Electrochromic system

• US 6,861,014 B2
• Filed: 04/29/2003
• Issued: 03/01/2005
• Est. Priority Date: 02/06/1997
• Status: Expired due to Term

• Current Assignee: University College Dublin
• Original Assignee: University College Dublin
• Inventors: Fitzmaurice, Donald, Cinnsealach, Rachel, Nagaraja, S. Rao, Enright, Brendan
• Primary Examiner(s): Tucker, Philip C.
• Application Number:
  US10/425,349
• Publication Number:
  US 20030201430A1
• Time in Patent Office: 672 Days
• Field of Search: 252/583, 252/586, 359/265, 359/270, 359/272, 428/315.5, 428/411.1, 428/469, 428/702, 428/704
• US Class Current: 252/583
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/1516 comprising organic material
• CPC Class Codes: Y10T 428/249978 Voids specified as micro
• CPC Class Codes: Y10T 428/31504 Composite [nonstructural laminate]

Abstract

An electrochromic system having a first electrode disposed on a transparent or translucent substrate, a second electrode, an electrolyte, an electron donor in solution in the electrolyte, and a nanoporous-nanocrystalline film. The nanoporous-nanocrystalline film has a semiconducting metallic oxide with a redox chromophore adsorbed thereto, intermediate the first and second electrodes.

Claims

1. An electrochromic system comprising:

a first electrode disposed on a transparent or translucent substrate;

a second electrode;

an electrolyte;

an electron donor in solution in the electrolyte; and

a nanoporous-nanocrystalline film comprising a semiconducting metallic oxide having a redox chromophore adsorbed thereto, intermediate the first and second electrodes.

2. An electrochromic system according to claim 1, wherein the nanoporous-nanocrystalline film comprises a semiconducting metal oxide having a redox chromophore adsorbed thereto, wherein the redox chromophore comprises a compound of the formula

wherein X is a charge balancing ion.

3. An electrochromic system according to claim 1, wherein the nanoporous-nanocrystalline film comprises a semiconducting metal oxide having a redox chromophore adsorbed thereto, wherein the redox chromophore comprises a compound of the formula

wherein X is a charge balancing ion;

R₁ is one of the following

and R₂ is one of the following;

—

O⁻

—

CH₂CN.

4. An electrochromic system according to claim 1, wherein the nanoporous-nanocrystalline film comprises a semiconducting metal oxide having a redox chromophore adsorbed thereto, wherein the redox chromophore comprises a compound of the formula

wherein X is a charge balancing ion;

R₁ is one of the following

and R₂ is

where m is an integer of from 1 to 6 and n is an integer of from 1 to 10.

5. The electrochromic system according to claim 4, where m is 1 or 2 and n is an integer of from 1 to 5 .

6. An electrochromic system according to claim 1, wherein the nanoporous-nanocrystalline film comprises a semiconducting metal oxide having a redox chromophore adsorbed thereto, wherein the redox chromophore comprises a compound of the formula

wherein X is a charge balancing ion;

R₁ is

wherein n is 2 or 3, and R₂ is one of the following;

—

O⁻

—

CH₂CN.

7. An electrochromic system according to claim 1, wherein the nanoporous-nanocrystalline film comprises a semiconducting metal oxide having a redox chromophore adsorbed thereto, wherein the redox chromophore comprises a compound of the formula

wherein X is a charge balancing ion;

R₁ is

wherein n is 2 or 3, and R₂ is

where m is an integer of from 1 to 6 and z is an integer of from 1 to 10.

8. An electrochromic system according to claim 1, wherein the semiconducting metallic oxide of the nanoporous-nanocrystalline film is an oxide of a metal selected from titanium, zirconium, hafnium, chromium, molybdenum, tungsten, vanadium, niobium, tantalum, silver, zinc, strontium, (Fe²⁺ and Fe³⁺) and nickel and perovskites thereof, preferably TiO₂, WO₃, MoO₃, ZnO or SnO₂.

9. An electrochromic system according to claim 2, wherein the semiconducting metallic oxide of the nanoporous-nanocrystalline film is an oxide of a metal selected from titanium, zirconium, hafnium, chromium, molybdenum, tungsten, vanadium, niobium, tantalum, silver, zinc, strontium, iron (Fe²⁺ and Fe³⁺) and nickel and perovskites thereof, preferably TiO₂, WO₃, MoO₃, ZnO or SnO₂.

10. An electrochromic system according to claim 3, wherein the semiconducting metallic oxide of the nanoporous-nanocrystalline film is an oxide of a metal selected from titanium, zirconium, hafnium, chromium, molybdenum, tungsten, vanadium, niobium, tantalum, silver, zinc, strontium, iron (Fe²⁺ and Fe³⁺) and nickel and perovskites thereof, preferably TiO₂, WO₃, MoO₃, ZnO or SnO₂.

11. An electrochromic system according to claim 4, wherein the semiconducting metallic oxide of the nanoporous-nanocrystalline film is an oxide of a metal selected from titanium, zirconium, hafnium, chromium, molybdenum, tungsten, vanadium, niobium, tantalum, silver, zinc, strontium, iron (Fe²⁺ and Fe³⁺) and nickel and perovskites thereof, preferably TiO₂, WO₃, MoO₃, ZnO or SnO₂.

12. An electrochromic system according to claim 1, wherein the electrolyte is in liquid form, preferably comprising at least one electrochemically inert salt optionally in molten form or in solution in a solvent, the salt preferably being selected from hexafluorophosphate, bis-trifluoromethanesulfonate, bis-trifluoromethyl-sulfonylamidure, tetraalkylammonium, dialkyl-1,3-imidazolium and lithium perchlorate or a mixture thereof and/or is a salt in molten form selected from trifluoromethanesulfonate, 1-ethyl, 3-methyl imidazolium bis-trifluoromethyl-sulfonylamidure and 1-propyl-dimethyl imidazolium bis-trifluoromethyl-sulfonylamidure or a mixture thereof, preferably lithium perchlorate;

and/or the solvent is selected from acetonitrile, butyronitrile, glutaronitrile, dimethylsulfoxide, dimethylformamide, dimethylacetamide, N-methyloxazolidinone, dimethyl-tetrahydropyrimidinone and γ

-butyrolactone or a mixture thereof.

13. An electrochromic system according to claim 2, wherein the electrolyte is in liquid form, preferably comprising at least one electrochemically inert salt optionally in molten form or in solution in a solvent, the salt preferably being selected from hexafluorophosphate, bis-trifluoromethanesulfonate, bis-trifluoromethyl-sulfonylamidure, tetraalkylammonium, dialkyl-1,3-imidazolium and lithium perchlorate or a mixture thereof and/or is a salt in molten form selected from trifluoromethanesulfonate, 1-ethyl, 3-methyl imidazolium bis-trifluoromethyl-sulfonylamidure and 1-propyl-dimethyl imidazolium bis-trifluoromethyl-sulfonylamidure or a mixture thereof, preferably lithium perchlorate;

and/or the solvent is selected from acetonitrile, butyronitrile, glutaronitrile, dimethylsulfoxide, dimethylformamide, dimethylacetamide, N-methyloxazolidinone, dimethyl-tetrahydropyrimidinone and γ

-butyrolactone or a mixture thereof.

14. An electrochromic system according to claim 3, wherein the electrolyte is in liquid form, preferably comprising at least one electrochemically inert salt optionally in molten form or in solution in a solvent, the salt preferably being selected from hexafluorophosphate, bis-trifluoromethanesulfonate, bis-trifluoromethyl-sulfonylamidure, tetraalkylammonium, dialkyl-1,3-imidazolium and lithium perchlorate or a mixture thereof and/or is a salt in molten form selected from trifluoromethanesulfonate, 1-ethyl, 3-methyl imidazolium bis-trifluoromethyl-sulfonylamidure and 1-propyl-dimethyl imidazolium bis-trifluoromethyl-sulfonylamidure or a mixture thereof, preferably lithium perchlorate;

and/or the solvent is selected from acetonitrile, butyronitrile, glutaronitrile, dimethylsulfoxide, dimethylformamide, dimethylacetamide, N-methyloxazolidinone, dimethyl-tetrahydropyrimidinone and γ

-butyrolactone or a mixture thereof.

15. An electrochromic system according to claim 4, wherein the electrolyte is in liquid form, preferably comprising at least one electrochemically inert salt optionally in molten form or in solution in a solvent, the salt preferably being selected from hexafluorophosphate, bis-trifluoromethanesulfonate, bis-trifluoromethyl-sulfonylamidure, tetraalkylammonium, dialkyl-1,3-imidazolium and lithium perchlorate or a mixture thereof and/or is a salt in molten form selected from trifluoromethanesulfonate, 1-ethyl,3-methyl imidazolium bis-trifluoromethyl-sulfonylamidure and 1-propyl-dimethyl imidazolium bis-trifluoromethyl-sulfonylamidure or a mixture thereof, preferably lithium perchlorate;

and/or the solvent is selected from acetonitrile, butyronitrile, glutaronitrile, dimethylsulfoxide, dimethylformamide, dimethylacetamide, N-methyloxazolidinone, dimethyl-tetrahydropyrimidinone and γ

-butyrolactone or a mixture thereof.

16. An electrochromic system according to claim 1, wherein the electrolyte is in liquid form and/or the electron donor is a metallocene or a derivative thereof, preferably ferrocene.

17. An electrochromic system according to claim 2, wherein the electrolyte is in liquid form and/or the electron donor is a metallocene or a derivative thereof, preferably ferrocene.

18. An electrochromic system according to claim 3 wherein the electrolyte is in liquid form and/or the electron donor is a metallocene or a derivative thereof, preferably ferrocene.

19. An electrochromic system according to claim 4, wherein the electrolyte is in liquid form and/or the electron donor is a metallocene or a derivative thereof, preferably ferrocene.