Electrochromic inks

Compositions – Electrically conductive or emissive compositions – Metal compound containing

Reexamination Certificate

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Details

C252S520400, C252S520500, C205S078000, C205S109000, C205S158000

Reexamination Certificate

active

06294111

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates in general to the manufacture of electrochromic devices, and, more particularly, to an apparatus and method for assembling electrochromic cells which, when activated, produce a visual change of state and may be adapted for use in a variety of devices.
BACKGROUND OF THE INVENTION
Electrochromic cells of various designs have been proposed for use in such diverse apparatus as graphics displays, wrist watch displays, variable transmission windows and mirrors, and voltage or state-of-charge indicators for batteries, among others. Although their specific constructions may vary considerably depending on their intended application, most electrochromic devices possess several common characteristic features. Typically, an electrochromic device is comprised of an electrochemical cell having a first electrically conductive electrode which functions as cathode, a second electrically conductive electrode which functions as an anode, and a medium through which the first and second electrodes communicate to effectuate a visible change in the cell under the application of a DC voltage applied to a circuit including the first and second electrodes. The medium through which the electrodes communicate normally assumes the form of solid, semi-solid or liquid electrolyte. Any of the electrodes and the electrolyte may comprise an electrochromic material which responds to the current induced by the applied DC voltage so as to produce the desired visible change in the cell.
The operation of an electrochemical cell may produce permanent or reversible ionization or deionization of metals contained in either the electrolyte and/or at least one of the electrodes which results in an oxidation or reduction (redox) reaction at the respective electrodes. The cell is usually a confined space wherein the first and second electrodes are separated from one another by the electrolyte, possibly in conjunction with a spacing means. In addition, the cell normally includes at least one substrate, which may be fabricated from flexible or rigid material, through which the metallic deposition or dissolution occurring within the cell may be observed. For example, the visible change in the cell may be observed through the substrate if the substrate is substantially transparent or if the substrate contains an orifice or window through which the visible change may be observed.
Examples of electrochemical devices defined by enclosed cells with rigid substrates and a liquid electrolyte in communication with first and second electrodes include U.S. Pat. Nos. 4,116,535, 4,188,095, 4,285,575 and 4,902,108.
U.S. Pat. No. 5,411,817 discloses a charge indicator for a battery, in which a layer, between an electrode pair, comprises an antioxidant, a photographic color coupler dispersion and a photographic color developer. Various possible compositions for this layer are disclosed, but within the constraints just described, no disclosure appears to be provided to the effect that the electrochemical process, in which electrolyte color is transformed, is reversible without reversing the polarity of the electrodes. The other alternative applications disclosed, as a disposable electric meter and a “phone card,” appear to imply that the electrochemical process is not reversible.
U.S. Pat. No. 3,720,869 discloses a method of determining a state-of-charge condition of an electrode in an electric cell by measuring the resistance of a cell electrode by its conversion between a metallic and non-metallic phase.
U.S. Pat. No. 3,667,039 discloses measuring instruments utilizing liquid crystalline elements that exhibit visible change in response to input signals above given threshold levels.
Several U.S. patents to Warszawski disclose light modulating devices as well as processes for making or using the same. These are U.S. Pat. Nos. 5,054,894, 5,056,899, 5,074,648, 5,078,480, 5,080,470 and 5,082,355. The substantive disclosures of all six of these patents are virtually identical. Thus, for convenience, these patents will be collectively referred to as the “Warszawski patents.”
The Warszawski patents disclose numerous embodiments in the way of realizing several different types of light modulating devices, e.g., in large-scale environments, such as large signs in public locales. These patents emphasize maintaining the structural integrity of the light modulating devices disclosed, particularly in the case of large-scale devices, such that the electrolyte-electrode interfaces will not be unduly affected by local discontinuities and/or stresses.
To this end, the Warszawski patents propose the use of electrolyte layers, between opposing electrodes, that maintain a high degree of flexibility, and it is specifically proposed that the electrolyte material be plastic or viscoelastic. Also for the purpose of maintaining structural cohesion, it is proposed that the electrolyte layers either be provided with a separate adhesive or be self-adhesive themselves, to ensure adequate bonding with the electrodes.
Although the Warszawski patents appear to contemplate the use of electrodes that are not necessarily flat, there appears to be no teaching or suggestion to the effect of rendering the electrodes themselves as flexible. Thus, it would appear the Warszawski patents, while contemplating the use of flexible electrolyte layers, assume that the electrodes flanking the electrolyte layer(s) will essentially be rigid. This would appear to be particularly true in the case of large-scale public signs.
With regard to the manufacture of the light modulating devices disclosed in the Warszawski patents, different techniques are proposed, such as thick-film application techniques and cut-out techniques. The thick-film application techniques involve silk screening, air gap, helical wire bar and related techniques. The cut-out techniques involve, for example, the production of a composite, that includes an electrode with the electrolyte, and then applying the composite to another electrode. Contemplated are techniques such as extrusion, rolling, calendering, coating and the like, as well as punching, stamping and laser cutting.
U.S. Pat. No. 4,497,881 describes a battery charge indicator that is essentially formed from components already present within the battery itself. Particularly, there is disposed within the battery a charge producing compound which apparently could constitute the electrolyte, the anode gel, the cathode material or a combination of two or more of such compounds. This charge producing compound is provided just within the outer cylindrical surface of the battery housing and is configured to adopt a given color, such as black, when the battery has a full charge and gradually changes to a different color, such as gray, when the battery charge is depleted. A small hole or window is provided in the outer surface of the battery housing in order to enable the user to view the color of the charge producing compound. This patent appears to emphasize the use of materials already present in a conventional battery, rather than adding additional compounds or structures for indicating color.
U.S. Pat. No. 4,917,973 discloses a secondary battery in which one of the electrodes of the battery itself changes color in accordance with the voltage between the positive and negative electrodes of the battery. A window or hole is provided for viewing the color change of the aforementioned electrode. This patent appears to be limited solely to secondary batteries, i.e. significantly small, generally disk-shaped batteries.
U.S. Pat. No. 5,256,500 teaches a battery, such as a lithium battery, having a built-in lifetime indicator. Primarily, this patent is directed to lithium batteries, but also contemplates that the invention disclosed therein be utilized in conjunction with other types of batteries, such as manganese batteries and nickel cadmium batteries. It is generally suggested that an “indication element”, as part of a “lifetime indicator” be provided within the battery itself. Various types of indicators are contemplated

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