Electrochromic optical switching device

• US 5,142,406 A
• Filed: 10/30/1990
• Issued: 08/25/1992
• Est. Priority Date: 10/30/1990
• Status: Expired due to Fees

• Current Assignee: Regents of the University of California (University of California)
• Original Assignee: Regents of the University of California (University of California)
• Inventors: Visco, Steven J., Lampert, Carl M.
• Primary Examiner(s): James, Andrew J.
• Assistant Examiner(s): LIMANEK, ROBERT P
• Application Number:
  US07/606,063
• Time in Patent Office: 665 Days
• Field of Search: 350/357, 359/269, 359/275
• US Class Current: 359/269
• CPC Class Codes: G02F 1/1525 characterised by a particular ion transporting layer, e.g. electrolyte
• CPC Class Codes: G02F 1/155 Electrodes
• CPC Class Codes: G02F 2201/121 common or background
• CPC Class Codes: G02F 2202/022 polymeric
• CPC Class Codes: G02F 2203/01 transmissive
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 4/60 of organic compounds
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

An electrochromic cell is disclosed which comprises an electrochromic layer, a polymerizable organo-sulfur layer which comprises the counter electrode of the structure, and an ionically conductive electronically insulating material which comprises the separator between the electrodes. In a preferred embodiment, both the separator and the organo-sulfur electrode (in both its charged and uncharged states) are transparent either to visible light or to the entire solar spectrum. An electrochromic device is disclosed which comprises such electrodes and separator encased in glass plates on the inner surface of each of which is formed a transparent electrically conductive film in respective electrical contact with the electrodes which facilitates formation of an external electrical connection or contact to the electrodes of the device to permit electrical connection of the device to an external potential source.

Claims

1. An electrochromic cell comprising:

a) an electrochromic electrode;

b) an organo-sulfur counter electrode comprising a compound having the general formula, in its charged state, of (R(S)_y)_n wherein y is 1-6;

n is 2 to 1,000,000; and

R is one or more of the same or different aliphatic or aromatic organic moieties having 1 to 20 carbon atoms which may include one or more oxygen, sulfur, or nitrogen heteroatoms when R comprises one or more aromatic rings, or one or more oxygen, sulfur, nitrogen, or fluorine atoms associated with the chain when R comprises an aliphatic chain, wherein the aliphatic chain may be linear, branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereon; and

c) an electronically insulative separator material capable of ionic transport in contact with both of said electrodes.

2. The electrochromic cell of claim 1 wherein both said organo-sulfur electrode and said separator are transparent.

3. The electrochromic cell of claim 1 wherein at least one of said organo-sulfur electrode and said separator are semi-transparent.

4. The electrochromic cell of claim 1 which further includes an electrolyte containing a group IA element selected from the group consisting of hydrogen, lithium, sodium, potassium, rubidium, and cesium.

5. The electrochromic cell of claim 1 wherein said separator is selected from the group consisting of polyethylene oxide, oxymethylene-linked polyethylene oxide, polypropylene oxide, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, poly[bis-((methoxyethoxy)ethoxy) phosphozene, tantalum oxide (Ta₂ O₅), cesium oxide (Cs₂ O), aluminum oxide (Al₂ O₃), magnesium fluoride (MgF₂), and silicon oxide (SiO or BiO₂).

6. The electrochromic cell of claim 1 wherein said electrochromic electrode, said organo-sulfur electrode, and said separator all comprise materials in a solid state.

7. The electrochromic cell of claim 4 which further comprises a transparent electrical conductor in electrical contact with said electrochromic electrode and a second transparent electrical conductor in contact with said organo-sulfur electrode.

8. The electrochromic cell of claim 7 wherein said transparent electrical conductor is selected from the group consisting of tin oxide (SnO₃), tin oxide doped with antimony and fluorine (SnO₂ :

F,Sb), indium oxide (In₂ O₃), indium oxide and tin (In₂ O₃ ;

Sn) (5-15% Sn), zinc oxide (ZnO), zinc oxide and indium (ZnO;

In), zinc oxide and aluminum (ZnO;

Al), cadmium stannate (Cd₂ SnO₄), cadmium stannite (CdSnO₃), cadmium oxide (CdO), copper sulfide (Cu₂ S), titanium nitride (TiN), titanium oxynitride (TiO_x N_1-x), copper, silver, gold, aluminum, nickel, stainless steel, chromium, titanium, rhodium, and brass.

9. The electrochromic cell of claim 7 wherein at least one of said transparent electrical conductors is in contact with a glass substrate.

10. The electrochromic cell of claim 7 wherein said transparent electrical conductors are in electrical communication with electrical contact members to permit charge and discharge of said electrodes by a potential source.

11. The electrochromic cell of claim 1 wherein said organo-sulfur electrode material is further characterized by a sulfur-sulfur bond, when in the charged state, which upon discharge of said organo-sulfur electrode, is broken to form an organo-sulfur metal salt with metal ions in said cell.

22. The electrochromic cell of claim 1 wherein said organo-sulfur electrode comprising said compound having the general formula, in the charged state, of (R(S)_y)_n has a value of y of from 3 to 4;

and a value of n of over 4.

23. The electrochromic cell of claim 22 wherein said organo-sulfur electrode material is further characterized by a sulfur-sulfur bond, when in the charged state, which upon discharge of said organo-sulfur electrode, is broken to form an organo-sulfur metal salt with metal ions in said cell.

12. An electrochromic device comprising:

a) a first transparent electrically conductive film;

b) an electrochromic electrode capable of being in a transparent electrical charge state having a surface in electrical contact with said first transparent electrically conductive film;

c) a transparent organo-sulfur counter electrode comprising a compound having the general formula, in its charged state, of (R(S)_y)_n wherein y is 2 to 3;

n is 5 or more; and

R is one or more of the same or different aliphatic or aromatic organic moieties having 1 to 20 carbon atoms which may include one or more oxygen, sulfur, or nitrogen heteroatoms when R comprises one or more aromatic rings, or one or more oxygen, sulfur, nitrogen, or fluorine atoms associated with the chain when R comprises an aliphatic chain, wherein the aliphatic chain may be linear, branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereon,

d) a second transparent electrically conductive film in contact with said organo-sulfur electrode;

e) an electronically insulative separator material capable of ionic transport containing an electrolyte containing a group IA element selected from the group consisting of hydrogen, lithium, sodium, and potassium, separating said electrochromic electrode from said organo-sulfur electrode; and

f) a glass substrate in contact with one of said transparent electrically conductive films.

13. The electrochromic device of claim 12 including a second glass substrate in contact with the other of said transparent electrically conductive films.

14. The electrochromic device of claim 13 which further includes electrical contact members electrically connected, respectively, to said first and second transparent electrically conductive films.

15. The electrochromic device of claim 14 wherein said electrochromic electrode, said organo-sulfur electrode, and said separator all comprise materials in a solid state.

16. The electrochromic device of claim 15 which further includes sealing means which seal the end edges of said device.

17. The electrochromic device of claim 12 wherein said electrochromic electrode comprises a material capable of passing from a non-transparent state to a transparent or semitransparent state, depending upon the state of charge of said material, selected from the group consisting of transition metal oxides, heteropolyacids, metal-oxide cermets, mixed oxide composites, hydrous Group VIII metal oxides, organic electrochromic materials, and redox compounds.

18. The electrochromic device of claim 12 wherein said electrochromic electrode comprises a material capable of existing in a transparent or semitransparent state and a nontransparent state, depending upon the state of electrical charge of said material, selected from the group consisting of tungsten oxide (WO₃), molybdenum oxide (MoO₃), niobium oxide (Nb₂ O₅), vanadium oxide (V₂,O₅), titanium oxide (TiO₂ or Ti₂ O₅), copper oxide (Cu₂ O or uncolored CuO), bismuth oxide (Bi₂ O₃), lead oxide (PbO or PbO₂), chromium oxide (Cr₂ O₃), rhodium oxide (RhO, Rh(OH)_x, Rh₂ O₃, or RhO):

, cobalt oxide (CoO), manganese oxide (MnO or Mn(OH)₂), ruthenium hydroxide (Ru(OH)_x), nickel oxide (NiO or Ni(OH)₂), osmium hydroxide (Os(OH)_x), iridium oxide (IrO, IrO₂, or Ir(OH)₃), tungsten oxide-vanadium oxide, tungsten oxide-titanium oxide, molybdenum oxide-vanadium oxide, molybdenum oxide-tungsten oxide, nickel oxide-manganese oxide, iridium oxide-tin oxide (SnO₂), iridium oxide-indium oxide (In₂ O₃), phospho-tungstic acid (H₃ PO₄ (WO₃)₁₂ nH₂ O), ferric ferrocyanide (Fe₄ [Fe(Cn)_6]3), lithium ferric ferrocyanide (Li_x Fe_4-x [Fe(Cn)_6]3), gold tungstate (Au-WO₃), platinum tungstate (Pt-WO₃), 4,4'"'"'dipyridinium ((C₅ H₄ N)₂), diheptylviolgen-dibromide ((C₇ H₁₅)₂ (NC₅ H₄)₂ Br₂), (bis-4(-ethylpyridine-4'"'"'-y)pyridium)perchlorate, 1,1'"'"'-dibenzyl-4,4'"'"'-bipyridinium difluorborate, 5,10-dihydro-5,10-dimethylphenazine, methylviologen compounds, pyridine (C₅ H₅ N), 4,4'"'"'-diamino-3,3'"'"'-dimethylbiphenyl, orthotolidine (C₁₄ H₁₈ N);

, anthraquinone, 2-tertiary butylanthraquinone (C₁₄ H₇ O₂ C(CH₃)₃), phenothiazines, methylene blue (C₁₆ H₁₈ ClN₃ S), tetra thiafulvalene (C₆ H₄ S₄), pyrazoline (C₃ H₆ N₂), polythiophene ((C₄ H₄ S)_x), polyaniline ((C₆ H₅ NH₂)_x), polytriphenylamine ([(C₆ H₅)N]_x), lutetium diphthalocyanine ((C₃₂ H₁₆ N₈)₂ Lu), and tris(5,5'"'"'-dicarbo(3-acrylatoprop-1-oxy)-2,2'"'"'bipyridine) ruthenium(II).

19. The electrochromic device of claim 12 wherein said transparent electrically conductive films comprise tin oxide.

20. The electrochromic device of claim 12 wherein said separator material comprises polyethylene oxide.

21. An electrochromic device having one level of transparency when in one electrical charge state and a lower level of transparency when in another electrical charge state comprising:

a) a first transparent electrically conductive planar tin oxide film, including an electrical contact member;

b) a planar electrochromic solid state electrode capable of being in a transparent electrical charge state having a surface in electrical contact with said first transparent electrically conductive film and comprising one or more materials selected from the group consisting of transition metal oxides, heteropolyacids, metal-oxide cermets, mixed oxide composites hydrous Group VIII metal oxides, organic electrochromic materials, and redox compounds;

c) a transparent planar solid state organo-sulfur electrode having the formula, when in a charged state, of (R(S)_y)_n wherein y is 2 to 3;

n is 5 to about 1,000,000; and

R is one or more of the same or different aliphatic or aromatic organic moieties having 1 to 20 carbon atoms which may include one or more oxygen, sulfur, or nitrogen heteroatoms when R comprises one or more aromatic rings, or one or more oxygen, sulfur, nitrogen, or fluorine atoms associated with the chain when R comprises an aliphatic chain, wherein the aliphatic chain may be linear, branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereon;

d) a second transparent electrically conductive tin oxide film in contact with said organo-sulfur electrode, including an electrical contact member;

e) an electronically insulative planar solid state separator comprising polyethylene oxide capable of ionic transport containing an electrolyte having one or more group IA elements selected from the group consisting of hydrogen, lithium, sodium, potassium, rubidium, and cesium separating said electrochromic electrode from said organo-sulfur electrode;

f) planar glass substrates in contact with said transparent electrically conductive films; and

g) sealing means to seal the end edges of said planar members of said electrochromic device.

24. An electrochromic cell comprising:

a) an electrochromic electrode;

b) an organo-sulfur counter electrode comprising a organo-sulfur compound capable of polymerizing to form --S--S-- bonds between sulfur-containing groups when in a charged state; and

c) an electronically insulative separator material capable of ionic transport in contact with both of said electrodes.

25. The electrochromic cell of claim 24 wherein said organo-sulfur counter electrode is semi-transparent, in both the charged and discharged states.

26. The electrochromic cell of claim 24 wherein said organo-sulfur counter electrode is transparent, in both the charged and discharged states, to electromagnetic radiation of at least a narrow band.