Enhanced cycle lifetime electrochromic systems

• US 5,516,462 A
• Filed: 03/18/1993
• Issued: 05/14/1996
• Est. Priority Date: 06/05/1990
• Status: Expired due to Fees

• Current Assignee: the united states of america as represented by the secretary of the navy
• Original Assignee: the united states of america as represented by the secretary of the navy
• Inventors: Henry, Ronald A., Fine, Dwight A., Miles, Melvin H.
• Primary Examiner(s): TUCKER, PHILIP C
• Application Number:
  US08/032,877
• Time in Patent Office: 1,153 Days
• Field of Search: 252/583, 252/586, 252/600, 359/272
• US Class Current: 252/583
• CPC Class Codes: G02F 1/1503 caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions

Abstract

Electrochromic systems providing enhanced cycle lifetime. The increase in cycle lifetime is a product of one or more of the following: novel or known asymmetric viologen compounds, mixed electrolyte systems, and mixed solvent systems.

Claims

1. An electrochromic system having an enhanced reversible electrochromic cycle lifetime comprising:

an electrochromic viologen compound; and

,

a mixed electrolyte system,

wherein said mixed electrolyte system is comprised of a solvent and a combination of two or more electrolytes selected from the group of combinations consisting of;

KBr/KC₂ H₃ O₂, KBr/K₂ SO₄, KCl/KNO₃, KCl/KC₂ H₃ O₂, KCl/K₂ SO₄, KNO₃ /KC₂ H₃ O₂, KNO₃ /K₂ SO₄, KC₂ H₃ O₂ /K₂ SO₄, KBr/KCl/KNO₃, KBr/KCl/KC₂ H₃ O₂, KBr/KCl/K₂ SO₄, KBr/KNO₃ /KC₂ H₃ O₂, KBr/KNO₃ /K₂ SO₄, KBr/KC₂ H₃ O₂ /K₂ SO₄, KCl/KNO₃ /KC₂ H₃ O₂, KCl/KNO₃ /K₂ SO₄, KCl/KC₂ H₃ O₂ /K₂ SO₄, KNO₃ /KC₂ H₃ O₂ /K₂ SO₄, KBr/KCl/KNO₃ /KC₂ H₃ O₂, KBr/KCl/KNO₃ /K₂ SO₄, KBr/KCl/KC₂ H₃ O₂ /K₂ SO₄, KCl/KNO₃ /KC₂ H₃ O₂ /K₂ SO₄, KBr/KNO₃ /KC₂ H₃ O₂ /K₂ SO₄, and KBr/KCl/KNO ₃ /K₂ SO₄ /KC₂ H₃ O₂,

wherein the reversible cycle lifetime is in excess of that obtainable using a single electrolyte system.

2. The electrochromic system of claim 1 wherein said viologen compound is 1,1'"'"'-bis-(2-methylbenzyl)-2-methyl-4,4'"'"'-bipyridine.

3. The electrochromic system of claim 1, wherein said viologen compound is:

##STR3## wherein X is a mono-valent negative ion;

wherein R and R'"'"' are selected from the group consisting of H and CH₃ ; and

,

wherein R" is an ortho-substituted benzyl.

4. The electrochromic system of claim 1, further comprising a mixed solvent system,

wherein said mixed solvent system is comprised of water and a non-water component comprised of at least one of the solvents selected from the group consisting of DMSO, acetone, ethanol, acetonitrile, 1-propanol, propylene glycol, and ethylene glycol,

wherein said non-water component is less than 25 weight percent of the mixed solvent, and

wherein the reversible cycle lifetime is in excess of that obtainable using a single solvent system.

5. The electrochromic system of claim 1,

wherein said combination of electrolytes is comprised of 0.20 molal KCl, 0.50 molal KNO₃, and 0.50 molal KC₂ H₃ O₂, and

wherein said viologen compound is 1,1'"'"'-bis-(2-methylbenzyl)-2-methyl-4,4'"'"'-bipyridine.

6. The electrochromic system of claim 1, wherein said electrolyte combination is 0.20 m KNO₃ and 0.20 m K₂ SO₄, and

wherein said viologen compound is 1, 1'"'"'-bis-(2-methylbenzyl)-2-methyl-4,4'"'"'-bipyridine.

7. The electrochromic system of claim 1, wherein said mixed electrolyte system is comprised of a solvent and a combination of three or more electrolytes selected from the group of combinations consisting of:

KBr/KCl/KNO₃, KBr/KCl/KC₂ H₃ O₂, KBr/KCl/K₂ SO₄, KBr/KNO₃ /KC₂ H₃ O₂, KBr/KNO₃ /K₂ SO₄, KBr/KC₂ H₃ O₂ /K₂ SO₄, KCl/KNO₃ /KC₂ H₃ O₂, KCl/KNO₃ /K₂ SO₄, KCl/KC₂ H₃ O₂ /K₂ SO₄, KNO₃ /KC₂ H₃ O₂ /K₂ SO₄, KBr/KCl/KNO₃ /KC₂ H₃ O₂, KBr/KCl/KNO₃ /K₂ SO₄, KBr/KCl/KC₂ H₃ O₂ /K₂ SO₄, KCl/KNO₃ /KC₂ H₃ O₂ /K₂ SO₄, KBr/KNO₃ /KC₂ H₃ O₂ /K₂ SO₄, and KBr/KCl/KNO₃ /K₂ SO₄ /KC₂ H₃ O₂.

8. The electrochromic system of claim 1,

wherein said viologen compound is 1,1'"'"'-bis-(2-methylbenzyl)-2-methyl-4,4'"'"'-bipyridine and,

wherein said system has a cycle lifetime of greater than 20,000 reversible cycles.

9. An electrochromic system having an enhanced reversible electrochromic cycle lifetime, the system comprising:

an electrochromic viologen compound;

a solvent consisting of water and at least one non-water component selected from the group consisting of DMSO, acetone, acetonrile, 1-propanol, propylene glycol, and ethylene glycol; and

electrolytes soluble in said solvent to release therein at least two kinds of anions selected from the group consisting of bromide, chloride, nitrate, sulfate, and acetate anions, each of said electrolytes being a salt present in said solvent in a proportion of at least 0.20 mole per kilogram of solvent.

10. The electrochromic system of claim 9 wherein said electrolytes are salts of an alkaline metal.

11. The electrochromic system of claim 10 wherein said alkaline metal is potassium.

12. The electrochromic system of claim 9 wherein said viologen compound includes the 1,1'"'"',-bis-(2-methylbenzyl)-4,4'"'"'-bipyridine structure.

13. The electrochromic system of claim 12 wherein said viologen compound is 1,1'"'"',-bis-(2-methylbenzyl)-2-methyl-4,4'"'"'-bipyridine.

14. The electrochromic system of claim 9 wherein:

said electrolytes are salts of an alkaline metal; and

said viologen compound is a 1,1'"'"',-bis-(2-methylbenzyl)-2-methyl-4,4'"'"'-bipyridine.