Electrochromic light valve and method of manufacturing it as well as its use

• US 5,631,765 A
• Filed: 11/12/1993
• Issued: 05/20/1997
• Est. Priority Date: 05/16/1991
• Status: Expired due to Fees

• Current Assignee: Fraunhofer Gesellschaft Zur Foerderung Der Angewandten Forsching E.V.
• Original Assignee: Fraunhofer Gesellschaft Zur Foerderung Der Angewandten Forsching E.V.
• Inventors: Strinitz, Heinz, Weinberg, Uta, Schlotter, Peter, Baur, Gunter
• Primary Examiner(s): Epps, Georgia Y.
• Assistant Examiner(s): Robbins, Thomas
• Application Number:
  US08/146,132
• Time in Patent Office: 1,285 Days
• Field of Search: 359/265, 359/273, 359/274
• US Class Current: 359/267
• 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 17/10761 containing vinyl acetal
• CPC Class Codes: G02F 1/1524 Transition metal compounds
• CPC Class Codes: G02F 1/155 Electrodes
• CPC Class Codes: G02F 2001/1555 Counter electrode

Abstract

The invention makes available an electrochromic right valve (1) with an active electrochromic layer (2) and a passive electrochromic layer (3). Between the two electrochromic layers is an electrolyte (4). Each of the electrochromic layers is connected to an associated electrode (5, 6). The active electrochromic layer can accept electrons from its electrodes and ions of a particular element from the electrolyte to become reversibly colored. The passive electrochromic layer acts as a reservoir for ions of the species concerned, donating such ions to and accepting them from the electrolyte. At the operating temperature of the electrochromic light valve, the passive layer is super-saturated with the element which provides the ions of the species concerned. The invention also covers a method of manufacturing the electrochromic light valve and uses of the valve.

Claims

1. Electrochromic light valve, comprising

(a) a pair of electrodes, at least one of said electrodes being transparent;

(b) an electrolyte layer arranged between said electrodes;

(c) an active electrochromic layer whose color can change, said active electrochromic layer being interposed between one of said electrodes and said electrolyte layer;

(d) an optically passive and transparent charge storage layer whose transparence remains essentially unchanged, said charge storage layer being interposed between the other of said electrodes and said electrolyte layer;

(e) said active electrochromic layer being arranged and adapted for reversibly changing its coloration by acceptance and donation of electrons from and to said one electrode;

(f) said active electrochromic layer for reversibly changing its coloration further being arranged and adapted for acceptance and donation of ions from and to said electrolyte;

(g) said charge storage layer being arranged and adapted for donating and accepting ions from and to said electrolyte;

(h) said charge storage layer further being arranged and adapted for donating and accepting electrons to and from said other electrode; and

(i) said charge storage layer further being supersaturated with at least one of an element and a compound providing and accepting ions.

2. Electrochromic light valve according to claim 1, characterized in that the passive electrochromic layer (3) is multiply supersaturated with the element that provides the ions of the species concerned or with the elements that provide the ions of the species concerned.

3. Electrochromic light valve according to claim 1, characterized in that the element which provides the ions of the species concerned is lithium or sodium.

4. Electrochromic light valve according to claim 1, characterized in that the elements which provide the ions of the species concerned are lithium and sodium.

5. Electrochromic light valve according to claim 1, characterized in that the passive electrochromic layer (3) comprises cerium oxide or contains cerium oxide.

6. Electrochromic light valve according to claim 1, characterized in that the active electrochromic layer (2) comprises one transition metal oxide or several transition metal oxides or contains one transition metal oxide or several transition metal oxides.

7. Electrochromic light valve according to claim 1, characterized in that the thickness of the active and/or the passive electrochromic layer (2, 3) is between 0.05 and 10 μ

m.

8. Electrochromic light valve according to claim 1, characterized in that the electrolyte (4) is polyvinylbutyral, which is donated with the element which provides the positive ions or with the elements which provide the positive ions.

9. Electrochromic light valve according to claim 1, characterized in that the electrolyte (4) is a liquid crystal or a liquid crystalline polymer with preferred ion conductivity perpendicular to the film plane.

10. Electrochromic light valve according to claim 1, characterized in that the electrode (5) associated with the active electrochromic layer (2) and/or the electrode (6) associated with the passive electrochromic layer (3) comprises indium-tin oxide or tin oxide or contains indium-tin oxide or tin oxide, and that the electrode (5) associated with the active electrochromic layer (2) and/or that the electrode (6) associated with the passive electrochromic layer (3) is saturated with the element which provides the ions of the species concerned or with the elements which provide the ions of the species concerned.

11. Electrochromic light valve according to claim 5, characterized in that the passive electrochromic layer (3) is a mixture of cerium(III) and/or cerium(IV) oxide and 10 mol % to 90 mol %, of titanium(II), titanium(III) or titanium(IV) oxide, the mol % values relating to the Ce and Ti metal contents.

12. Electrochromic light valve according to claim 5, characterized in that the passive electrochromic layer (3) is a mixture of cerium(III) and/or cerium(IV) oxide and 10 mol % to 90 mol % of tungsten oxide, the mol % values relating to the Ce and W metal contents.

13. Electrochromic light valve according to claim 6, characterized in that the transition metal oxide is WO_u, where u is in the range from 2 to 3.

14. Electrochromic light valve according to claim 9, characterized in that the liquid crystal or the liquid crystalline polymer is of the nematic or discotic type.

15. Electrochromic light valve according to claim 14, characterized in that the electrode (5) associated with the active electrochromic layer (2) and/or the electrode (6) associated with the passive electrochromic layer (3) is saturated with lithium and/or sodium.

16. Method of manufacturing an electrochromic light valve according to one of claims 1 to 15, in which an optically passive and transparent charge storage layer, which contains at least one of an element and a compound providing and accepting ions, is produced, characterized in that the optically passive and transparent charge storage layer is supersaturated with the at least one of an element and a compound which provides and accepts the ions.

17. Method according to claim 16, characterized in that in order to form the supersaturated passive electrochromic layer (3), a carrier substance layer for an element which provides the ions of the species concerned, or for several elements which provide the ions of the species concerned, is initially manufactured, which does not contain the element or the elements or is not yet supersaturated with it/them, and that the element or elements is/are donated to this carrier substance layer until it is supersaturated.

18. Method according to claim 17, characterized in that the carrier substance layer which does not contain the element or the elements, or does not contain it/them to supersaturatlon, has this element or these elements donated in an electrolyte at a temperature substantially above the operating temperature of the light valve (1), until no further substantial acceptance of the element or the elements takes place per unit of time.

19. Method according to claim 17, characterized in that the donation is carried out before the light valve (1) is assembled.

20. Method according to claim 17, characterized in that the carrier substance layer, which does not contain the element or the elements or does not contain it/them to supersaturation, is doped by coating with the element or the elements and diffusion, the diffusion taking place at a temperature substantially above the operating temperature of the light valve (1).

21. Method according to claim 17, characterized in that the carrier substance is or contains an amorphous or polycrystalline oxide or mixed oxide.

22. Method according to claim 21, characterized in that the amorphous or polycrystalline oxide is cerium oxide or titanium oxide.

23. Method according to claim 21, characterized in that the amorphous or polycrystalline mixed oxide is Ce_y Ti_z O_u.

24. Method according to claim 21, characterized in that the mixed oxide is a mixture of cerium(III) and/or cerium(IV) oxide and 10 mol % to 90 mol % of titanium(II), titanium(III) or titanium(IV) oxide, the mol % values relating to the Ce and Ti metal contents.

25. Method according to claim 21, characterized in that the mixed oxide is a mixture of cerium(III) and/or cerium(IV) oxide and 10 mol % to 90 mol % of tungsten oxide the mol % values relating to the Ce and W metal contents.

26. Method according to claim 16, characterized in that the supersaturated passive electrochromic layer (3) is manufactured in a single process step by being simultaneously constructed from the element or the elements and a carrier substance for this element or these elements, this element or these elements being incorporated into this layer (3) when the layer (3) is being constructed, in a quantity such that the layer (3) is supersaturated with the element or the elements in the course of its construction.

27. Method according to claim 26, characterized in that the passive electrochromic layer (3) is manufactured by means of sputtering or reactive sputtering of a target which contains the starting substances for the carrier substance and the element or the elements.

28. Method according to claim 26, characterized in that the passive electrochromic layer (3) is manufactured by simultaneous vapor deposition of the carrier substance layer and the element or the elements.

29. Method according to claim 27, characterized in that the target is a metallic target which contains or consists of cerium and/or titanium and lithium and/or sodium and the reactive sputtering is carried out in an atmosphere containing oxygen.

30. Method according to claim 29, characterized in that the target contains or comprises Li_x1 Ce_y1 Ti_z1 and/or Na_x2 Ce_x2 Ti_z2.

31. Method according to claim 27, characterized in that the target contains or consists of cerium oxide and/or titanium oxide and lithium and/or sodium.

32. Method according to claim 31, characterized in that the target contains or consists of Li_x1 Ce_y1 Ti_z1 O_u1 and/or Na_x2 Ce_y2 Ti_z2 0_u2.

33. Method according to claim 16, characterized in that the passive electrochromic layer (3) is constructed from several individual layers of a carrier substance or several carrier substances and/or the element or the elements which are manufactured over one another and after one another.

34. Method according to claim 33, characterized in that individual layers of carrier substance(s) and individual layers of the element or the elements are produced over one another in turns.

35. Method according to claim 33, characterized in that the individual layers are produced by sputtering and/or reactive sputtering.

36. Method according to claim 33, characterized in that the individual layers are produced by vapor deposition.

37. Method according to claim 16, characterized in that the element is lithium or sodium.

38. Method according to claim 16, characterized in that the elements are lithium and sodium.

39. Method according to claim 16, characterized in that the passive electrochromic layer (3), preferably before the light valve (1) is assembled, is provided, in particular saturated and/or doped in the manner stated, with another element of any other kind or with several elements of any other kind.

40. Method according to claim 16, characterized in that the active electrochromic layer (2), preferably before the light valve (1) is assembled, is provided, in particular doped, with an element which provides the ions of the species concerned or with several elements which provide the ions of the species concerned, up to a specified degree below the saturation limit.

41. Method according to claim 16, characterized in that the electrode (5) associated with the active electrochromic layer (2) and/or the electrode (6) associated with the passive electrochromic layer (3) is saturated with the element which provides the ions of the species concerned or with the elements which provide the ions of the species concerned.

42. Method according to claim 41, characterized in that the electrode (5) associated with the active electrochromic layer (2) and/or the electrode (6) associated with the passive electrochromic layer (3) is saturated with lithium and/or sodium.

43. Use of the electrochromic light valve manufactured according to claim 16 as windowpanes, optical components and spectacle lenses whose light transmission is controllable by absorption and/or reflection.

44. Use of the light valve manufactured according to claim 16 as a controllable absorber and/or reflector in the solar field or as an electrically chargeable energy store.

45. Use of the electrochromic light valve manufactured according to claim 16 as an electrically tunable medium in the resonator of a Fabry and Perot interferometer.