Switchable window based on electrochromic polymers

• US 20050200935A1
• Filed: 03/01/2005
• Published: 09/15/2005
• Est. Priority Date: 06/25/2001
• Status: Active Grant

• Current Assignee: University of Washington
• Original Assignee: University of Washington
• Inventors: Taya, Minoru, Xu, Chunye, Liu, Lu, Legenski, Susan E.
• Granted Patent: US 7,256,923 B2
• Time in Patent Office: Days
• US Class Current: 359/265
• CPC Class Codes: C07D 493/04 Ortho-condensed systems
• CPC Class Codes: C08G 2261/1424 containing ether groups, including alkoxy
• CPC Class Codes: C08G 2261/3221 containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
• CPC Class Codes: C08G 2261/3223 containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
• CPC Class Codes: C08G 2261/44 Electrochemical polymerisation, i.e. oxidative or reductive coupling
• CPC Class Codes: C08G 2261/54 electrochromatic
• CPC Class Codes: C08G 61/124 with a five-membered ring containing one nitrogen atom in the ring
• CPC Class Codes: C08G 61/126 with a five-membered ring containing one sulfur atom in the ring
• CPC Class Codes: C09K 2211/1408 Carbocyclic compounds
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/15165 Polymers
• CPC Class Codes: G02F 1/153 Constructional details
• CPC Class Codes: G02F 1/1533 structural features not otherwise provided for
• CPC Class Codes: G02F 1/163 Operation of electrochromic cells, e.g. electrodeposition cells; Circuit arrangements therefor
• CPC Class Codes: G02F 2001/15145 the electrochromic layer comprises a mixture of anodic and cathodic compounds

Abstract

Syntheses of a new blue EC monomer (ProDOT-MePro), and a new red EC monomer (ProDOP-Et2) are described. Two additional new types of EC monomers based on 3,4-alkylenedioxythiophene include fluorinated EC monomers and an EC monomer including silicon. EC polymer devices having more than one different color EC polymer to enable additional colors to be provided using subtractive color mixing are also described, as well as EC polymer devices incorporating a logo, image, or text, are generally obscured when the device is colored, but become visible when the device is not colored. Also described are EC polymer devices that include a cathodic EC polymer layer, a gel electrolyte, a counter electrode, and a reference electrode. Working prototypes of such devices exhibit significant increases in the speed of transition of the EC device from a colored state to a transparent state.

Claims

1. An electrochromic device comprising:

(a) a transparent electrode layer;

(b) a cathodic polymer layer;

(c) an electrolyte layer comprising a solid electrolyte;

(d) a reference electrode electrically coupled to the electrolyte layer, the reference electrode increasing a speed with which the device switches between a first state and a second state; and

(e) a counter electrode layer.

2. The electrochromic device of claim 1, wherein the cathodic polymer layer comprises PProDOT-MePro.

3. The electrochromic device of claim 1, wherein the cathodic polymer layer comprises PProDOP-Et2.

4. The electrochromic device of claim 1, wherein the reference electrode comprises silver.

5. The electrochromic device of claim 1, further comprising at least one of a logo, a text, and a graphical image, such that when the electrochromic device is in a first state, the at least one of the logo, the text, and the graphical image is substantially obscured, and when the electrochromic device is in a second state, the at least one of the logo, the text, and the graphical image is readily visible.

6. The electrochromic device of claim 5, wherein the electrochromic device is included in an aircraft window.

7. The electrochromic device of claim 6, wherein the at least one of the logo, text, and the graphical image comprises an airline logo.

8. The electrochromic device of claim 5, wherein the electrochromic device is included in a sign.

9. The electrochromic device of claim 8, wherein the laminated electrochromic device is included in an emergency exit sign.

10. The electrochromic device of claim 1, further comprising:

(a) an additional transparent electrode layer;

(b) an additional cathodic polymer layer, the additional cathodic polymer layer having a different color than the cathodic polymer layer;

(c) an additional electrolyte layer comprising a solid electrolyte; and

(d) an additional counter electrode layer, such that the cathodic polymer layer and the additional cathodic polymer layer are configured to enable the electrochromic device to achieve a different color using subtractive color mixing.

11. The electrochromic device of claim 1, wherein the counter electrode comprises vanadium pentoxide.

12. An electrochromic device comprising:

(a) a transparent electrode layer;

(b) a cathodic polymer layer;

(c) an electrolyte layer comprising a solid electrolyte;

(d) a counter electrode layer; and

(e) at least one of a logo, a text, and a graphical image, such that when the electrochromic device is in a first state, the at least one of the logo, the text, and the graphical image is substantially obscured, and when the electrochromic device is in a second state, the at least one of the logo, the text, and the graphical image is readily visible.

13. The electrochromic device of claim 12, wherein the electrochromic device is included in an aircraft window.

14. The electrochromic device of claim 12, wherein the laminated electrochromic device is included in an emergency exit sign.

15. The electrochromic device of claim 12, further comprising a reference electrode electrically coupled to the electrolyte layer, the reference electrode increasing a speed with which the device switches between a first state and a second state.

16. The electrochromic device of claim 12, wherein the counter electrode comprises vanadium pentoxide.

17. An electrochromic device comprising:

(a) a first cathodic polymer switchable between a first state and a second state, the first cathodic polymer exhibiting a first color in the first state, and being generally transparent in the second state; and

(b) a second cathodic polymer switchable between a first state and a second state, the second cathodic polymer exhibiting a second color in the first state, and being generally transparent in the second state, the first cathodic polymer and the second cathodic polymer being disposed in relation to each other so that when the first cathodic polymer is in the first state and the second cathodic polymer is in the first state, the electrochromic device exhibits a third color, the third color being achieved by subtractive color mixing of the first cathodic polymer and the second cathodic polymer.

18. The electrochromic device of claim 17, wherein the charges of the first cathodic polymer and the second cathodic polymer are matched to substantially reduce transmission of visible light when the first cathodic polymer and the second cathodic polymer are in the first state.

19. An electrochromic device comprising:

(a) a transparent electrode layer;

(b) a cathodic polymer layer;

(c) an electrolyte layer comprising at least one of;

(i) gamma butyrolactone, propylene carbonate, lithium perchlorate, and polymethylmethacrylate; and

(ii) ethylene carbonate, propylene carbonate, lithium perchlorate, and polymethylmethacrylate; and

(d) a counter electrode layer.

20. The electrochromic device of claim 19, further comprising a reference electrode electrically coupled to the electrolyte layer, the reference electrode increasing a speed with which the device switches between a first state and a second state.

21. The electrochromic device of claim 19, further comprising at least one of a logo, a text, and a graphical image, such that when the electrochromic device is in a first state, the at least one of the logo, the text, and the graphical image is substantially obscured, and when the electrochromic device is in a second state, the at least one of the logo, the text, and the graphical image is readily visible.

22. The electrochromic device of claim 19, wherein the counter electrode comprises vanadium pentoxide.

23. An electrochromic device comprising:

(a) a transparent electrode layer;

(b) a cathodic polymer layer;

(c) an electrolyte layer comprising a solid electrolyte; and

(d) a counter electrode layer comprising vanadium pentoxide.

24. An electrochromic monomer having the formula 3-methyl-3′

-propyl-3,4-dihydro-2H-thieno(3,4-b)(1,4)dioxepine.

25. A blue electrochromic polymer having the formula poly[3-methyl-3′

-propyl-3,4-dihydro-2H-thieno(3,4-b)(1,4)dioxepine].

26. An electrochromic monomer having the formula 3,3-diethyl-3,4-dihydro-2H,7H-(1,4)dioxepino(2,3-c)pyrrole.

27. A red electrochromic polymer having the formula poly[3,3-diethyl-3,4-dihydro-2H,7H-(1,4)dioxepino(2,3-c)pyrrole].

28. An electrochromic monomer having the formula 3,4-bis-R-thiophene, wherein R comprises one of:

(a) 2,2,2-trifluoro-ethoxy;

(b) 2-fluoro-ethoxy;

(c) 2, 3, 4, 5, 6, pentafluorobenzoxy; and

(d) 2,2-difluoro-1-3-propoxy.

29. An electrochromic monomer having the formula 6,6-dimethy-6,7-dihydro-5H-4,8-dioxa-2-thia-6-sila-azulene.

30. A method for synthesizing an electrochromic polymer suitable for use as a cathodic layer within a laminated electrochromic device, comprising the steps of:

(a) providing a first quantity of 3,4-dimethoxythiophene and a second quantity of 2-methyl-3-propyl-propanediol;

(b) dissolving the first and second quantities in a sufficient quantity of toluene, such that substantially all of the first and second quantities dissolve in the toluene to form a solution; and

(c) refluxing the solution for a defined period of time, such that;

(i) the solution boils;

(ii) the toluene vaporizes, condenses, and returns to the solution; and

(iii) the first and second quantities react to form [3-methyl-3′

-propyl-3,4-dihydro-2H-thieno(3,4-b)(1,4)dioxepine].

31. The method of claim 30, wherein the step of providing a first quantity of 3,4-dimethoxythiophene and a second quantity of 2-methyl-3-propyl-propanediol comprises the step of providing substantially equivalent molar quantities of 3,4-dimethoxythiophene and 2-methyl-3-propyl-propanediol.

32. The method of claim 30, further comprising the step of adding a catalyst to the solution before the step of refluxing the solution.

33. The method of claim 32, wherein the step of adding the catalyst comprises the step of adding p-toluenesulfonic acid to the solution;

and further comprising the step of adding the catalyst to the solution before the step of refluxing the solution.

34. The method of claim 30, wherein the step of refluxing comprising the step of refluxing under an inert atmosphere.

35. The method of claim 30, wherein the step of refluxing comprising the step of refluxing for at least 18 hours.

36. The method of claim 30, further comprising the step of purifying the [3-methyl-3′

-propyl-3,4-dihydro-2H-thieno(3,4-b)(1,4)dioxepine] by elution with hexane and dichloromethane.