Annually, about four percent of the total U.S. energy consumption results from window inefficiencies due to poor insulation and high transmission of solar radiation that allows an undesired heat gain or loss in the building that increases cooling or heating costs. The removal or covering of windows requires an increase in costs for lighting and reduces the aesthetics and other benefits of natural light that have been demonstrated to increase a workforce's productivity and sense of well-being. Where blinds are used to avoid disruptive glare, frequently they are not reopened when the glare ceases.
To address these shortcomings, dynamic windows are at the forefront of energy efficient window research. Electrochromic windows that can controllably modulate visible light, and/or heat flux characteristics upon application of a controlled voltage are promising candidates to mitigate inefficiencies in windows, as the heat flux characteristics of the window can be manually or automatically controlled. However, no system has been demonstrated that independently and simultaneously varies the heat flow (near infrared (NIR) and/or middle infrared (MIR) transmittance) and the visible transparency of the window. While indium tin oxide (ITO) can be used as the transparent electrode(s) in dynamic windows, its inherent properties present many drawbacks for its use in flexible electrochromic devices (f-ECDs). For example, ITO on plastic cracks and becomes unusable when repeatedly bent, making it unsuitable for retrofitting existing windows. Furthermore, ITO reflects infrared (IR) light, and, therefore, does not permit IR transmittance at levels as high as might be desired.
In addition to smart window applications, absorptive/transmissive IR f-ECDs on suitable IR transparent conducting substrates could be used as bendable, lightweight IR shutters and filters for IR detectors and imaging systems. The IR technology area would greatly benefit from introducing f-ECDs as replacement of high-cost heavy mechanical counterparts.
Embodiments of the subject invention relate to an ECD that simultaneously allows independent heat and light control by regulation of one or more electrochromic cells in the ECD. The electrochromic system, according to embodiments of the invention, comprises at least one electrochromic cell, where those ECDs having a plurality of cells include at least one electrode of at least one of the cells that comprises a single walled carbon nanotube (SWNT) comprising film.
Each of the cells includes a working electrode, an electrochromic layer, an electrolyte layer, and a charge balancing layer. In one embodiment, a single electrochromic cell uses an electrochromic material that changes its absorbance/transmittance or reflectance in the visible and/or infrared spectral regions, allowing the simultaneous control of visible and IR modulation or just infrared contrast. The ECD can be used as a “smart window” or as an IR shutter/filter in a detecting/imaging system. In another embodiment, one of a plurality of independent electrochromic cells uses an electrochromic material that changes its absorbance or reflectance in the visible, while a second cell uses an electrochromic material that changes its absorbance or reflectance in the infrared. Therefore, by independently controlling the potential applied to the electrochromic cells, heating radiation (IR) and visible light passage can be independently controlled when the system is employed as a “smart window.”
The ECD can further comprise temperature and/or light sensors for automatic control. In one embodiment, a light sensor is included in a circuit to the cell using a visible absorptive or reflecting electrochromic material and a temperature sensor is included in the circuit to the cell using an infrared absorbing or reflecting electrochromic material.
The ECD can be free-standing or it can be in the form of a laminate that can be applied to an existing surface. The ECD allows manual or automatic control of the light and heat (infrared) through the system.
Embodiments of the invention are directed to electrochromic devices (ECDs) allowing control of IR absorbance or reflection independently of visible light or simultaneously with the visible modulation. The device can be free-standing or can be a laminate that can be attached to a surface of another device. For example, in one embodiment of the invention, the substrate upon which an ECD is deposited can be a glass or a plastic that constitutes the majority of the mass of an existing window. Single walled nanotube (SWNT) films have been developed for applications as transparent conductors, as disclosed in U.S. Pat. No. 7,261,852, which is incorporated herein by reference.
An ECD 16, according to an embodiment of the invention, comprises two independent cells in the form of a laminate, as shown in
In embodiments of the invention, the substrates 1, 7, or 13 are transparent and can be, for example, a plastic such as polyethylene (PE), polypropylene (PP), poly(ethylene terephthalate) (PET), poly(ethylene naphthalates) (PEN), poly(phenylene sulfide) (PSS), polycarbonate (PC), a polysulfone, a polyethersulfone, poly(methylmethacrylate) (PMMA), or any other transparent or transparent UV-stabilized material. In another embodiment of the invention, the substrates 1, 7, or 13 are transparent and can be an elastomer, for example, polydimethylsiloxane (PDMS) or other silicone, polybutadiene, polyisoprene, or any copolymers thereof In other embodiments of the invention, the substrate 1, 7, or 13 can be a glass, semiconductor, or other materials of suitable transmissivity in the desired electrochromic wavelength region. In embodiments of the invention, where the device is a new or replacement window, the transparent substrate 1, 7, or 13 can be the major portion of the window. Where the transparent substrate is the exterior portion of the window, the use of a tough plastic, for example, PC or PET, can reduce the thermal conductivity and increase the impact resistance relative to that of similarly thick glass windows, which are commonly employed in existing structures.
The SWNT comprising films 2, 6, 8, and 12 can be fabricated on the substrates 1, 7, or 13, as taught in Rinzler et al., U.S. Pat. No. 7,261,852, which is incorporated herein by reference. Any other methods of depositing a transparent and conductive SWNT comprising film on the substrate can be employed. The SWNT comprising film can include metallic nanowires, graphene sheets, conducting polymers and/or other semiconducting or insulating materials in a controlled manner. The SWNTs can be undoped or doped. The SWNT dopant can be, for example, sulfuric acid, nitric acid, ammonia, or a halogen.
In some embodiments of the invention, so called “sticky foot” polymers, as described in PCT Patent Application publication WO/2008/046010, are included with one or more of the SWNT films 2, 6, 8, and 12 to promote incorporation of conjugated and/or electrically conducting polymers. Such “sticky foot” polymers promote attachment, as approximately a monolayer, to the surface of the SWNTs. Functionalized “sticky foot” polymers can have pendant substituents, for example, perfluoroalkyl chains, ethylene oxide chains, alkyl chains, siloxane chains or combinations thereof, to increase or decrease the hydrophobicity of the SWNT film's surface.
The charging balancing layers 5 and 9 do not change color, yet undergo electrochemical redox reactions that balance the cell's charge during switching. In addition to conjugated polymers, other electroactive materials can be used to balance the charge during switching. Polymers that can be used as the charging balancing layer 5 or 9 include redox polymers that have specific spatially and electrostatically isolated highly localized electrochemically active sites. A typical redox polymer consists of a system where a redox-active transition metal based pendant group is covalently bound to a polymer backbone. The polymer backbone can be conjugated or non-conjugated. Non-limiting examples of redox active polymers that can be employed in embodiments of the invention include: poly(vinyl ferrocene) and copolymers thereof; poly(vinyltripyridyl cobalt dichloride) and copolymers thereof; poly(4-vinylpyridyl osmium bis-bipyridyl dichloride) and copolymers thereof; poly(pyrrole-co-N-benzyl ruthenium bis-bipyridyl chloride); poly(N-2-cyanoethyl-3,4-propylenedioxypyrrole); and polymers bearing the redox-active 2,2,6,6-tetramethylpiperidin-N-oxyl group, such as poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) and poly [2,3-bis(2,2,6,6-tetramethylpiperidine-N-oxycarbonyl)-norbornene].
The electrolyte layers 4 and 10 can be a gel electrolyte, a solid electrolyte, or an ionic liquid. In one embodiment of the invention, electrolyte layers 4 or 10 are gel electrolytes, such as an acetonitrile (ACN), propylene carbonate (PC), ethylene carbonate (EC), other alkylcarbonate, or mixed alkylcarbonates solutions containing poly(methyl methacrylate) and electrolyte salts, such as TBAPF6 or ionic liquids (ILs). Electrolyte salts contain organic cations, including, but not limited to, tetraalkylammonium or alkali metal cations, including Li+, Na+, K+, and Cs+with non-nucleophilic anions, including, but not limited to, tetrafluoroborate, perchlorate, triflate, bis(trifluoromethylsulfonyl)imide, or hexafluoroantimonate. Examples of ILs include, but are not limited to: pyridinium chloride; 1-butyl-3-methylimidazolium 1-ethyl-3-methylimidazolium dicyanamide; bis(trifluoro-methylsulfonyl)imide; and 1-butyl-3,5-dimethyl-pyridinium bromide. In another embodiment of the invention, electrolyte layers 4 or 10 can be solid state electrolytes. Solid electrolytes include polar polymer hosts, such as: poly(ethylene oxide); poly(propylene oxide); methoxyethoxyethoxy substituted polyphosphazene; polyether based polyurethanes; and other polymers that are able to dissolve metal salts and give ionically conducting complexes. Room temperature conductivities of 10−5 to 10−3 S/cm are typically attained. Enhanced electrochromic switching speeds can be attained where higher ionic conductivities are reached with these electrolytes at elevated temperature.
In one embodiment of the invention, the electrochromic layer 3 changes absorbance in the visible region and the electrochromic layer 12 changes absorbance or reflectance in the infrared. In other embodiments, the electrochromic layer 3 and/or layer 12 changes transmissivity in other regions of the EM spectrum, including UV, visible, near IR, short IR, mid IR, far IR, and microwave, as designed for the specific application of the system. In another embodiment of the invention, the electrochromic layers 3 and/or 12 reflect visible or infrared light, respectively. In other embodiments of the invention, at least one of the electrochromic layers 3 and/or 12 comprises an inorganic semiconductor. Electrochromic polymers that can be used for the electrochromic layer 3, include those comprising PProDOT, PEDOT, Ppy, PANI, and polymers taught in U.S. Pat. Nos. 7,807,758 and 6,791,738, and International Application Publication Nos. WO/2011/003076, WO/2010/138566, WO2010/062948, WO/2009/058877, WO/2009/117025, and WO/2008/118704, where all of these patents and published patent applications are incorporated by reference herein.
Electrochromic materials that absorb or reflect in the IR and can be used, according to embodiments of the invention, for the electrochromic layer 12, include, but are not restricted to: ruthenium(II) dioxolene complexes, polymers, and copolymers derived therefrom; tris(pyrazolyl)borato-molybdenum complexes, polymers, and copolymers derived therefrom; substituted and unsubstituted N,N,N′,N′-tetraphenyl-p-phenylenediamines (TPPA), polymers, and copolymers derived therefrom; substituted anthraquinone imides, polymers, and copolymers derived therefrom; dicarbonylhydrazine containing dinuclear ruthenium complexes, polymers, and copolymers derived therefrom; and poly(N-alkylalkylenedioxypyrrole)s; and metal oxide semiconductors, for example nickel, and/or tungsten oxide comprising semiconductors.
In other embodiments of the invention, the ECD includes two independent electrochromic cells coupled by the double-sided SWNT electrode, where the configuration of the electrochromic, electrolyte, and charge balancing layers differs from the configuration of
In another embodiment of the invention, the ECD includes at least one electrode comprising a SWNT film and the other electrode comprises a transparent conductor, such as a transparent conducting oxide (TCO), for example, indium-tin-oxide (ITO), MWNTs, DWNTs, graphene, and carbon nanohorns. Carbon comprising conductors can be doped or undoped. In another embodiment of the invention, the substrate is coated with a thin semi-transparent metalized layer, allowing partial reflection/partial transmittance of radiation. In yet another embodiment of the invention, the substrate is coated with a metalized layer, for example, a gold layer, to allow attenuated reflectance of radiation.
In another embodiment of the invention, the ECD comprises a single cell 28, as shown in
Another embodiment of the invention is directed to a window comprising at least one ECD laminate on at least one surface of the window. In another embodiment of the invention, a window fixture comprises at least one ECD laminate positioned essentially parallel to at least one surface of the window, where an enclosed volume exists between the electrochromic laminate and the window. In one embodiment, the volume between the ECD laminate and the window is filled with a gas, generally a dry gas, for example, dry air or an inert gas, such as nitrogen or argon, or is evacuated to form a vacuum between the window and the laminate.
In an embodiment of the invention, a window comprises the ECD, where the window is a transparent substrate of the ECD. In this embodiment of the invention, the ECD can be a flat plate, or can display curvature having any other shape, for example, a dome. Windows, according to this embodiment of the invention, can be used for structures that are not buildings, for example, face shields, wind shields for automobiles and other vehicles, or any other applications where the shape is preferentially not a flat plate but where independent control of the transmittance of visible and IR radiation is advantageous.
In an embodiment of the invention, the ECD can include one or more light sensors. The light sensors can detect any desired wavelengths or range of wavelengths on one or both faces of the ECD. The sensor can detect one or more wavelengths or a range of wavelengths in the visible and/or infrared portion of the electromagnetic spectrum. For example, two sensors can be included that independently detect the quantity of visible and IR light on one side of the ECD, such that the applied potential difference across the electrodes of one or both electrochromic cells of the ECD can be diminished or increased to change the visible or IR radiation transparency of the ECD in a desired manner based on the intensity of the radiation measured by the sensors. In another embodiment of the invention, one or more temperature sensors can be included on one or both faces of the ECD, such that the measured temperature can be used to trigger change of the applied potential difference across the electrodes of one or more electrochromic cells of the ECD. Other sensors, for example motion detectors, can be interfaced with the ECD. The signals from light and/or temperature sensors can be input to a microprocessor or other programmable device to permit the adjustment of the potential difference across the electrochromic cells of the ECD in a predetermined manner. The light and/or temperature sensors can be integral with the ECD or can be remote to the surfaces of the ECD. In this manner, the ECD can behave as a “smart window” that promotes solar heating in a structure when the exterior temperature is below a desired temperature, discourages solar heating when the exterior temperature is above a desired temperature, and independently allows a desired, often maximal, amount of sunlight to penetrate the window.
In another embodiment of the invention, the ECD comprises a single cell, similar to that shown in
All patents and patent applications referred to or cited herein are incorporated by reference in their entirety, including all figures and tables, to the extent they are not inconsistent with the explicit teachings of this specification.
It should be understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application.
The present application claims the benefit of U.S. Provisional Application Ser. No. 61/503,015, filed Jun. 30, 2011, which is hereby incorporated by reference herein in its entirety, including any figures, tables, or drawings.
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/US2012/044569 | 6/28/2012 | WO | 00 | 12/19/2013 |
Number | Date | Country | |
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61503015 | Jun 2011 | US |