polymer, can be observed around ±0.4 V. Although the redox potential of the EC polymer is around ±0.4 V, a potential of about ±1.2 V is actually used to operate this flexible ECD, because the redox of the V2O5- TiO2 counter film requires a higher potential, i.e., approximately 0.8 V-I. O V, as shown by a CV curve 70 in FIGURE 5.
[0040] The measurement of light transmittance (i.e., T%) by the device was carried out using a UV-vis-NIR spectrometer. Several flexible devices were fabricated and a typical (average) T% for visible light wavelengths was measured, yielding the results shown in FIGURE 6. A flat line curve 80 at the top of the graph in this Figure represents T% in the transparent state of the devices, and indicates that the device provides high transmittance in the visible light range. A "U" shaped curve 82 at the bottom of the graph is the T% in the opaque state and has a minimum transmittance in the range of 550 nm-600 nm, which is the most sensitive portion of the visible light spectrum, to human eyes. Here, the contrast ratio of light transmittance at a certain wavelength (AT%) is defined as the difference between T% for the transparent and the opaque states at that wavelength. The highest contrast ratio, ΔT%max, for these exemplary display devices appears at a wavelength of about 580 nm, as indicated by the double arrowhead line in FIGURE 6.
[0041] FIGURES 7A-7D illustrate the measured results of reversing the potential applied to four devices, in regard to the cyclic light transmittance. This technique is used to test the response time and repeatability of the display devices. In this test, the potential was stepped between -1.2 V and ±1.2 V, with a delay time of about 2 seconds between each stepped change in the potential polarity.
[0042] The light transmittance was measured at 580 nm wavelength. For different devices, different T%max, T%n, and AT% were measured. For a device 1, a curve 90 indicates that the range was from 54% for the transparent state, to 2% for the opaque state, with ΔT%=52%. For device 2, a curve 92 indicates that the range was from 62% to 5%, with ΔT%~57%. For device 3, a curve 94 indicates that the range was from 57% to 3%, with ΔT%~54%. And, for device 4, a curve 96 indicates that the range was from 56% to 3%, with ΔT%=53. The range of these parameters is controlled by the thickness of the EC polymer film, i.e., the thicker the EC polymer film, the darker will be the film; and conversely, the thinner the EC polymer film, the lighter will be the film. The thickness of the EC polymer film can be controlled during film deposition by adjusting parameters such as deposition potential and charging time. The response time of the flexible devices is relatively fast, since they can be switched from a completely transparent state to a completely opaque state (and vice versa) in about 1 second.
[0043] The exemplary flexible ECDs that were produced as described above exhibited good stability over 40,000 cycles of switching between states. A test setup 100 for the flexible ECDs is illustrated in FIGURES 8 A and 8B. In this test setup, the flexible ECD was changed from a colored or opaque state 102 as shown in FIGURE 8 A to a transparent state 102', as shown in FIGURE 8B, by applying the appropriate potential through leads 104 and 106, which are clipped to terminals 108 and 110, respectively. During these tests, the light transmittance for the colored state displayed almost no change. The light transmittance of the transparent state decreased slightly during the first 5,000 cycles, but became stable after that. At the beginning of this test, the light transmittance was about 55.2% ± 2.4%, and after 40,000 cycles, it had decreased to about 52.1% ± 2.6%.
[0044] FIGURES 9A and 9B respectively illustrate a device made in accord with the novel approach described above in a normal flat state 120, and in a flexed or bent state 120', which is achieved when a force F is applied to opposite edges of the flexible ECD causing the edges to move toward each other and the center of the flexible ECD to bend outwardly. The capability of the flexible ECD to bend without being damaged enables it to be used in any application where such bending of the device may occur. In contrast, prior art rigid ECDs would be damaged if an attempt were made to flex them in this manner.
[0045] Although the concepts disclosed herein have been described in connection with the preferred form of practicing them and modifications thereto, those of ordinary skill in the art will understand that many other modifications can be made thereto within the scope of the claims that follow. Accordingly, it is not intended that the scope of these concepts in any way be limited by the above description, but instead be determined entirely by reference to the claims that follow.

Claims

The invention in which an exclusive right is claimed is defined by the following:
1. A method for producing a flexible electrochromic panel, comprising the steps of:
(a) depositing a working electrochromic film on a first flexible polymer substrate, the working electrochromic film being selected for its ability to repetitively change between at least:
(i) a first state in which the working electrochromic film exhibits a first transmittance characteristic; and
(ii) a second state in which the working electrochromic film exhibits a second transmittance characteristic, where the first and second transmittance characteristics are substantially different, as a result of the working electrochromic film undergoing a redox process;
(b) depositing an ion storage film on a second flexible polymer substrate, the ion storage film chemically interacting with the working electrochromic film during the redox process, wherein the first and the second flexible polymer substrates are selected for a characteristic flexibility that enables them to be readily bent in an arc;
(c) coupling the first and the second flexible polymer substrates together with a film sealant that is disposed between the first and the second flexible polymer substrates, the film sealant serving as a spacer and defining a volume that is disposed between the working electrochromic film and the ion storage film;
(d) introducing an electrolyte into the volume defined by the film sealant; and
(e) sealing the flexible electrochromic panel to exclude moisture and oxygen, and to maintain the electrolyte within the volume, the flexible electrochromic panel being capable of being bent in a substantial curve without experiencing damage.
2. The method of Claim 1, wherein the step of introducing the electrolyte comprises the step of introducing a liquid electrolyte.
3. The method of Claim 1, wherein the step of sealing the flexible electrochromic panel comprises the step of curing the film sealant with ultraviolet light.
4. The method of Claim 1, wherein the film sealant also defines an inlet port in fluid communication with the volume, and wherein the step of injecting the electrolyte solution into the volume comprises the step of introducing the electrolyte through the inlet port.
5. The method of Claim 4, wherein the step of sealing includes the step of sealing the inlet port with a sealant material after the electrolyte has been introduced into the volume.
6. The method of Claim 1, further comprising the step of providing terminals on the flexible electrochromic panel to enable a voltage to be applied to the working electrochromic film and to the ion storage film for selectively changing the working electrochromic film between the first state and the second state.
7. The method of Claim 1 , further comprising the step of coating the first and the second flexible polymer substrates with an indium tin oxide (ITO) coating before the steps of depositing the working electrochromic film and the ion storage film.
8. The method of Claim 1, further comprising the step of using a polyethylene terephthalate (PET) material for the first and the second flexible polymer substrates.
9. The method of Claim 1, further comprising the step of using a vanadium oxide-titanium oxide composite for the ion storage film.
10. The method of Claim 9, further comprising the step of baking the ion storage film deposited on the second flexible polymer substrate at a sufficiently elevated temperature so as to evaporate a liquid from the vanadium oxide-titanium oxide composite that is deposited on the second flexible polymer substrate, while avoiding thermal damage to the second flexible polymer substrate.
11. The method of Claim 1, further comprising the step of using a PPrODOT-Me2 polymer for the working electrochromic film.
12. A flexible electrochromic panel, comprising:
(a) a first flexible polymer substrate on which is deposited a working electrochromic film, the working electrochromic film being selected for its ability to repetitively change between at least:
(i) a first state in which the working electrochromic film exhibits a first transmittance characteristic; and
(ii) a second state in which the working electrochromic film exhibits a second transmittance characteristic, where the first and second transmittance characteristics are substantially different, as a result of the working electrochromic film undergoing a redox process;
(b) a second flexible polymer substrate on which is deposited an ion storage film, the ion storage film chemically interacting with the working electrochromic film during the redox process, wherein the first and the second flexible polymer substrates are characterized by being relatively flexible and readily bent in an arc;
(c) a film sealant that couples the first and the second flexible polymer substrates together and serves as a spacer between them, the film sealant defining a volume that is disposed between the working electrochromic film and the ion storage film; and
(d) an electrolyte disposed within the volume defined by the film sealant, the electrolyte providing and conducting ions between the working electrochromic film and the ion storage film during the redox process, to enable the working electrochromic film to change between the first and the second states.
13. The flexible electrochromic panel of Claim 12, wherein the film sealant is formed of a material that is cured by exposure to an ultraviolet light, to adhesively join the first flexible polymer substrate to the second flexible polymer substrate.
14. The flexible electrochromic panel of Claim 12, wherein the film sealant further defines an inlet port that provides a fluid path into the volume for introducing the electrolyte into the volume.
15. The flexible electrochromic panel of Claim 14, further comprising a sealant material introduced into the inlet port to seal the inlet port after the electrolyte has been introduced into the volume.
16. The flexible electrochromic panel of Claim 12, further comprising terminals that are electrically coupled to the working electrochromic film and to the ion storage film, for selectively applying a potential to cause the working electrochromic film to change between the first state and the second state.
17. The flexible electrochromic panel of Claim 12, wherein the first and the second flexible polymer substrates each include an indium tin oxide (ITO) coating respectively underlying deposits of the working electrochromic film and the ion storage film.
18. The flexible electrochromic panel of Claim 12, wherein the first and the second flexible polymer substrates are each formed of a polyethylene terephthalate (PET) material.
19. The flexible electrochromic panel of Claim 12, wherein the ion storage film comprises a vanadium oxide-titanium oxide composite.
20. The flexible electrochromic panel of Claim 12, wherein the working electrochromic film comprises a PPrODOT-Me2 polymer.
21. The flexible electrochromic panel of Claim 12, wherein the electrolyte comprises a liquid electrolyte.
22. The flexible electrochromic panel of Claim 12, further comprising a barrier disposed around one or more edges to seal the flexible electrochromic panel, preventing entry of liquid and oxygen from a surrounding environment.
PCT/US2008/078599 2008-10-02 2008-10-02 Flexible panel based on electrochromic polymers WO2010039141A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US2008/078599 WO2010039141A1 (en) 2008-10-02 2008-10-02 Flexible panel based on electrochromic polymers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2008/078599 WO2010039141A1 (en) 2008-10-02 2008-10-02 Flexible panel based on electrochromic polymers

Publications (1)

Publication Number Publication Date
WO2010039141A1 true WO2010039141A1 (en) 2010-04-08

Family

ID=42073751

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2008/078599 WO2010039141A1 (en) 2008-10-02 2008-10-02 Flexible panel based on electrochromic polymers

Country Status (1)

Country Link
WO (1) WO2010039141A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9099575B2 (en) 2013-07-16 2015-08-04 Cree, Inc. Solid state lighting devices and fabrication methods including deposited light-affecting elements

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4702963A (en) * 1981-04-03 1987-10-27 Optical Coating Laboratory, Inc. Flexible polymer film with vapor impermeable coating
US4761061A (en) * 1985-09-19 1988-08-02 Asahi Glass Company Ltd. Method for fabrication of electrochromic device and the same fabricated by the method
US20050025980A1 (en) * 2001-04-24 2005-02-03 Anoop Agrawal Electrochromic safety glazing
US6950220B2 (en) * 2002-03-18 2005-09-27 E Ink Corporation Electro-optic displays, and methods for driving same
US20070292606A1 (en) * 2006-06-20 2007-12-20 Eclipse Energy Systems Electrochromic Device with Self-forming Ion transfer Layer and Lithium Fluoro-Nitride Electrolyte

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4702963A (en) * 1981-04-03 1987-10-27 Optical Coating Laboratory, Inc. Flexible polymer film with vapor impermeable coating
US4761061A (en) * 1985-09-19 1988-08-02 Asahi Glass Company Ltd. Method for fabrication of electrochromic device and the same fabricated by the method
US20050025980A1 (en) * 2001-04-24 2005-02-03 Anoop Agrawal Electrochromic safety glazing
US6950220B2 (en) * 2002-03-18 2005-09-27 E Ink Corporation Electro-optic displays, and methods for driving same
US20070292606A1 (en) * 2006-06-20 2007-12-20 Eclipse Energy Systems Electrochromic Device with Self-forming Ion transfer Layer and Lithium Fluoro-Nitride Electrolyte

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9099575B2 (en) 2013-07-16 2015-08-04 Cree, Inc. Solid state lighting devices and fabrication methods including deposited light-affecting elements

Similar Documents

Publication Publication Date Title
US7826124B2 (en) Flexible panel based on electrochromic polymers
US10254616B2 (en) Variable transmittance optical filter with substantially co-planar electrode system
Ma et al. Flexible electrochromic device based on poly (3, 4-(2, 2-dimethylpropylenedioxy) thiophene)
US7999992B2 (en) Charge conducting medium
US7586663B1 (en) Gel polymer electrolytes
Heuer et al. Electrochromic window based on conducting poly (3, 4‐ethylenedioxythiophene)–poly (styrene sulfonate)
US7450291B2 (en) Multi-cell electrochromic devices
Xu et al. Switchable window based on electrochromic polymers
TWI486697B (en) Electro-chromic display element, display apparatus, and driving method
US11698565B2 (en) Electrochromic device and method for manufacturing electrochromic device
US20130235323A1 (en) Electrochromic devices prepared from the in situ formation of conjugated polymers
US20110211245A1 (en) Transparent electroactive system
Ma et al. Electrochromic kinetics of nanostructured poly (3, 4-(2, 2-dimethylpropylenedioxy) thiophene) film on plastic substrate
Seshadri et al. Optimization, preparation, and electrical short evaluation for 30 cm2 active area dual conjugated polymer electrochromic windows
CN210123513U (en) Patterned electrochromic device and electrochromic glass
WO2010039141A1 (en) Flexible panel based on electrochromic polymers
WO2006094052A2 (en) Gel polymer electrolytes
US20200272013A1 (en) Electrochromic device based on three-dimensional motion of lithium ions and application thereof
Nishikitani et al. Thermal and optical behavior of electrochromic windows fabricated with carbon-based counterelectrode
TWI450009B (en) Electrochromic device and method of manufacturing the same
EP4343418A1 (en) Electrochromic element and eyeglass lens
JP2003015164A (en) Electrochromic element
Ma et al. Color Switchable Goggle Lens Based on Electrochromic Polymer Devices
Dong et al. Conducting polymer-based patterned electrochromic window for vehicle sun strips
AU2006265759B2 (en) Charge conducting medium

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08824386

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08824386

Country of ref document: EP

Kind code of ref document: A1