SWITCHABLE WINDOW BASED ON ELECTROCHROMIC POLYMERS

• US 20080055701A1
• Filed: 10/31/2007
• Published: 03/06/2008
• Est. Priority Date: 06/25/2001
• Status: Active Grant

• Current Assignee: University of Washington
• Original Assignee: University of Washington
• Inventors: Legenski, Susan, Taya, Minoru, Xu, Chunye, Liu, Lu
• Granted Patent: US 7,547,658 B2
• Time in Patent Office: Days
• US Class Current: 359/266
• 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 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.

2. The electrochromic device of claim 1, 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.

3. An electrochromic device comprising:

(a) a transparent electrode layer;

(b) a cathodic polymer layer;

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

(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.

4. The electrochromic device of claim 3, 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.

5. The electrochromic device of claim 3, 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. A method for making a high quality vanadium oxide film suitable for use in an electrochromic device, comprising the steps of:

(a) providing a substantially transparent and conductive substrate;

(b) attaching an additional conductive material to a portion of the substantially transparent and conductive substrate to which a potential will be applied; and

(c) depositing a thin film of vanadium oxide onto the substantially transparent and conductive substrate using cyclic voltammetry.

7. The method of claim 6, wherein the step of attaching the additional conductive material comprises the step of attaching a strip of copper at a border of the substantially transparent and conductive substrate.

8. The method of claim 6, wherein the step of depositing the thin film of vanadium oxide onto the substantially transparent and conductive substrate using cyclic voltammetry comprises the steps of:

(a) introducing the substantially transparent and conductive substrate into a solution comprising hydrated vanadium oxide nano-particles; and

(b) depositing the vanadium oxide using a deposition speed ranging from about 5-150 mV/s, an applied voltage ranging from about 1-3 V, and a plurality of deposition cycles ranging from about 10-100.

9. The method of claim 8, wherein the step of depositing a thin film of vanadium oxide onto the substantially transparent and conductive substrate using cyclic voltammetry comprises the step of increasing the voltage and number of sweeps as the size of the substantially transparent and conductive substrate is increased.

10. The method of claim 8, wherein the step of depositing a thin film of vanadium oxide onto the substantially transparent and conductive substrate using cyclic voltammetry further comprises the step of using a substrate angle ranging from about 60-90 degrees.

11. The method of claim 6, further comprising the step of heating the substantially transparent and conductive substrate after deposition of the vanadium oxide film to remove moisture.

12. A method for synthesizing a desired product, the desired product comprising a monomer suitable for polymerization to achieve an electrochromic polymer that is substantially opaque in a first state and substantially transparent in a second state, wherein the monomer comprises 6,6-Diethyl-6,7-dihydro-2H,5H-4,8-dioxa-2-aza-azulene, the method comprising the steps of:

(a) providing at first solution including a first intermediate reagent, the first intermediate reagent comprising 6,6-Diethyl-6,7-dihydro-2H,5H-4,8-dioxa-2-aza-azulene-1,3-dicarboxylic acid; and

(b) heating the first solution to facilitate a reaction that will produce the desired product.

13. The method of claim 12, further comprising the steps of:

(a) extracting the desired product from the first solution after the first solution is heated, wherein the step of extracting the desired product from the first solution after the first solution is heated comprises;

(i) introducing the first solution in the water to form an aqueous solution;

(ii) extracting the desired product from the aqueous solution using dichloromethane, thereby forming a dichloromethane layer;

(iii) salting out the dichloromethane layer;

(iv) drying the dichloromethane layer; and

(v) filtering the dichloromethane layer to remove the desired product; and

(b) isolating the desired product using sublimation at a temperature of about 90-110°

C. under a vacuum.

14. The method of claim 12, further comprising the step of producing the first intermediate reagent by:

(a) providing a second solution including a second intermediate reagent and a base, the second intermediate reagent comprising 6,6-Diethyl-6,7-dihydro-2H,5H-4,8-dioxa-2-aza-azulene-1,3-dicarboxylic acid dimethyl ester; and

(b) heating the second solution to facilitate a reaction that will produce the first intermediate reagent.

15. The method of claim 14, further comprising the step of producing the second intermediate reagent by:

(a) providing a third solution including a third intermediate reagent, the third intermediate reagent comprising 2-Benzyl-6,6-diethyl-6,7-dihydro-2H,5H-4,8-dioxa-2-aza-azulene-1,3-dicarboxylic acid dimethyl ester; and

(b) heating the third solution to facilitate a reaction that will produce the second intermediate reagent.

16. The method of claim 15, further comprising the step of producing the third intermediate reagent by:

(a) providing a fourth solution including a fourth intermediate reagent, the fourth intermediate reagent comprising 1-Benzyl-3,4-dihydroxy-1H-pyrrole-2,5-dicarboxylic acid dimethyl ester; and

(b) heating the fourth solution to facilitate a reaction that will produce the third intermediate reagent.

17. The method of claim 16, wherein:

(a) the first solution comprises triethanolamine;

(b) the first solution is heated to about 170-190°

C. under an inert atmosphere;

(c) the base in the second solution comprises sodium hydroxide;

(d) the second solution is stirred during heating at a temperature of about 50 to 70°

C. under an inert atmosphere for about 3-6 hours;

(e) the third solution comprises anisole, sulfuric acid and trifluoroacetic acid; and

(f) the third solution is refluxed under an inert atmosphere for about one hour;

(g) the fourth solution comprises 2,2-diethyl-1,3-propanediol, triphenylphosphine, diethyl azodicarboxylate, and tetrahydrofuran;

(h) the fourth third solution is refluxed under an inert atmosphere for about 10 to 20 hours;

(i) the step of producing the first intermediate reagent further comprises the steps of;

(i) using an acid to neutralize any excess base after heating the second solution; and

(ii) extracting the first intermediate reagent from the second solution by filtering the second solution and drying the filtrate under a vacuum; and

(j) the step of producing the second intermediate reagent further comprises the steps of;

(i) quenching the fourth solution after refluxing using water;

(ii) adding silica gel to the fourth solution and water mixture;

(iii) evaporating the resulting mixture to dryness; and

(iv) isolating the third intermediate reagent using chromatography.

18. A method for synthesizing a desired product, the desired product comprising 3,4-bis-(2,2,2-trifluoroethoxy)-thiopene, a monomer suitable for polymerization to achieve a fluorinated electrochromic polymer, the method comprising the steps of:

(a) providing a first solution comprising a first intermediate reagent, the first intermediate reagent comprising 3,4-bis-(2,2,2-trifluoroethoxy)-thiophene-2,5-dicarboxylic acid; and

(b) heating the first solution to facilitate a reaction that will produce the desired product.

19. A monomer suitable for polymerization to achieve a fluorinated electrochromic polymer, the monomer comprising 3,4-bis-(2,2,2-trifluoroethoxy)-thiopene.

20. A method for synthesizing a fluorinated electrochromic monomer suitable for polymerization to achieve a fluorinated electrochromic polymer, the fluorinated electrochromic monomer being a fluorinated derivative of 3,4-dihydroxy-thiophene, the fluorinated derivative corresponding to 3,4-bis-(R-oxy)-thiophene, with R comprising a fluorinated functional group, the method comprising the steps of:

(a) producing a first intermediate reagent comprising a fluorinated derivative of 3,4-dihydroxy-thiophene-2,5-dicarboxylic acid dimethyl ester, the fluorinated derivative corresponding to 3,4-bis-(R-oxy)-thiophene-2,5-dicarboxylic acid dimethyl ester, by performing the steps of;

(i) providing a first solution comprising 3,4-dihydroxy-thiophene-2,5-dicarboxylic acid dimethyl ester and a fluorinated alcohol comprising R, the fluorinated functional group; and

(ii) heating the first solution to facilitate a reaction that will produce the first intermediate reagent;

(b) producing a second intermediate reagent comprising a fluorinated derivative of 3,4-dihydroxy-thiophene-2,5-dicarboxylic acid, the fluorinated derivative corresponding to 3,4-bis-(R-oxy)-thiophene-2,5-dicarboxylic acid, by performing the steps of;

(i) adding the first intermediate reagent to a second solution; and

(ii) heating the second solution to facilitate a reaction that will produce the second intermediate reagent; and

(c) using the second intermediate reagent to produce the fluorinated derivative of 3,4-dihydroxy-thiophene, by performing the steps of;

(i) adding the second intermediate reagent to a third solution; and

(ii) heating the third solution to facilitate a reaction that will produce the fluorinated derivative of 3,4-dihydroxy-thiophene.

21. A monomer suitable for polymerization to achieve a fluorinated electrochromic polymer, the monomer comprising a fluorinated derivative of 3,4-dihydroxy-thiophene, the fluorinated derivative corresponding to 3,4-bis-(R-oxy)-thiophene, with R comprising a fluorinated functional group.

22. The monomer of claim 21, wherein R comprises at least one fluorinated functional group selected from a group consisting of:

(a) 2,2,2-trifluoroethanol less the hydroxyl group, such that R has the formula of CF₃CH₂—

;

(b) 2-fluoroethanol less the hydroxyl group, such that R has the formula of CH₂FCH₂—

;

(c) 2,3,4,5,6-pentfluorobenzyl alcohol less the hydroxyl group, such that R has the formula of C₆F₅CH₂—

; and

(d) 2,2-difluoro-1,3-propanediol less one hydroxyl group, such that R has the formula of CH₂OHCF₂CH₂—

.

23. A monomer suitable for polymerization to achieve an electrochromic polymer, the monomer including silicon and comprising 6,6-dimethy-6,7-dihydro-5H-4,8-dioxa-2-thia-6-sila-azulene.

24. A method for synthesizing an electrochromic monomer suitable for polymerization to achieve an electrochromic polymer, the electrochromic monomer including silicon and comprising 6,6-dimethy-6,7-dihydro-5H4,8-dioxa-2-thia-6-sila-azulene, the method comprising the steps of:

(a) providing a first solution comprising a first intermediate reagent, the first intermediate reagent comprising 6,6-Dimethyl-6,7-dihydro-5H-4,8-dioxa-2-thia-6-sila-azulene-1,3-dicarboxylic acid; and

(b) heating the first solution to facilitate a reaction that will produce the desired product.

25. A method for synthesizing an electrochromic monomer suitable for polymerization to achieve an electrochromic polymer, the electrochromic monomer including silicon and comprising 6,6-dimethy-6,7-dihydro-5H4,8-dioxa-2-thia-6-sila-azulene, the method comprising the steps of:

(a) producing a first intermediate reagent, the first intermediate reagent comprising 6,6-Dimethyl-6,7-dihydro-5H-4,8-dioxa-2-thia-6-sila-azulene-1,3-dicarboxylic acid dimethyl ester, by;

(i) providing a first solution comprising 3,4-Dihydroxy-thiophene-2,5-dicarboxylic acid dimethyl ester; and

(ii) refluxing the first solution for a predefined period of time in order to facilitate a reaction that produces the first intermediate reagent;

(b) producing a second intermediate reagent, the second intermediate reagent comprising 6,6-Dimethyl-6,7-dihydro-5H-4,8-dioxa-2-thia-6-sila-azulene-1,3-dicarboxylic acid, by;

(i) dissolving the first intermediate reagent in a second solution comprising sodium hydroxide; and

(ii) refluxing the second solution for a predefined period of time in order to facilitate a reaction that produces the second intermediate reagent; and

(c) producing the desired product, by;

(i) dissolving the second intermediate reagent in a third solution that comprises quinoline;

(ii) adding a catalyst to the third solution in order to facilitate a reaction that produces the desired product;

(iii) heating the third solution to a predefined temperature for a predefined amount of time in order to facilitate a reaction that produces the desired product; and

(iv) extracting the desired product.