Electrochromic organic polymer synthesis and devices utilizing electrochromic organic polymers

• US 6,747,780 B2
• Filed: 06/25/2002
• Issued: 06/08/2004
• Est. Priority Date: 06/25/2001
• Status: Expired due to Term

• Current Assignee: Washington University In St Louis
• Original Assignee: University of Washington
• Inventors: Taya, Minoru, Xu, Chunye
• Primary Examiner(s): Schwartz, Jordan M.
• Assistant Examiner(s): Stultz, Jessica T
• Application Number:
  US10/180,222
• Publication Number:
  US 20020196518A1
• Time in Patent Office: 714 Days
• Field of Search: 359/273, 359/265, 359/267, 359/275, 359/272, 359/321-322, 348/817, 345/49, 345/105, 252/583, 252/600, 204/290.07, 428/426, 546/257, 544/347
• US Class Current: 359/265
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/15165 Polymers
• CPC Class Codes: G02F 2001/1502 complementary cell
• CPC Class Codes: H10K 85/1135 Polyethylene dioxythiophene [PEDOT]; Derivatives thereof

Abstract

Large contrast ratio and rapid switching laminated electrochromic (EC) polymer device includes transparent electrode, cathodic EC polymer, gel electrolyte, and counter-electrode. Preferably the cathodic EC polymer is a poly(3,4-propylenedioxythiophene) derivative, PProDOT-Me₂. Counter-electrode is a conductive coating deposited on transparent substrate, with preferred coatings including gold and highly conductive carbon. Lithography and sputtering can be employed to pattern a gold layer, while screen printing can be employed to similarly pattern graphite. Empirical studies of preferred device indicate a color change of high contrast ratio of transmittance (>50% T) is rapidly (0.5-1s) obtained upon applied 2.5V, repeatable to at least 10,000 times, as estimated by electrochemistry. Dual layer EC devices including PProDOT-Me₂ are also disclosed, as are methods for synthesizing preferred EC polymers. Preferred synthesis method for obtaining PProDOT-Me₂ involves refluxing reagents in toluene in the presence of catalyst, while continually removing methanol byproduct from refluxing solution.

Claims

1. 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 2,2-dimethyl-1,3-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 at least eight hours, 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 [3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine].

2. The method of claim 1, wherein the step of heating the solution comprises the step of heating the solution to a temperature of about one hundred ten degrees Celsius.

3. The method of claim 1, wherein the step of providing a first quantity of 3,4-dimethoxythiophene and a second quantity of 2,2-dimethyl-1,3-propanediol comprises the step of providing substantially equivalent molar amounts of 3,4-dimethoxythiophene and 2,2-dimethyl-1,3-propanediol.

4. The method of claim 1, further comprising the step of adding a catalyst to the solution before the step of refluxing the solution.

5. The method of claim 4, wherein the step of adding a catalyst comprises the step of adding p-toluenesulfonic acid to the solution.

6. The method of claim 5, wherein the step of adding p-toluenesulfonic acid to the solution comprises the step of adding a quantity of p-toluenesulfonic acid comprising less than 10 percent of a molar equivalent of the first quantity of 3,4-dimethoxythiophene that is dissolved in the toluene.

7. The method of claim 5, wherein the quantity of p-toluenesulfonic acid added to the solution comprises substantially 1.5 percent of a molar equivalent of the first quantity of 3,4-dimethoxythiophene that is dissolved in the toluene.

8. The method of claim 1, further comprising the step of adding calcium chloride to the condensed toluene before returning the condensed toluene to the solution, to remove a methanol byproduct from the condensed toluene.

9. A method for synthesizing an electrochromic polymer suitable for use as an anodic layer within a laminated electrochromic device;

comprising the steps of;

(a) producing a first intermediate reagent by;

(i) providing a first quantity of (3,4-ethylenedioxythiophene) (EDOT), a second quantity of n-butyl lithium; and

a third quantity of chilled tetrahydrofuran (THF), the third quantity being sufficient to substantially dissolve the first and second quantities;

(ii) introducing the first and second quantities into the chilled THF to form a first solution;

(iii) maintaining the first and second quantities in the chilled THF for a time sufficient to produce a Grignard reagent; and

(iv) treating the Grignard reagent with a quantity of magnesium bromide diethyl etherate sufficient to produce a brominated compound, the brominated compound comprising the first intermediate reagent;

(b) producing a second intermediate reagent by;

(i) providing a fourth quantity of a dibromocarbazole, a fifth quantity of lithium hydride; and

a sixth quantity of dimethyl foramide (DMF), the sixth quantity being sufficient to substantially dissolve the fourth and fifth quantities;

(ii) introducing the fourth and fifth quantities into the DMF to form a second solution;

(iii) cooling the second solution below room temperature; and

(iv) methylating the dibromocarbazole to produce a methylated dibromocarbazole intermediate product, the methylated dibromocarbazole intermediate product comprising the second intermediate reagent; and

(c) combining the first and second intermediate reagents in the presence of a catalyst to produce [3,6-bis(2-(3,4-ethylenedioxythiophene))-N-methylcarbazole.

10. The method of claim 9, wherein the step of methylating the dibromocarbazole comprises the step of adding methyl iodine to the second solution.

11. The method of claim 9, wherein the step of providing a third quantity of chilled tetrahydrofuran (THF) comprises the step of providing the third quantity at a temperature of less than 0°

C.

12. The method of claim 9, wherein the step of maintaining the first and second quantities in the chilled THF for a time sufficient to produce a Grignard reagent comprises the step of maintaining the first and second quantities in the chilled THF for about one hour.

13. The method of claim 9, wherein the step of methylating the second solution comprises the step of slowly increasing the temperature of the second solution for substantially two hours.

14. The method of claim 9, further comprising the step of purifying the second intermediate reagent before combining the first and second intermediate reagents.

15. The method of claim 14, wherein the step of purifying the second intermediate reagent comprises the steps of washing the second intermediate reagent with water, washing the second intermediate reagent with ether, and drying the second intermediate reagent with sodium sulfate.

16. The method of claim 9, wherein the step of combining the first and second intermediate reagents comprises the steps of adding the second intermediate reagent to the first solution containing the first intermediate reagent and THF to form a third solution, adding a catalyst to the third solution, and maintaining the third solution at a temperature of about 50°

C. for a period of about twelve hours.

17. The method of claim 9, wherein the catalyst comprises nickel.