Electrochromic device

• US 4,728,177 A
• Filed: 09/04/1985
• Issued: 03/01/1988
• Est. Priority Date: 09/04/1984
• Status: Expired due to Fees

• Current Assignee: British Technology Group Ltd.
• Original Assignee: National Research Development Corporation
• Inventors: Green, Mino
• Primary Examiner(s): Arnold, Bruce Y.
• Application Number:
  US06/772,456
• Time in Patent Office: 909 Days
• Field of Search: 350/357, 235/382.5
• US Class Current: 359/270
• CPC Class Codes: G02F 1/1524 Transition metal compounds
• CPC Class Codes: G02F 1/153 Constructional details
• CPC Class Codes: G06K 1/126 by photographic or thermographic registration recording apparatus for measuring instruments G01D15/00
• CPC Class Codes: G06K 19/14 the marking being sensed by radiation
• CPC Class Codes: G07F 7/086 by passive credit-cards adapted therefor, e.g. constructive particularities to avoid counterfeiting, e.g. by inclusion of a physical or chemical security-layer for security documents G07D7/00; for the reading of record-carriers in general G06K7/00; for the design of coded credit-cards G06K19/10

Abstract

A thin, flexible, portable device (11) may be used as a credit card. The device is encapsulated by front and rear plastics layers. Viewed from the front the device comprises a first electrode of a transparent electrically conductive layer (13); a layer (14) of an electrochromic, metal-sensitive compound which is capable of dissolving metal atoms and which changes color in so doing; a layer of a solid, fast ion conducting electrolyte (15); a second layer of electrochromic material (16), acting as a second electrode; and a layer of electrically conductive material (17). The solid electrolyte layer (15) is substantially non-conductive at room temperature but is highly conductive of metal ions at a raised temperature. To erase information, the entire device is heated to 150° C., and a potential difference is applied between the front electrode (14) and the rear electrode (16), driving all metal atoms out of the front electrochromic material into the rear electrode (16). To write information, a reverse potential is applied and selected localized areas of the device are heated, so that coloration atoms are driven into the electrochromic layer (14) only at selected areas.

Claims

1. An electrochromic device comprising at least one electrochromic zone and means for selectively supplying to and withdrawing from said zone guest atoms which produce a colour change in said zone, which means is substantially inoperable at room temperature but is operable at elevated temperature.

2. An electrochromic device as claimed in claim 1 comprising

a first electrode comprising a layer of a transparent electrically conducting material,

a layer of an electrochromic material comprising a metal-sensitive compound which is capable of dissolving metal atoms and which changes colour in so doing,

a layer of solid electrolyte, the solid electrolyte being a fast ion conductor in which a fast ion is an ion of the metal which dissolves in the metal-sensitive compound to change the colour thereof, the layer of metal-sensitive compound being in contact with the first electrode and being in contact with the fast ion conductor, and

a second electrode, the second electrode being in contact with the said fast ion conductor and being capable of providing and accepting ions the same as the said fast ions of the fast ion conductor, in which the mobility of the fast ions or corresponding atoms in at least one of the said electrolyte, the second electrode and the electrochromic layer, is or are temperature dependent, there being substantially no mobility at room temperature but the mobility increasing substantially with increase of temperature, whereby the device may be written into or erased by application of a potential difference across the two electrodes at a substantially raised temperature, the display being stable and non-changeable by application of similar potential differences at room temperature.

3. A device according to claim 2 in which the said solid electrolyte is made sufficiently opaque to isolate the said second electrode optically when the device is viewed through the first electrode, the second electrode being used as a sink and source of ions to pass through the solid electrolyte to the electrochromic layer at the front of the device, a contrast being produced between a view of the solid electrolyte and a view of the electrochromic layer when coloured by metal atoms.

4. A device according to claim 2 in which the said second electrode comprises a layer of a material comprising a metal-sensitive compound, which is capable of dissolving the same metal atoms as the first mentioned electrochromic layer.

5. A device according to claim 4 wherein the material of the second electrode changes colour in response to said metal atoms, thus constituting a second electrochromic chromic layer, the said solid electrolyte layer being substantially transparent, and the two electrochromic layers being of different thickness and such that the same quantity of colouration atoms in the thicker layer produces a deeper colouration and in the thinner layer produces a lesser colouration, whereby when the device is heated and appropriate potentials are applied, metal atoms can be transferred from one electrochromic layer to the other through the solid electrolyte so as to produce either a greater or lesser colouration of the device.

6. A device according to claim 4 in which the metal-sensitive compound is an oxide of a transition metal selected from the group comprising tungsten oxide (WO₃), molybdenum oxide (MoO3₃), vanadium oxide (V₂ O₅), iridium oxide (Ir0₂) and niobium oxide (Nb₂ O₅), and solid solutions of at least two thereof.

7. A device according to claim 4 wherein the material of the second electrode is an oxide bronze which, at least in thin layers, undergoes no substantial visible colour change on a substantial change in the quantity of said metal atoms dissolved therein.

8. A device as claimed in claim 7 wherein the said oxide bronze is based on a solid solution of MoO₃ an V₂ O₅.

9. A device as claimed in claim 8 wherein the formula ratio of MoO₃ to V₂ O₅ is substantially 1:

1.

10. A device according to claim 2 in which the said fast ion is an alkali metal selected from the group comprising lithium, sodium and potassium.

11. A device according to claim 2 in which the said first electrode and the said second electrode each extend over a substantial display area of the device on which display area information is to be written, and both electrodes are provided with electrical contacts for applying a general electrical potential difference across the first electrochromic layer and the solid electrolyte layer over the whole display area of the device, the arrangement of the device being such that information can be written in operation at different locations within the said display area by localised heating of the device during application of the general potential difference over the whole display area.

12. An electrochromic device as claimed in claim 1 comprising

a first electrode comprising a layer of a transparent electrically conducting material,

a layer of an electrochromic material comprising a metal-sensitive compound which is capable of dissolving metal atoms and which changes colour in so doing,

a layer of a solid electrolyte, the solid electrolyte being a fast ion conductor in which a fast ion is an ion of the metal which dissolves in the metal-sensitive compound to change the colour thereof, and the layer of metal-sensitive compound being in contact with the first electrode and being in contact with the fast ion conductor, and

a second electrode, the second electrode being in contact with the said fast ion conductor and being capable of providing and accepting ions the same as the said fast ions of the fast ion conductor,

in which the solid electrolyte is substantially non-conductive at room temperature but is readily conductive of the said fast ions at increased temperature, whereby a visible display may be written into or erased from the device by application of a potential difference across the two electrodes at a substantially raised temperature, the display being stable and non-changeable by application of similar potential differences at room temperature.

13. A device according to claim 1 in which the mobility of atoms and/or ions in the device is sufficiently increased to allow writing and erasing of information at temperatures of 110°

C.

14. A device according to claim 1 in which the device is a thin, flexible, portable device and generally of the size and form of a credit card.

15. A device according to claim 1 in which the electrochromic zone is provided by an oxide bronze of a transition material in its highest oxidation state.

16. A device according to claim 2 in which the said solid electrolyte is a polymeric/inorganic solid electrolyte containing an alkali metal.

17. A device according to claim 16 in which the said solid electrolyte comprises a combination of an alkylene oxide selected from the group consisting of polyethylene oxide and polypropylene oxide with an alkali metal compound.

18. A device according to claim 2 in which the device has a display area on which information is to be displayed, and there are provided a plurality of electrical contacts leading to different locations within the display area, whereby different required potentials can be applied to different selected locations of the display area g during an overall heating of the whole display area, to effect writing and erasing of information in the display area.

19. Information storage and display apparatus comprising as an information storage and display medium an electrochromic device comprising:

a first electrode including a layer of a transparent electrically conducting material;

a layer of an electrochromic material including a metal-sensitive compound which is capable of dissolving metal atoms and which changes color in so doing;

a layer of solid electrolyte, the solid electrolyte being a fast ion conductor in which a fast ion is an ion of the metal which dissolves in the metal-sensitive compound to change the colour thereof, the layer of metal-sensitive compound being in contact with the first electrode and being in contact with the fast ion conductor;

a second electrode, the second electrode being in contact with said fast ion conductor and being capable of providing and accepting ions the same as said fast ions of the fast ion conductor, in which the mobility of the fast ions or corresponding atoms in at least one of said electrolyte, said second electrode and said electrochromic layer, is or are temperature dependent, there being substantially no mobility at room temperature but the mobility increasing substantially with increase of temperature, whereby the device may be written into or erased by application of a potential difference across the two electrodes at a substantially raised temperature, the display being stable and non-changeable by application of similar potential differences at room temperature, and in which said first electrode and said second electrode each extend over a substantial display area of the device on which display area information is to be written, and both electrodes are provided with electrical contacts for applying a general electrical potential difference across the first electrochromic layer and the solid electrolyte layer over the whole display area of the device, the arrangement of the device being such that information can be written at different locations within said display area by localized heating of the device during application of the general potential difference over the whole display area and comprising as means for writing information into or erasing information from said device;

an enclosure;

an aperture allowing insertion of the device into the enclosure; and

means for applying a general electrical potential difference across the device over the whole of the display area of the device, and means for selectively applying heat to individual locations in the display area.

20. Information storage and display apparatus comprising as an information storage and display medium an electrochromic device comprising:

a first electrode including a layer of a transparent electrically conducting material;

a layer of an electrochromic material including a metal-sensitive compound which is capable of dissolving metal atoms and which changes color in so doing;

a layer of solid electrolyte, the solid electrolyte being a fast ion conductor in which a fast ion is an ion of the metal which dissolves in the metal-sensitive compound to change the color thereof, the layer of metal-sensitive compound being in contact with the first electrode and being in contact with the fast ion conductor;

a second electrode, the second electrode being in contact with said fast ion conductor and being capable of providing and accepting ions the same as the said fast ions of the fast ion conductor, in which the mobility of the fast ions or corresponding atoms in at least one of said electrolyte, said second electrode and said electrochromic layer, is or are temperature dependent, there being substantially no mobility at room temperature but the mobility increasing substantially with increase of temperature whereby the device may be written into or erased by application of a potential difference across the two electrodes at a substantially raised temperature, the display being stable and non-changeable by application of similar potential differences at room temperature, and in which the device has a display area on which information is to be displayed, and there are provided a plurality of electrical contacts leading to different locations within the display area, whereby different required potentials can be applied to different selected locations of the display area during an overall heating of the whole display are, to effect writing and erasing of information in the diaplay area, and comprising as means for writing information into or erasing information from said device;

an enclosure;

an aperture allowing insertion of the display device into the enclosure; and

means for applying a general, overall heating effect over the whole of a display area of the device, and means for selectively applying a potential difference across the device at individual locations in the display area.