Chromogenic glazing

• US 20030227663A1
• Filed: 10/25/2002
• Published: 12/11/2003
• Est. Priority Date: 05/04/2000
• Status: Active Grant

• Current Assignee: Schott AG (Carl-Zeiss-Stiftung)
• Original Assignee: SCHOTT CORPORATION AND DONNELLY CORPORATION
• Inventors: Hansen, Stephan, Zhang, Raymond, Agrawal, Anoop, Tonazzi, Juan Carlos Lopez
• Granted Patent: US 6,795,226 B2
• Time in Patent Office: Days
• US Class Current: 359/265
• CPC Class Codes: B32B 17/10036 comprising two outer glass sheets
• CPC Class Codes: B32B 17/10174 Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
• CPC Class Codes: B32B 17/10513 Electrochromic layer
• CPC Class Codes: G02F 1/1503 caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
• CPC Class Codes: G02F 1/1524 Transition metal compounds
• CPC Class Codes: G02F 1/1525 characterised by a particular ion transporting layer, e.g. electrolyte
• CPC Class Codes: G02F 1/153 Constructional details
• CPC Class Codes: G02F 1/155 Electrodes
• CPC Class Codes: G02F 1/157 Structural association of cells with optical devices, e.g. reflectors or illuminating devices
• CPC Class Codes: G02F 1/161 Gaskets; Spacers; Sealing of cells; Filling or closing of cells
• CPC Class Codes: G02F 1/163 Operation of electrochromic cells, e.g. electrodeposition cells; Circuit arrangements therefor
• CPC Class Codes: G02F 2001/1555 Counter electrode

Abstract

A transparent chromogenic assembly in which color changes are selectively effectable over predefined areas comprises a pair of facing transparent substrates (15, 21, 28) each covered with a conductive layer divided into individual energizeable areas each provided with a set of busbars (187, 188). A passive layer may be superimposed over one of the substrates, its color being chosen so that the color and the transmissivity of the passive layer accommodates the range of color change and transmissivity of the electrochromic layer to maintain the transmitted color of the panel in a warm or neutral shade. Various other chromogenic windows, devices and systems are also disclosed.

Claims

1. A transparent chromogenic assembly, comprising:

a. a pair of facing transparent substrates defining a cavity for enclosing an electrolyte medium;

facing surfaces of the substrates each having a conductive transparent coating, said conductive coating of at least one of said substrates being interrupted along a demarcation line having a thickness of at least 0.01 mm to insulate contiguous areas on opposite sides of said line from one another, the conductive coating of at least one of the substrates being overlain with an electrochromic layer; and

b. a set of busbars deposed toward the periphery of each of said areas.

2. A transparent chromogenic assembly according to claim 1 further including an adhesive spacer element interposed between said substrates.

3. A transparent chromogenic assembly according to claim 2 wherein said spacer element is adapted to insulate a portion of said busbars from exposure to said electrolyte.

4. A transparent chromogenic assembly according to claim 1 wherein each set of said busbars is individually energizeable to effect a color change through a respective one of said areas.

5. A transparent chromogenic assembly according to claim 1 wherein said electrolyte exhibits chromogenic properties.

6. A transparent chromogenic assembly according to claim 1 wherein a portion of said busbars is provided with a passivation coating to insulate said portion from said electrolyte.

7. A transparent chromogenic assembly according to claim 1 wherein a portion of each set of busbars extends from the facing surface of a respective substrate over an edge thereof to form an electrical connector.

8. A transparent chromogenic assembly according to claim 1 wherein each set of said busbars adjoins at least two sides of a respective one of said areas.

9. A transparent chromogenic assembly according to claim 1 wherein said transparent conductive coating comprises a material selected from the group consisting of a doped oxide of tin and indium-tin oxide.

10. A transparent chromogenic assembly according to claim 1 wherein at least one of said substrates is either tempered, strengthened or tempered and strengthened.

11. A transparent chromogenic assembly according to claim 2 wherein said electrochromic layer comprises at least one transition metal oxide.

12. A transparent chromogenic assembly according to claim 11 wherein said one transition metal oxide comprises tungsten oxide.

13. A transparent chromogenic assembly according to claim 1 having a counterelectrode layer on a surface of said substrates facing the surface containing said electrochromic layer.

14. A transparent chromogenic assembly according to claim 13 wherein said counterelectrode mixture contains an oxide selected from the group consisting of lithium oxide, nickel oxide, vanadium oxide and manganese oxide.

15. A transparent chromogenic assembly according to claim 1 wherein said electrolyte medium has at least one dissociable salt and one UV stabilizer.

16. A transparent chromogenic assembly according to claim 1 wherein said electrolyte medium includes a solvent or plasticizer containing a sulfolane.

17. A transparent chromogenic assembly according to claim 16 wherein said electrolyte medium is converted to a solid material by incorporation of a material selected from the group consisting of polymers, in-situ polymerizable monomers and nano-partical inorganic oxides.

18. A transparent chromogenic assembly according to claim 16 wherein said electrolyte is thickened by incorporation of a material selected from the group consisting of polymers and nano-particle inorganic oxides.

19. A transparent chromogenic panel for use on the exterior of a transportation vehicle exposed to the weather requiring an average current less than 10 μ

A/cm² of active area to maintain any desired state of transmission at a temperature of up to 85°

C. for a duration of at least 8 hours.

20. A transparent electrochromic panel according to claim 19 having inorganic electrochromic and counterelectrodes defining said active area, said electrodes being selected principally from the transition metal oxides, such as tungsten oxide and vanadium oxide, respectively, and having a liquid or solid polymer matrix electrolyte containing a sufficient amount of a sulfolane to act as a solvent and/or plasticizer for said electrolyte and a water content lower than 2000 ppm, preferably as low as 10 ppm.

21. A transparent chromogenic panel according to claim 19 which imparts to the perceiver a warm or neutral perceived color comprising:

an active component layer and a passive component layer in which the active component layer is selected from the group consisting of electrochromic, liquid crystal, user-controllable-photochromic, polymer-dispersed-liquid crystal or suspended particle devices and the passive component layer is selected from the group consisting of substrates or covers for the active layer, said active and said passive layers being chosen so that the color and the transmissivity of the passive layer accommodates the range of color change in the active layer to maintain the transmitted color of the panel in a warm or neutral shade, where warm colors on the L*C*h color sphere scale correspond to C having a value between 15 and 45;

h having a value between 100 and 20, and where the value of L depends on the darkness of the glass or preferred degree of photopic transmission desired.

22. A transparent electrochromic panel as in claim 21 wherein the neutral colors correspond to C less than 15, preferably less than 5, and h between 0 and 360, while L can be any number yielding the desired photopic transmission.

23. A transparent electrochromic panel according to claim 21 wherein said active component layer comprises:

a. a pair of facing glass substrates separated by a spacer to define a cavity for an electrolyte medium, facing surfaces of said substrates each having a conductive transparent coating, said conductive coating being interrupted on at least one of said substrates to define individual areas, the conductive coating of at least one of the substrates being overlain with an electrochromic layer;

b. a set of individually energizable busbars deposed toward the periphery of each of said areas to effect a respective color change therethrough.

24. A method of making an electrochromic panel having a pair of facing glass substrates forming a cell cavity for an electrolyte;

facing surfaces of the substrates each having a conductive transparent coating where each of these faces is coated with ion-intercalatable electrodes, at least one of which is electrochromic, wherein one of said electrodes is reduced after the cell cavity is formed, comprising the steps of;

(a) filling said cavity with a reducing fluid medium containing at least one of an anodic and a cathodic redox material;

(b) applying a voltage at least once to reduce one of said electrodes;

(c) flushing the reducing liquid from the cavity; and

(d) filling said cavity with the electrolyte.

25. The method of claim 24, wherein said reducing fluid medium includes at least one of a dissociable salt and an acid.

26. The method of claim 24 wherein said redox material is a metallocene.

27. The method of claim 26 wherein said metallocene is selected from the group consisting of ferrocene, a ferrocene derivative, cobaltocene and a mixture thereof.

28. The method of claim 25 wherein said dissociable salt is selected from the group consisting of lithium, sodium and potassium.

29. The method of claim 24 wherein said one of said substrates is provided with an electrochromic layer the composition of which includes at least an oxide of tungsten.

30. The method of claim 24 wherein at least one of said ion-intercalatable electrodes contains at least one oxide selected from the group consisting of vanadium oxide, nickel oxide and manganese oxide.

31. The method of claim 24 wherein the electrolyte contains each of the following:

at least one dissociable salt;

at least one UV stabilizer;

at least one polar solvent; and

a water content less then 2000 ppm.

32. The method of claim 31 wherein the polar solvent is selected from the group consisting of sulfolane, methyl sulfolane, propylene carbonate, gamma-butyrolactone and polyethylene glycol.

33. The method of claim 24 wherein said electrolyte is converted to a solid material by incorporation of a material selected from the group consisting of polymers, in-situ polymerizable monomers and nano-partical inorganic oxides.

34. The method of claim 24 wherein said electrolyte is thickened by incorporation of a material selected from the group consisting of polymers and nano-partical inorganic oxides.

35. The method of claim 24, wherein said reducing fluid is forced out of said cell cavity by a flushing medium consisting of at least one of a polar solvent, non-polar solvent or an inert gas.

36. The method of claim 24, wherein said step of flushing is repeated one or more times prior to filling said cavity with said electrolyte.

37. A transparent chromogenic device with controlled variation of an area of coloration, said device comprising:

(a) a pair of facing transparent substrates defining a cavity enclosing an electrolyte medium;

(b) facing surfaces of the substrates each having a conductive transparent coating;

(c) each conductive transparent coating having at least two bus bars in contact therewith, wherein each of said two bus bars contacting each conductive transparent coating are positioned in a spaced-apart relationship defining a portion of said device in which the area of coloration of said device is variably controlled; and

(d) a controller that provides a means for controlling the area of coloration by varying a voltage drop across said device.

38. The transparent chromogenic device according to claim 37, further comprising an electrochromic layer disposed on at least one of the conductive transparent coatings.

39. The transparent chromogenic device according to claim 37, wherein said electrolyte medium is electrochromic.

40. The transparent chromogenic device according to claim 37, wherein said means for controlling the area of coloration includes a switch for applying a voltage between a first one of said two bus bars contacting a first one of the conductive transparent coatings and an opposing first one of said two bus bars contacting a second one of the conductive transparent coatings.

41. The transparent chromogenic device according to claim 40, wherein said means for controlling the area of coloration includes a resistor communicating between a second one of said two bus bars contacting the first one of the conductive transparent coatings and an opposing second one of said two bus bars contacting the second one of the conductive transparent coatings.

42. The transparent chromogenic device according to claim 41, wherein said resistor is a variable resistor.

43. A transparent chromogenic device having both coloration and heating capability, said device comprising:

(a) a pair of facing transparent conductors defining a cavity enclosing an electrolyte medium;

(b) a transparent substrate on an outer face of at least one of said transparent conductors;

(c) at least one transparent conductor having at least two bus bars in contact therewith, wherein said two bus bars contacting said transparent conductor are positioned in a spaced-apart relationship defining a portion of said device which may be colored or heated; and

(d) a controller that provides a means to selectively apply a voltage to color said device or heat said device.

44. The transparent chromogenic device according to claim 43, wherein said device is comprised of two transparent substrates each on an outer face of each conductor.

45. The transparent chromogenic device according to claim 43, further comprising an electrochromic layer disposed on at least one of the transparent conductors.

46. The transparent chromogenic device according to claim 43, wherein said electrolyte medium is chromogenic.

47. The transparent chromogenic device according to claim 43, wherein said controller includes an electrical circuit that is selectively controlled to (i) cause coloration of said device by creating a voltage potential between at least one of said two bus bars contacting a first one of the transparent conductors and at least one bus bar contacting a second one of the transparent conductors and (ii) cause heating of said device by creating a voltage potential between at least said two bus bars contacting at least one of said transparent conductors.

48. A solar powered chromogenic window system comprising:

(a) a chromogenic glazing;

(b) a solar power source for providing power to said chromogenic glazing; and

(c) either a central control system or user controlled interface that is in wireless communication with said solar power source.

49. A front-side window of a vehicle having at least a chromogenic portion comprising:

(a) a pair of facing transparent conductors with an electrolyte medium disposed therebetween in an area of said window defined by a look-through portion of said window for a driver of said vehicle looking at a side-view mirror of said vehicle;

(b) a transparent substrate on an outer face of at least one of said transparent conductors; and

(c) a set of busbars disposed toward at least a portion of the periphery of said area of each conductor.

50. The front-side window according to claim 49, wherein said window is comprised of two transparent substrates each on an outer face of each conductor.

51. The front-side window according to claim 49, further comprising an electrochromic layer disposed on at least one of the transparent conductors.

52. The front-side window according to claim 49, wherein said electrolyte medium is electrochromic.

53. A chromogenic glazing having improved wireless signal transmission capability, said glazing comprising:

(a) a pair of facing transparent conductors defining a cavity enclosing an electrolyte medium; and

(b) a transparent substrate on an outer face of at least one of said transparent conductors,

wherein said improvement resides in the absence of the transparent conductors in a defined area or the inclusion of at least one optical transceiver in said device.

54. The chromogenic glazing according to claim 53, wherein said glazing is comprised of two transparent substrates each on an outer face of each conductor.

55. The chromogenic glazing according to claim 53, further comprising an electrochromic layer disposed on at least one of the transparent conductors.

56. The chromogenic glazing according to claim 53, wherein said electrolyte medium is chromogenic.

57. A method of controlling the uniformity of appearance of a glazing comprised of a plurality of chromogenic panels, said method comprising the steps of:

(a) receiving image data from at least one optical sensor individually scanning said chromogenic panels;

(b) using said image data to adjust the power supplied to each individual chromogenic panel to a predetermined light transmission value.

58. The method according to claim 57, wherein said predetermined light transmission value for each chromogenic panel is substantially equivalent.

59. The method according to claim 57, wherein said predetermined light transmission value for each chromogenic panel is set to create a desired image in said glazing.

60. A chromogenic glazing system comprising:

(a) at least one chromogenic glazing communicating with a control system;

(b) a photosensor that communicates with said control system; and

(c) a temperature sensor that communicates with said control system, wherein data received by said control system from said photosensor and temperature sensor is processed to select a predetermined amount of power to be supplied to said chromogenic glazing.

61. The chromogenic glazing according to claim 60, wherein said temperature sensor determines a temperature of an interior compartment of a vehicle or building.

62. The chromogenic glazing according to claim 60, wherein said temperature sensor determines a temperature of ambient conditions outside a vehicle or building.

63. A chromogenic window comprising:

(a) a non-polarizing chromogenic layer disposed between two transparent conductors;

(b) a transparent substrate on an outer face of at least one of said transparent conductors; and

(c) at least one coating or layer selected from the group consisting of;

(i) at least one polarizing filter;

(ii) a self-cleaning coating; and

(iii) a hydrophilic coating.

64. The chromogenic window according to claim 63, wherein said window is comprised of two transparent substrates each on an outer face of each conductor.

65. The chromogenic window according to claim 63, wherein at least one of said coating or layer is laminated to said chromogenic window.

66. The chromogenic window according to claim 63, wherein said window further comprises at least one of an IR or UV blocking layer.

67. A chromogenic device comprising:

(a) a pair of facing conductors defining a cavity enclosing an electrolyte medium wherein at least one of said conductors is transparent; and

(b) a transparent substrate on an outer face of at least one of said transparent conductors, wherein said substrate is a glass substrate comprised of phosphate or is laminated with a phosphate containing material.

68. The chromogenic device according to claim 67, wherein both conductors are transparent and said device is comprised of two transparent substrates each on an outer face of each conductor.

69. The chromogenic device according to claim 67, further comprising an electrochromic layer disposed on an inner face of at least one of said transparent conductors.

70. A chromogenic device comprising:

(a) a pair of facing conductors defining a cavity enclosing an electrolyte medium, wherein at least one of said conductors is transparent; and

(b) a transparent substrate on an outer face of at least one of said transparent conductors, wherein said substrate is a glass substrate comprised of a rare earth oxide selected from the group consisting of neodymium oxide, erbium oxide, ytterbium oxide or mixtures thereof.

71. The chromogenic device according to claim 70, wherein both conductors are transparent and said device is comprised of two transparent substrates each on an outer face of each conductor.

72. The chromogenic device according to claim 70, further comprising an electrochromic layer disposed on an inner face of at least one of said transparent conductors.

73. A method of sealing fill holes in a chromogenic assembly having a glass substrate comprising the step of covering each of said holes with a metal cap, wherein the difference between the linear thermal expansion coefficient of the glass substrate and the metal cap is less than 5×

10<sup>−

6</sup> cm/cm/°

C. when measured between 25 and 300°

C.

74. A chromogenic assembly comprising:

(a) a pair of facing conductors defining a cavity enclosing an electrolyte medium wherein at least one of said conductors is transparent; and

(b) a transparent substrate on an outer face of at least one of said transparent conductors, wherein said transparent substrate is a strengthened substrate or a strengthened transparent substrate is laminated to said transparent substrate.

75. The chromogenic assembly according to claim 74, wherein both conductors are transparent and said device is comprised of two transparent substrates each on an outer face of each conductor.

76. The chromogenic assembly according to claim 75, wherein both transparent substrates are strengthened transparent substrates.

77. A chromogenic window comprising:

(a) chromogenic layer disposed between two transparent conductors;

(b) a transparent substrate on an outer face of at least one of said transparent conductors; and

(c) at least one laminated layer on an outer surface of said window selected from the group consisting of;

(i) a glass breakage sensing layer;

(ii) an antenna layer;

(iii) a heater layer;

or

(iv) a bullet proof layer.