Electrochromic devices

• US 4,613,211 A
• Filed: 11/21/1983
• Issued: 09/23/1986
• Est. Priority Date: 11/21/1983
• Status: Expired due to Fees

• Current Assignee: Chevron Research Company (Chevron Corp.)
• Original Assignee: Chevron Research Company (Chevron Corp.)
• Inventors: Schroeder, Albert H., Papir, Yoram S.
• Primary Examiner(s): NOT, DEFINED
• Application Number:
  US06/554,153
• Time in Patent Office: 1,037 Days
• Field of Search: 350/357
• US Class Current: 359/270
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/15165 Polymers
• CPC Class Codes: H01M 4/60 of organic compounds
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

An electrochromic device which incorporates a reversibly color-changing organic polymer film as the display electrode. The display polymer film is capable of undergoing reversible oxidation and/or reduction to a charged, colored, conductive state. Upon reversing the charge, the polymer returns to its virgin color. The display films are comprised of linear fused heterocyclic ring systems, optionally with connecting units, or linear monocyclic ring systems and connecting units. The device requires low currents to operate and switch from the virgin state to the colored state. It also can optionally be operated to exhibit several colors.

Claims

1. An electrochromic device comprising:

a case, said case has a transparent face and a face opposite thereto which is capable of highlighting the display colors of the device during the write cycle;

a display electrode within said case and adjacent said transparent face, said display electrode comprises a transparent conductive electrode and a display polymer film attached thereto, said display polymer film comprises a linear tractable electroactive polymer, said polymer is capable of undergoing reversible oxidation, reversible reduction or both to form a linear charged, colored polymer incorporating charge-compensating ionic dopants, said polymer comprises diradical repeat units selected from the group consisting of a heterocyclic ring system including at least one Group 5B or Group 6B atom, wherein none of the ring carbon atoms are saturated, a heterocyclic ring system including at least one Group 5B or Group 6B atom wherein none of the ring carbon atoms are saturated and a connecting unit, and mixtures thereof, wherein said diradical repeat unit in the form of a monomeric repeat unit is capable of undergoing reversible oxidation, reversible reduction or both to form a stable ionic species and wherein said connecting unit is a conjugated system or atom or group of atoms which maintain π

-orbital overlap with the heterocyclic ring system;

a counter electrode adjacent to said light-colored face;

an electrolyte; and

means for applying a voltage and current to said display electrode and said counter electrode.

2. The electrochromic device according to claim 1 wherein said display polymer Group 5B or 6B heteroatom is selected from the group consisting of N, P, As, O, S. Se, Te or mixtures thereof and none of the heteroatoms occupies the ring fusion positions and the P, As, O, S, Se, Te atoms do not occupy adjacent ring positions.

3. The electrochromic device according to claim 2 wherein said heteratom is selected from the group consisting of N, S, O, or mixtures thereof.

4. The electrochromic device according to claim 3 wherein the heteroatoms are nitrogen and no more than two nitrogen atoms are bonded sequentially within the heterocyclic ring system.

5. The electrochromic device according to claim 3 wherein the diradicals are positional diradicals selected from the group consisting of thianthrenes;

phenoxathiins;

phenoxazine;

N-alkyphenothiazine;

dihydrophenazine;

dialkyldihydrophenazine;

dibenzodioxin;

benzoxazole;

benzothiazole;

benzoselenazole;

N-alkyl-substituted benzimidazole;

1,7-dimethyl-benzo[1,2,-d;

4,5-d'"'"']diimidazole;

benzo[1,2-d;

5,4-d'"'"']bisthiazole;

benzo[1,2-d;

4,5-d'"'"']bisthiazole;

benzo[1,2-d;

4,5-d'"'"']bis-selenazole;

benzo[1,2-d;

5,4-d'"'"']bis-selenazole;

benzo[1,2-d;

4,5-d'"'"']bistellurazole;

selenazole[5,4-f]benzothiazole;

1,8-dialkyl-benzo[1,2-d;

3,4-d'"'"']diimidazole;

benzo[1,2-d;

5,4-d'"'"']bisoxazole;

benzo[1,2-d;

4,5-d'"'"']bisoxazole;

benzo[1,2-d;

3,4-d'"'"']bisoxazole;

benzo[1,2-d;

3,4-d'"'"']bis-thiazole;

triazole and 1,4-phenylene;

thiadiazole and 1,4-phenylene;

oxadiazole and 1,4-phenylene;

oxazole and 1,4-phenylene;

thiazole and 1,4-phenylene;

cinnoline;

quinazoline;

quinoxaline;

2-phenylquinoxaline;

4-phenylquinoline;

phthalazine;

1,5-naphthyridine;

1,6-naphthyridine;

1,7-naphthyridine;

1,8-naphthyridine;

2,6-naphthyridine;

copyrine;

1,2,4-benzotriazine;

pyrido[3,2-d]pyrimidine;

pyrido[4,3-d]pyrimidine;

pyrido[3,4-d]pyrimidine;

pyrido[2,3-d]pyrimidine;

pyrido[2,3-b]pyrazine;

pyrido[3,4-b]pyrazine;

pyrido[2,3-d]pyridazine;

pyrido[3,4-d]pyridazine;

pyridazino[4,5-c]pyridazine;

pyrimido[5,4-d]pyrimidine;

pteridine;

pyrimido[4,5-d]pyridazine;

pyrimido[4,5-d]pyrimidine;

pyrazino[2,3-b]pyrazine;

pyrazino[2,3-d]pyridazine;

pyridazino[4,5-d]pyridazine;

pyrimido[4,5-c]pyridazine;

pyrazino[2,3-c]pyridazine;

pyrido[3,2-d]-as-triazine;

pyrimido[4,5-e]-as-triazine; and

pyrido[2,3-e]-as-triazine;

as-triazino[6,5-d]-as-triazine; and

mixtures of these diradicals.

6. The electrochromic device according to claim 5 wherein said counter electrode is Pt, Au, Ag/Ag halide.

7. The electrochromic device according to claim 5 wherein the solvent of the electrolyte solution is selected from the group consisting of acetonitrile;

polypropylene carbonate;

tetrahydrofuran;

propionitrile;

butyronitrile;

phenylacetonitrile;

dimethylformamide;

dimethoxyethane;

dimethylsulfoxide;

pyridine;

or mixtures thereof.

8. The electrochromic device according to claim 7 wherein the supporting electrolyte dissolved in the solvent is a salt selected from the group consisting of a cation-anion pair wherein the cations are selected from the group consisting of Li⁺, Na⁺, K⁺, Cs⁺, Mg⁺⁺, (CH₃)₄ N⁺, (C₂ H₅)₄ N⁺, (C₃ H₇)₄ N⁺, or (C₄ H₉)₄ N⁺, and the anions are selected from the group consisting of F^-, Cl^-, Br^-, I^-, ClO₄^-, BF₄^-, PF₆^-, AsF₆^-, or NO₃^-.

9. The electrochromic device according to claim 8 wherein said polymer is a polymer comprising diradical units of the positional diradicals of quinoline, isoquinoline, quinoxaline, said diradicals interspersed with connecting units, substituted derivatives thereof, or mixtures thereof.

10. The electrochromic device according to claim 9 wherein the polymer is selected from the group consisting of ##STR15## wherein Z is a connecting unit or nothing;

##STR16## wherein n is the degree of polymerization.

11. The electrochromic device according to claim 9 wherein Rⁱⁱⁱ is a substituent group selected from H, alkyl of 1 to 4 carbons, alkoxy of 1 to 4 carbon atoms, an alkylthio of 1 to 4 carbon atoms, a cycloaliphatic group of 5 or 6 carbon atoms, an alkenyl group of 2 to 4 carbon atoms, an aryl group of 6 to 10 carbon atoms, an aryl group of 6 to 10 carbon atoms substituted by 1 to 3 alkyl groups of 1 to 4 carbon atoms, alkenyl groups to 1 to 4 carbon atoms, alkynyl groups of 1 to 4 carbon atoms, alkoxy groups of 1 to 4 carbon atoms, 1 to 3 cyano groups, 1 to 3 halogen atoms, dialkyl amino groups of 1 to 4 carbon atoms, an alkylthiol of 1 to 4 carbon atoms, a 5- or 6-member, nitrogen-containing, unsaturated heterocyclic group;

R^vii is H or CH₃ ; and

the display polymer has the following formula;

##STR17##

12. The electrochromic device according to claim 8 wherein the polymer is selected from the group consisting of poly-2,2'"'"'-(p-phenylene)-1,1'"'"'-dimethyl-5,5'"'"'-bibenzimidazole;

poly-2,2'"'"'-(p-phenylene)-5,5'"'"'-bibenzoxazole;

poly-2,2'"'"'-(p-phenylene)-5,5'"'"'-bibenzothiazole;

poly-2,6-(p-phenylene)-benzo[1,2-d;

5,4-d'"'"']bisoxazole;

poly-2,6-(p-phenylene)-1,7-dimethyl-benzo[1,2-d;

4,5-d'"'"']diimidazole;

poly-2,6-(p-phenylene)-benzo[1,2-d;

4,5-d'"'"']bisthiazole;

poly-2,6-(m-phenylene)benzo[1,2-d;

4,5-d'"'"']bisthiazole;

poly-1,4-phenylene-2,5-(1,3,4-oxadiazole);

copolymer of oxadiazole and thiadiazole with 1,4-phenylene connecting units;

copolymer of oxadiazole and thiadiazole;

poly-1,4-phenylene-2,5-(1,3,4-thiadiazole);

poly-1,4-phenylene-2,4-(1,3-thiazole);

poly-1,4-phenylene-2,5-(1-phenyl-1,3,4-triazole);

poly-1,4-phenylene-2,5-(1,4-dithiin);

poly-2,6-(4-phenylquinoline);

poly-2,6-(4-phenylquinoline) plus a connecting unit;

poly-2,2'"'"'-(m-phenylene)-6,6'"'"'-bibenzoxazole;

poly-2,2'"'"'-(m-phenylene)-1,1'"'"'-diemthyl-6,6'"'"'-bibenzimidazole;

poly-2,2'"'"'-(m-phenylene)-6,6'"'"'-bibenzothiazole;

poly-2,2'"'"'-(N-methyl-p,p'"'"'-aminodiphenylene)-6,6'"'"'-bibenzoxazole;

poly-2,5-phenoxazine;

poly-2,5'"'"'-(3,7-dimethyl)phenoxazine;

poly-2,5-(1,4-phenylene)phenoxazine;

poly-3,7-(N-methylphenothiazine)-2,5-(1,3,4-oxadiazole);

poly 3,7-(phenoxathiin-4,4'"'"' dithiobiphenylene;

poly-(1,4-dithiophenylene-2,6-thianthrene);

poly-4,4'"'"'-N-methyl-aminodiphenylene-2,5-(1,3,4-oxidiazole);

poly-2,2'"'"'-(p-phenylene)-6,6'"'"'-bibenzoxazole;

poly-2,2'"'"'-(p-phenylene)-6,6'"'"'-bibenzothiazole;

poly-2,2'"'"'-(p-phenylene)-1,1'"'"'-dimethyl-6,6'"'"'-bibenzimidazole.

13. The electrochromic device according to claim 8 wherein said means for applying a current and voltage biases the display electrode to reducing conditions and the display polymer is selected from the group consisting of poly-2,2'"'"'-(p-phenylene)-1,1'"'"'-dimethyl-5,5'"'"'-bibenzimidazole;

poly-2,2'"'"'-(p-phenylene)-5,5'"'"'-bibenzoxazole;

poly-2,2'"'"'-(p-phenylene)-5,5'"'"'-bibenzothiazole;

poly-2,6-(p-phenylene)-benzo[1,2-d;

5,4d'"'"']bisoxazole;

poly2,6-(p-phenylene)-1,7-dimethyl-benzo[1,2-d;

4,5d'"'"']diimidazole;

poly-2,6-(p-phenylene)-benzo[1,2-d;

4,5d'"'"']bisthiazole;

poly-2,6-(m-phenylene)benzo[1,2-d;

4,5-d'"'"']bisthiazole;

poly-1,4-phenylene-2,5-(1,3,4-oxadiazole);

copolymer of oxadiazole and thiadiazole with 1,4 phenylene connecting units;

copolymer of oxadiazole and thiadiazole;

poly-1,4-phenylene-2,5-(1,3,4-thiadiazole);

poly-1,4-phenylene-2,4-(1,3-thiazole);

poly-1,4-phenylene-2,5-(1-phenyl-1,3,4-triazole);

poly-1,4-phenylene-2,5-(1,4-dithiin);

poly-2,6-(4-phenylquinoline);

poly-2,6-(4-phenylquinoline) plus a connecting unit;

poly-2,6-[4-(4'"'"'-chlorophenyl)quinoline]; and

poly-2,6-[4-(4'"'"'-methoxyphenyl)quinoline].

14. The electrochromic device according to claim 8 wherein said means for applying a current and voltage biases the display electrode to oxidizing conditions and said display polymer is selected from the group consisting of poly-2,2'"'"'-(m-phenylene)-6,6'"'"'-bibenzoxazole;

poly-2,2'"'"'-(m-phenylene)-1,1'"'"'-dimethyl-6,6'"'"'-bibenzimidazole;

poly-2,2'"'"'-(m-phenylene)-6,6'"'"'-bibenzothiazole;

poly-2,2'"'"'-(N-methyl-p,p'"'"'-aminodiphenylene)-6,6'"'"'-bibenzoxazole;

poly-2,5-phenoxazine;

poly-2,5'"'"'-(3,7-dimethyl)phenoxazine;

poly-2,5-(1,4-phenylene)phenoxazine;

poly-3,7-(N-methylphenothiazine)-2,5-(1,3,4-oxadiazole;

poly-3,7-(phenoxathiin-4,4'"'"'-dithiobiphenylene;

poly-(1,4-dithiophenylene-2,6-thianthrene); and

poly-4,4'"'"'-N-methylaminodiphenylene-2,5-(1,3,4-oxadiazole).

15. The electrochromic device according to claim 8 wherein the display polymer is a polymer selected from the group consisting of poly-2,2'"'"'-(m-phenylene)-6,6'"'"'-bibenzoxazole;

poly-2,2'"'"'-(m-phenylene)-1,1'"'"'-dimethyl-6,6'"'"'-bibenzimidazole;

poly-2,2'"'"'-(m-phenylene)-6,6'"'"'-bibenzothiazole;

poly-2,2'"'"'-(N-methyl-p,p'"'"'-aminodiphenylene)-6,6'"'"'-bibenzoxazole;

poly-2,5-phenoxazine;

poly-2,5'"'"'-(3,7-dimethyl)phenoxazine;

poly-2,5-(1,4-phenylene)phenoxazine;

poly-3,7-(N-methylphenothiazine)-2,5-(1,3,4-oxadiazole;

poly-3,7-)phenoxathiin-4,4'"'"'-dithiobiphenylene;

poly-(1,4-dithiophenylene-2,6-thianthrene);

poly-4,4'"'"'-N-methylaminodiphenylene-2,5-(1,3,4-oxadiazole);

poly-2,2'"'"'-(p-phenylene)-6,6'"'"'-bibenzoxazole;

poly-2,2'"'"'-(p-phenylene)-6,6'"'"'-bibenzothiazole; and

poly-2,2'"'"'-(p-phenylene)-1,1'"'"'-dimethyl-6,6'"'"'-bibenzimidazole.

16. The electrochromic device according to claim 8 wherein the display electrode and counter electrode contain display polymers.

17. The electrochromic device according to claim 16 wherein the display polymers are reversible n-type and p-type display polymers selected from the group consisting of poly-2,2'"'"'-(p-phenylene)-6,6'"'"'-bibenzoxazole;

poly-2,2'"'"'-(p-phenylene)-6,6'"'"'-bibenzothiazole; and

poly-2,2'"'"'-(p-phenylene)-1,1'"'"'-dimethyl-6,6'"'"'-bibenzimidazole.

18. The electrochromic device according to claim 8 wherein the display polymer in its colored form and associated with compensating ionic dopants has the formula:

##STR18## wherein a is 0 or 1;

b is 0 or 1;

c is 0 or 1;

n is an integer from 2 to 2000;

d is an integer from 1 to 4000;

S is an integer 1, 2, or 3;

R is a diradical of unsaturated heterocyclic ring system containing at least one Group 5B or 6B heteroatom, wherein none of the ring carbon atoms are saturated;

R'"'"' is the same diradical as R or a different diradical unsaturated heterocyclic ring system;

X is a diradical connecting unit;

Y is the same diradical connecting unit as X or a different diradical connecting unit; and

M is a charge-compensating ionic dopant of opposite electrical charge to the charge of the polymer backbone wherein the polymer backbone is capable of undergoing reversible oxidation or reversible reduction or both to form said linear charged polymer backbone, said diradical or diradical-connecting unit in the form of a monomeric repeat unit is capable of undergoing reversible oxidation or reversible reduction or both to form a stable ionic species, and wherein R and R'"'"', contain no exocyclic double bonds, and wherein said connecting unit is a conjugated system or atom or group of atoms which maintain π

-orbital overlap with the heterocyclic ring system.

19. The electrochromic device according to claim 18 wherein said means for applying a current and voltage produces at least two separate colors in the display polymer during the write cycle.

20. The electrochromic device according to claim 9 wherein the counter electrode comprises silver coated with silver halide and the display electrode comprises poly-2,6-(4-phenylquinoline).

21. The electrochromic device according to claim 1 wherein said display polymer film is a polymer having the formula:

##STR19## wherein Y is a connecting unit, Z is nothing or an alkyl C₁ -C₄ group, Rⁱⁱⁱ is a substituent group selected from H, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, an alkylthio of 1 to 4 carbon atoms, a cycloaliphatic group of 5 or 6 carbon atoms, a 5- or 6-member, nitrogen-containing, unsaturated heterocyclic group, an aryl group of 6 to 10 carbon atoms wherein said aryl gruop is substituted by 1 to 3 alkyl groups of 1 to 4 carbon atoms, alkenyl groups of 1 to 4 carbon atoms, alkynyl groups of 1 to 4 carbon atoms, alkoxy groups of 1 to 4 carbon atoms, 1 to 3 cyano groups, 1 to 3 halogen atoms, dialkyl amino groups of 1 to 4 carbon atoms, or an alkylthiol of 1 to 4 carbon atoms; and

n is the degree of film forming polymerization.