Electrochromic device based on poly-(3,4-dioxy-thiopene) derivatives

• US 6,175,441 B1
• Filed: 03/11/1999
• Issued: 01/16/2001
• Est. Priority Date: 03/13/1998
• Status: Expired due to Term

• Current Assignee: Heraeus Clevios GmbH (Heraeus Holding GMBH)
• Original Assignee: Heuer
• Inventors: Osenberg, Frank, Wehrmann, Rolf, Jonas, Friedrich, Heuer, Helmut Werner
• Primary Examiner(s): Epps, Georgia
• Assistant Examiner(s): Spector, David N.
• Application Number:
  US09/266,372
• Time in Patent Office: 677 Days
• Field of Search: 345/105, 345/179, 359/265, 359/266, 359/267, 359/270, 359/273, 359/275, 359/274, 524/408, 524/430, 428/457, 428/690, 428/704
• US Class Current: 359/273
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/15165 Polymers
• CPC Class Codes: G02F 2001/1555 Counter electrode
• CPC Class Codes: Y10T 428/31678 Of metal

Abstract

Electrochromic assemblies having a layer structure, characterized in that one layer is an electrically conductive, electrochromic polydioxythiophene and a further layer comprises as ion storage compounds selected from the group consisting of the formulae (I) to (VI)

Me¹O₂  (I),

Me²₂O₅  (II),

Li_xMe¹O₂  (III),

Li_xMe²₂O₅  (IV),

Li_xMe¹O_2+x/2  (V),

Li_xMe²₂O_5+x/2  (VI),

where

Me¹ and Me² are each a metal of transition group III, IV and V of the Mendeleev Periodic Table, and

x is from 0.001 to 5.

Claims

1. An electrochromic assembly having a layer structure, characterized in that one layer is an electrically conductive, electrochromic polydioxythiophene and a further layer comprises ion storage compounds selected from the group consisting of the formulae (I) to (VI)

2. The electrochromic assembly according to claim 1, characterized in that

Me¹ is zirconium, cerium or titanium and

Me² is vanadium or niobium.

3. The electrochromic assembly according to claim 1, characterized in that the compounds present as ion storage are selected from the following groups:

V₂O₅,

Li_xV₂O₅,

Li_xV₂O_5+x/2,

CeO₂,

Li_xCeO₂,

Li_xCeO_2+x/2,

Nb₂O₅,

Li_xNb₂O₅.

4. The electrochromic assembly according to claim 1, characterized in that the ion storage present is one of the following mixtures:

TiO₂—

CeO₂,

CeO₂—

V₂O₅,

TiO₂—

V₂O₅,

Li_xCeO₂—

Li_xV₂O₅,

Li_xTiO₂—

Li_xCeO₂,

V₂O₅—

Nb₂O₅,

Li_xV₂O₅—

Li_xNb₂O₅.

5. The electrochromic assembly according to claim 1, characterized in that the polydioxythiophenes are built up of structural units of the formula (VII)

where

A¹ and A² are, independently of one another, substituted or substituted C₁-C₄-alkyl or together form substituted or unsubstituted C₁-C₄-alkylene, and

n is an integer from 2 to 10,000,

and polyanions are present as counterions.

6. Electrochromic assemblies according to claim 1, characterized in that polydioxythiophenes are built up of structural units of the formula (VIla) or (VIb)

where

R₁ and R₂ are, independently of one another, hydrogen, substituted or unsubstituted (C₁-C₁₈)-alkyl, (C₂-C₁₂)-alkenyl, (C₃-C₇)-cycloalkyl, (C7-C₁₅)-aralkyl, (C₆-C₁₀)-aryl, (C₁-C₁₈)-alkyloxy or (C₂-C₁₈)-alkyloxy ester and

R₃ and R₄ are, independently of one another, hydrogen, but not both at the same time, or (C₁-C₁₈)-alkyl, (C₂-C₁₂)-alkenyl, (C₃-C₇)-cycloalkyl, (C₇-C₁₅)-aralkyl, (C₆-C₁₀)-aryl, (C₁-C₁₈)-alkyloxy or (C₂-C₁₈)-alkyloxy ester, each substituted by at least one sulphonate group,

n is from 2 to 10,000.

7. The electrochromic assembly according to claim 1, characterized in that polydioxy-thiophenes are built up of structural units of the formula (VII a-1) or (VII b-1)

where R₃is (C₁-C₁₈)-alkyl, (C₂-C₁₂)-alkenyl, (C₃-C₇)-cycloalkyl, (C₇-C₁₅)-aralkyl, (C₆-C₁₀)-aryl, (C₁-C₁₈)-alkyloxy or (C₂-C₁₈)-alkyloxy ester, each substitutued by at least one sulphonate group, and n is from 2 to 10,000.

8. The electrochromic assembly as claimed in claim 7, characterized in that the polyanions are anions of polymeric carboxylic acids and/or polymeric sulphonic acids.

9. The electrochromic assembly according to claim 1, characterized in that at least one transparent electrically conductive coating on a substrate is present.

10. The electrochromic assembly according to claim 1, characterized in that a plate mirrored with a metal is present as conductive layer for making electrical contact.

11. The electrochromic assembly according to claim 1, characterized in that a transparent gel electrolyte comprising the following components:

Polymer (crosslinked or uncrosslinked),

Li salt,

Solvent or solvent mixture is present.

12. The electrochromic assembly according to claim 1, characterized in that photo-crosslinkable polymers are present.

13. The electrochromic assembly according to claim 11 characterized in that organic and/or inorganic fillers and/or additives are present in the gel electrolyte.