Electrochromic display and method for making same

• US 4,236,792 A
• Filed: 12/28/1978
• Issued: 12/02/1980
• Est. Priority Date: 12/28/1978
• Status: Expired due to Term

• Current Assignee: Timex Corporation (Tanager Group BV)
• Original Assignee: Timex Corporation (Tanager Group BV)
• Inventors: Bissar, Saadi J.
• Primary Examiner(s): Davie, James W.
• Application Number:
  US05/973,832
• Time in Patent Office: 705 Days
• Field of Search: 350/357, 29/570, 427/77, 427/78, 427/108
• US Class Current: 359/269
• CPC Class Codes: G02F 1/1524 Transition metal compounds

Abstract

Disclosed is an electrochromic display having an electrolyte of optimized cationic mobility and a counter electrode of optimized electronic mobility. Preferably the display comprises (a) a front substrate with selectively actuable transparent electrodes and image-forming electrochromic layers thereon, (b) an acidified aqueous electrolyte containing a sufficient quantity of highly mobile hydrogen ions for coloration of the electrochromic layers and (c) a rear substrate spaced from the front substrate carrying a counter electrode in contact with the electrolyte, the counter electrode being in the form of a layer comprising predominantly an alkali tungsten bronze, preferably sodium and or potassium tungsten bronze, in the high temperature heat treated condition which exhibits enhanced electronic mobility. A process for making the display is also disclosed.

Claims

1. A process for making an electrochromic display comprising the steps of:

(a) providing a front substrate having transparent electrodes and image-forming electrochromic layers thereon;

(b) providing a rear substrate for carrying a counter electrode, the front and rear substrates being positioned in spaced working relation;

(c) forming a counter electrode on said rear substrate by

1. forming a layer of tungsten trioxide on said substrate;

2. converting a major portion of said tungsten trioxide layer to alkali tungstate to provide a first mixture of alkali tungstate and tungsten trioxide;

3. heating the first mixture to a sufficiently high temperature for a selected time to form a second mixture comprising a major portion of alkali tungsten bronze and a controlled minor portion of tungsten trioxide, the alkali tungsten bronze being in the high temperature heat treated condition which exhibits high electronic mobility for counter electrode purposes;

(d) filling the space between the substrates with electrolyte containing sufficient cationic coloring centers to impart coloration to said electrochromic layers; and

(e) sealing the front and rear substrates together.

2. The method of claim 1 wherein the heat treated alkali tungsten bronze formed in step (c) (3) is represented by the formula M_x WO₃ where M is an alkali metal and X is from about 0.1 to about 0.6.

3. The method of claim 2 wherein said first mixture is heated to about 800°

C. to about 1000°

C. in step (c) (3) to form said second mixture containing alkali tungsten bronze.

4. The method of claim 2 wherein the alkali metal is selected from sodium and potassium.

5. The method of claim 1 wherein the tungsten trioxide layer is formed by vacuum deposition on a substrate.

6. The method of claim 1 wherein the tungsten trioxide layer is formed by surface oxidizing a tungsten substrate.

7. The method of claim 1 including the additional step after step (c) (3) of selectively removing said tungsten trioxide from the second mixture, leaving a layer of predominantly heat treated alkali tungsten bronze as the counter electrode.

8. The method of claim 7 wherein selective removal is effected by contacting the second mixture with water in which the tungsten trioxide is soluble and the alkali tungsten bronze is not.

9. The method of claim 1 wherein the major portion of the tungsten trioxide layer is converted to alkali tungstate by reaction with an alcoholic solution of alkali hydroxide.

10. The method of claim 9 wherein the alkali hydroxide is selected from sodium hydroxide or potassium hydroxide so that after step (c) (3) a sodium or potassium tungsten bronze remains as the counter electrode.

11. In making a counter electrode useful in electrochromic displays, the steps of:

(a) forming a layer of tungsten trioxide by vacuum deposition on a substrate;

(b) converting a major portion of said tungsten trioxide layer to alkali tungstate to provide a first surface mixture of alkali tungstate and tungsten trioxide;

(c) heating the first mixture to a sufficiently high temperature for a selected time to form a second mixture comprising a major portion of alkali tungsten bronze and a controlled minor portion of tungsten trioxide, the alkali tungsten bronze being in the high temperature heat treated condition which exhibits high electronic mobility for counter electrode purposes.

12. The method of claim 11 wherein the heat treated alkali tungsten bronze formed in step (c) is represented by the formula M_x WO₃ where M is an alkali metal and X is from about 0.1 to about 0.6.

13. The method of claim 12 wherein said first mixture is heated in step (c) to about 800°

-1000°

C. to form said second mixture containing alkali tungsten bronze.

14. The method of claim 12 wherein the alkali metal is selected from sodium and potassium.

15. The method of claim 11 including the additional step after step (c) of selectively removing said tungsten trioxide from the second mixture, leaving a layer of predominantly heat treated alkali tungsten bronze as the counter electrode.

16. The method of claim 15 where selective removal is effected by contacting the second mixture with water in which the tungsten trioxide is soluble and the alkali tungsten bronze is not.

17. The method of claim 11 wherein the major portion of tungsten trioxide layer is converted to alkali tungstate by reaction with an alcoholic solution of alkali hydroxide.

18. The method of claim 17 wherein the alkali hydroxide is selected from sodium hydroxide and potassium hydroxide so that after step (c) a sodium or potassium tungsten bronze remains as the counter electrode.

19. In making a counter electrode useful in electrochromic displays, the steps of:

(a) forming a layer of tungsten trioxide by surface oxidizing a tungsten substrate;

(b) converting a major portion of said tungsten trioxide layer to alkali tungstate to provide a first surface mixture of alkali tungstate and tungsten trioxide;

(c) heating the first mixture to a sufficiently high temperature for a selected time to form a second mixture comprising a major portion of alkali tungsten bronze and a controlled minor portion of tungsten trioxide, the alkali tungsten bronze being in the high temperature heat treated condition which exhibits high electronic mobility for counter electrode purposes.

20. The method of claim 19 wherein the heat treated alkali tungsten bronze formed in step (c) is represented by the formula M_x WO₃ where M is an alkali metal and X is from about 0.1 to about 0.6.

21. The method of claim 20 wherein said first mixture is heated in step (c) to about 800°

-1000°

C. to form said second mixture containing alkali tungsten bronze.

22. The method of claim 20 wherein the alkali metal is selected from sodium and potassium.

23. The method of claim 19 including the additional step after step (c) of selectively removing said tungsten trioxide from the second mixture, leaving a layer of predominantly heat treated alkali tungsten bronze as the counter electrode.

24. The method of claim 19 wherein the major portion of the tungsten trioxide layer is converted to alkali tungstate by reaction with an alcoholic solution of alkali hydroxide.

25. An electrochromic display of sandwich construction, comprising:

(a) a front substrate with selectively actuable transparent electrodes and image-forming electrochromic layers thereon;

(b) an electrolyte having sufficient cationic coloring centers therein to impart coloration to said layers when the display is actuated;

(c) a rear substrate spaced from the front substrate for carrying a counter electrode layer in contact with the electrolyte, said counter electrode layer comprising a major portion of high temperature heat treated alkali tungsten broze and a controlled minor portion of tungsten trioxide, said heat treated alkali tungsten bronze functioning as a highly mobile electronic center during actuation of the display.

26. The display of claim 25 wherein the alkali tungsten bronze is heat treated to about 800°

to 1000°

C. and is represented by the formula M_x WO₃ where M is an alkali metal and X is about 0.1 to 0.6.

27. The display of claim 26 wherein the alkali metal is selected from sodium and potassium.

28. The display of claim 25 wherein the rear substrate on which the alkali tungsten bronze layer is disposed is tungsten.

29. The display of claim 25 wherein the electrolyte is an acidified aqueous solution and said counter electrode layer comprises from about 90 to 100 wt.% alkali tungsten bronze.

30. An electrochromic display of sandwich construction, comprising:

(a) a front substrate with selectively actuable transparent electrodes and image forming electrochromic layers thereon;

(b) an acidified aqueous electrolyte having sufficient hydrogen ion coloring centers therein to impart coloration to said electrochromic layers when the display is actuated;

(c) a rear substrate spaced from the front substrate for carrying a counter electrode layer in contact with the electrolyte, said counter electrode layer comprising alkali tungsten bronze in the high temperature heat treated condition which exhibits high electronic mobility for counter electrode purposes.

31. The display of claim 30 wherein the alkali tungsten bronze is heat treated at about 800°

to 100°

C. and is represented by the formula M_x WO₃ where M is an alkali metal and X is about 0.1 to 0.6.

32. The display of claim 31 wherein the alkali metal is selected from sodium and potassium.