UV-stabilized electrochromic assembly based on poly(3,4-ethylenedioxythiophene) derivatives

• US 6,403,741 B1
• Filed: 05/27/1999
• Issued: 06/11/2002
• Est. Priority Date: 05/29/1998
• Status: Expired due to Fees

• Current Assignee: HC Starck GmbH (OPUS Investment SARL)
• Original Assignee: Bayer AG
• Inventors: Wehrmann, Rolf, Heuer, Helmut-Werner
• Primary Examiner(s): Wu, David W.
• Assistant Examiner(s): CHEUNG, WILLIAM K
• Application Number:
  US09/320,988
• Time in Patent Office: 1,111 Days
• Field of Search: 359/265, 359/270, 359/273, 359/275, 252/500, 252/583, 252/186, 526/256
• US Class Current: 526/256
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/15165 Polymers
• CPC Class Codes: G02F 1/157 Structural association of cells with optical devices, e.g. reflectors or illuminating devices

Abstract

UV-stabilized electrochromic assemblies having a layer structure, characterized in that one layer contains an electrically conductive, electrochromic polydioxythiophene and a further layer contains an inorganic ion-storage compound based on metal oxides or a mixture of such ion-storage compounds, where the gel electrolyte contains a mixed-in UV absorber.

Claims

1. A UV-stabilized electrochromic assembly having a UV-stabilized gel electrolyte comprising a dissolved UV absorber in a layer structure, wherein

(1) one layer is an electrically conductive electrochromic polydioxythiophene comprising structural units of the formula (XXII)

 

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, and

(2) a further ion-storage layer is one or more ion-storage compounds selected from the group consisting of

Me¹O₂ (I),

Me²₂O₅ (II),

Li_xMe¹O₂ (III),

Li_xMe²₂O₅ (IV),

Li_xMe¹O_2+x/2 (V),

Li_xMe²₂O_5+x/2 (VI),

Me³O (VII),

Me³O_x (VIII),

M_xMe³O (IX),

M_xMe³O₂ (X),

M_xMe³O_y (XI),

Me⁴O₃ (XII),

M_xMe⁴O₃ (XIII)

M_xMe⁴<sub>(1−

x)</sub>Me⁴_xO₃ (XIV)

Me³(OH)₂ (XV),

Me³O(OH) (XVI),

MMe³O₂ (XVII),

Me³O₂ (XVIII),

Me³₂O₃ (XIX),

Me³₂O₃.H₂O (XX), and

LiMe⁵O₃ (XXI),

 

wherein

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

Me³ and Me⁴ each represent a metal of transition group VI or VIII of the Mendeleev Periodic Table,

Me⁵ represents a metal of transition group V of the Mendeleev Periodic Table,

x represents a number from 0.001 to 5,

y represents a number from 0.001 to 5, and

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

2. A UV-stabilized electrochromic assembly according to claim 1 wherein

Me¹ represents zirconium, cerium, or titanium,

Me² represents vanadium, or niobium,

Me³ represents nickel or iridium,

Me⁴ represents molybdenum or tungsten, and

Me⁵ represents vanadium, niobium, or tantalum.

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

V₂O₅,

Li_XV₂O₅,

Li_XV₂O_5+X/2,

CeO₂,

Li_XCeO₂,

Li_XCeO_2+x/2,

Nb₂O₅,

Li_xNb₂O₅,

Li_xNb₂O_5+x/2,

LiNbO₃,

NiO,

NiO₂,

Ni(OH)₂,

NiO(OH),

LiNiO₂,

Ni₂O₃,

Ni₂O₃•

H₂O,

Li_xNiO, and

WO₃•

4. A UV-stabilized electrochromic assembly according to claim 1 wherein the ion-storage layer is

TiO₂−

CeO₂,

CeO₂−

V₂O₅,

TiO₂−

V₂O₅,

Li_xCeO₂−

Li_xV₂O₅,

Li_xTiO₂−

Li_xV₂O₅,

Li_xTiO₂−

Li_xCeO₂,

V₂O₅−

Nb₂O₅,

Li_xV₂O₅−

Li_xNb₂O₅,

NiO−

CeO₂, or

NiO−

TiO_{2 •}

Mo-5178RCE

5. A UV-stablized 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.

6. A UV-stabilized electrochromic assembly according to claim 5 wherein polyanion counterions are anions of polymeric carboxylic acid and/or polymeric sulphonic acids.

7. A UV-stabilized electrochromic assmebly 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-C₁₅)-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.

8. A UV-stabilized electrochromic assembly according to claim 7 wherein the polyanion counterions are anions of polymeric carboxylic acid and/or polymeric sulphonic acids.

9. A UV-stabilized electrochromic assembly according to claim 1 wherein the electrochromic assemblies contain at least one transparent electrically conductive coating on a substrate.

10. A UV-stabilized electrochromic assembly according to claim 1 wherein a plate (substrate) which has been mirrored by means of a metal is used as a conductive layer for connection to a power source.

11. A UV-stabilized electrochromic assembly according to claim 1 additionally comprising a transparent gel electrolyte layer containing a crosslinked or uncrosslinked polymer, a lithium salt, a solvent or solvent mixture, and one or more light stabilizers.

12. A UV-stabilized electrochromic assembly according to claim 8 wherein the polymer is a photocrosslinkable polymer.

13. A UV-stabilized electrochromic assembly according to claim 1 wherein the UV absorber is selected from the group consisting of benzophenones, benzotriazoles, organonickel compounds, salicylic esters, cinnamic esters, benzylidene malonates, benzoic esters, oxalanilides, stearically hindered amines, polymeric sterically hindered amines, hydroxyphenyltriazines, and mixtures thereof.

14. A UV-stabilized electrochromic assembly according to claim 8 wherein the gel electrolyte contains light stabilizers and organic and/or inorganic fillers and/or additives.