Electrochromic assembly based on poly(3,4-ethylene-dioxythiophene) derivatives with a counterelectrode containing metal oxides from transition group VI or VIII

• US 6,323,988 B1
• Filed: 05/27/1999
• Issued: 11/27/2001
• Est. Priority Date: 05/29/1998
• Status: Expired due to Fees

• Current Assignee: Heraeus Clevios GmbH (Heraeus Holding GMBH)
• Original Assignee: Bayer AG
• Inventors: Wehrmann, Rolf, Heuer, Helmut-Werner
• Primary Examiner(s): Sugarman, Scott J.
• Assistant Examiner(s): Lucas, Michael A
• Application Number:
  US09/320,987
• Time in Patent Office: 915 Days
• Field of Search: 359/265, 359/273, 359/276, 359/245, 359/275, 359/296
• US Class Current: 359/265
• CPC Class Codes: G02F 1/15165 Polymers

Abstract

The invention relates to electrochromic assemblies having a layer structure, characterized in that one layer is an electrically conductive, electrochromic polydioxythiophene and a further layer is an ion-storage compound selected or a mixture of ion-storage compounds of the formulae (I) to (XIV).

Me¹O (I) Me¹(OH)₂ (IX) Me¹O_X (II) Me¹O(OH) (X) M_XMe¹O (III) MMe¹O₂ (XI) M_XMe¹O₂ (IV) Me¹O₂ (XII) M_xMe¹O_y (V) Me¹₂O₃ (XIII) Me²O₃ (VI) Me¹₂O₃.H₂O (XIV) M_XMe²O₃ (VII) M_XMe²_(1−x)O₃ (VIII)

where

Me¹ and Me² each represent a metal transition group VI or VII of the Mendeleev Periodic Table,

M represents a metal of main group I of the Mendeleev Periodic Table or a proton,

x represents a number from 0.001 to 5,

y represents a number from 0.001 to 5.

Claims

1. An electrochromic assembly comprising one or more layers, wherein one layer is an electrically conductive electrochromic polydioxythiophene and a further ion-storage layer is one or more ion-storage compounds selected from the group consisting of compounds having the formulas

2. An electrochromic assembly according to claim 1 wherein

Me¹ represents nickel or iridium, and

Me² represents molybdenum or tungsten.

3. An electrochromic assembly according to claim 1 wherein the ion-storage layer is one or more ion-storage compounds selected from the group consisting of compounds having the formulas

NiO_x,

Ni(OH)₂,

NiO(OH),

Ni₂O₃·

H₂O,

Li_xNiO_y,

H_yNiO_x,

WO₃,

Li_xWO₃,

IrO₃ , and

MoO₃,

wherein

x represents a number from 0.001 to 5, and

y represents a number from 0.001 to 5.

4. An electrochromic assembly according to claim 1 wherein the ion-storage layer contains

TiO₂,

CeO₂,

V₂O₅, Nb₂O₅,

Li_xCeO₂, Li_xV₂O₅,

Li_xTiO₂—

Li_xV₂O₅,

Li_xTiO₂, and/or

Li_xNb₂O₅,

wherein x represents a number from 0.001 to 5.

5. An electrochromic assembly according to claim 1 wherein the electrically conductive electrochromic polydioxythiophene comprises structural units of the formula (XV)

wherein

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

n represents an integer from 2 to 10,000, and polyanion counterions.

6. An electrochromic assembly according to claim 1 wherein the electrically conductive electrochromic polydioxythiophene comprises structural units of the formulas

wherein

R₁ and R₂ represent, independently of one another, hydrogen or a 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 group,

R₃ and R₄ represent, independently of one another, hydrogen or a (C₁-C₁₈)-alkyl, (C₂-C₁₂)-alkenyl, (C₃-C₇)-cycloalkyl, (C₇-C₁₅)-aralkyl, (C₆-C₁₀)-aryl, (C₁-C₁₈)-alkyloxy, or (C₂-C₁₈)-alkyloxy ester group substituted by at least one sulphonate group, with the proviso that R₃ and R₄ cannot both be hydrogen, and

n represents an integer from 2 to 10,000, and polyanion counterions.

7. An electrochromic assembly according to claim 6 wherein polyanion counterions are anions of polymeric carboxylic acid and/or polymeric sulphonic acids.

8. An electrochromic assembly according to claim 1 wherein the electrically conductive electrochromic polydioxythiophene comprises structural units of the formulas

wherein

R₃ represents hydrogen or a (C₁-C₁₈)-alkyl, (C₂-C₁₂)-alkenyl, (C₃-C₇)-cycloalkyl, (C₇-C₅)-aralkyl, (C₆-C₁₀)-aryl, (C₁-C₁₈)-alkyloxy, or (C₂-C₁₈)-alkyloxy ester group substituted by at least one sulphonate group, and

n represents an integer from 2 to 10,000, and polyanion counterions.

9. An electrochromic assembly according to claim 8 wherein polyanion counterions are anions of polymeric carboxylic acid and/or polymeric sulphonic acids.

10. An electrochromic assembly according to claim 1 wherein the electrochromic assemblies contain at least one transparent electrically conductive coating on a substrate.

11. An electrochromic assembly according to claim 1 wherein an electrically conductive polydioxythiophene is a conductive electrode material.

12. An electrochromic assembly according to claim 1 wherein a plate which has been mirrored by means of a metal is used as a conductive layer for connection to a power source.

13. An electrochromic assembly according to claim 1 additionally comprising a transparent gel electrolyte layer containing a crosslinked or uncrosslinked polymer, a lithium salt, and a solvent or solvent mixture.

14. An electrochromic assembly according to claim 13 wherein the polymer is a photocrosslinkable polymer.

15. An electrochromic assembly according to claim 13 wherein the gel electrolyte contains organic and/or inorganic fillers and/or additives.