Electrochromic counter electrode

• US 6,859,297 B2
• Filed: 08/07/2001
• Issued: 02/22/2005
• Est. Priority Date: 08/07/2001
• Status: Expired due to Term

• Current Assignee: Alliance For Sustainable Energy LLC
• Original Assignee: Midwest Research Institute
• Inventors: Pitts, J. Roland, Lee, Se-Hee, Tracy, C. Edwin, Jorgensen, Gary J.
• Primary Examiner(s): Epps, Georgia
• Assistant Examiner(s): CHOI, WILLIAM C
• Application Number:
  US10/480,014
• Publication Number:
  US 20040150867A1
• Time in Patent Office: 1,295 Days
• Field of Search: 359/265, 359/267, 359/269, 359/273, 359/275, 359320-322, 252/583, 252/600
• US Class Current: 359/273
• CPC Class Codes: G02F 1/1524 Transition metal compounds
• CPC Class Codes: G02F 2001/1502 complementary cell

Abstract

The present invention discloses an amorphous material comprising nickel oxide doped with tantalum that is an anodically coloring electrochromic material. The material of the present invention is prepared in the form of an electrode (200) having a thin film (202) of an electrochromic material of the present invention residing on a transparent conductive film (203). The material of the present invention is also incorporated into an electrochromic device (100) as a thin film (102) in conjunction with a cathodically coloring prior art electrochromic material layer (104) such that the devices contain both anodically coloring (102) and cathodically coloring (104) layers. The materials of the electrochromic layers in these devices exhibit broadband optical complimentary behavior, ionic species complimentary behavior, and coloration efficiency complimentary behavior in their operation.

Claims

1. A metal oxide capable of undergoing reversible lithium metal insertion, said metal oxide being characterized upon lithium ion insertion by electrochromism, lithium ion mobility under an applied emf that is substantially similar to that of electrochromic tungsten oxide, and a lack of long range crystal structure, said metal oxide comprising:

a first transition metal present as a stable, amorphous metal oxide matrix; and

a second transition metal doped into said stable amorphous metal oxide matrix.

2. The metal oxide of claim 1 wherein, said first transition metal comprises essentially nickel and said second transition metal comprises essentially tantalum.

3. The metal oxide of claim 2, wherein the atomic ratio of tantalum:

nickel is in the range of about 5;

95 to about 95;

5.

4. The metal oxide of claim 3, further comprising inserted lithium atoms.

5. The metal oxide of claim 1, further comprising inserted lithium atoms.

6. The metal oxide of claim 5, wherein said metal oxide electrochromism is characterized by anodic electrochromic coloring.

7. A thin metal oxide film capable of undergoing reversible lithium metal insertion residing on a transparent substrate, said thin metal oxide film being characterized by displaying, upon lithium metal insertion, reversible anodically coloring electrochromism, said thin metal oxide film comprising:

a first transition metal present as a stable amorphous metal oxide matrix; and

a second transition metal doped into said stable amorphous metal oxide matrix.

8. The thin metal oxide film of claim 7, wherein said first transition metal comprises essentially nickel and said second transition metal comprises essentially tantalum.

9. The thin film of claim 8, wherein said first transition metal is present in the thin film in the range from about 5-95 atomic percent relative to said second transition metal.

10. The metal oxide of claim 9, further comprising inserted lithium atoms.

11. The metal oxide of claim 8, further comprising inserted lithium atoms.

12. The thin metal oxide film of claim 7, further comprising inserted lithium atoms.

13. A metal oxide film capable of undergoing lithium metal insertion, said metal oxide being formed on a substrate by reactive oxygen ion sputtering from a target containing both tantalum and nickel and having an atomic ratio of Tantalum:

Nickel of between about 5;

95 and about 95;

5, and lacking any long range ordered structure as determined by XRD.

14. The metal oxide film of claim 13, wherein the ratio of Ta:

Ni surface area in the sputtering target is between about 5;

95 and about 95;

5.

15. The metal oxide film of claim 14, wherein said substrate is a glass bearing a transparent conductive oxide coating selected from tin oxide and indium doped tin oxide.

16. The metal oxide film of claim 13, further comprising inserted lithium atoms.

17. An electrode containing a lithium metal injected metal oxide film layer, said metal oxide film layer being formed on a transparent glass substrate with a transparent layer of a conductive oxide interposed between said metal oxide film layer and said transparent glass substrate, wherein said metal oxide film is formed by reactive oxygen ion sputtering from a target containing both tantalum and nickel, and wherein said metal oxide film is subjected to a lithium metal injection process, said metal oxide film being characterized by the following properties:

an atomic ratio of Tantalum;

Nickel of between about 5;

95 and about 95;

5;

an absence of any long range crystal structure as determined by XRD;

electrochromic behavior such that said metal oxide film undergoes electrochromic coloring when connected to a cathode of an emf source having sufficient potential to drive said coloring and electrochromic bleaching when connected to the anode of an emf source having sufficient potential to drive said bleaching; and

an electrochromic coloration efficiency of greater than 5 cm²/C measured at about 400 nm.

18. The electrode of claim 17, wherein the atomic ratio of Ta:

Ni and the amount of lithium metal injected into said metal oxide film layer are selected to yield a cathodically coloring electrochromic electrode having broad band optical complimentary behavior, ionic species complimentary behavior, and coloration efficiency complimentary behavior with a tungsten oxide electrochromic electrode.

19. An electrochromic device, the device comprising:

a glass support;

a first conductive layer;

a tantalum nickel oxide layer wherein said layer is formed by sputtering and injected with lithium;

an electrolyte layer;

a tungsten oxide layer, wherein said layer is formed by vacuum evaporation; and

a second conductive layer in ohmic contact with said tungsten oxide layer.

20. The electrochromic device of claim 19 wherein said first and second conductive layers are indium doped tin oxide glass, and wherein said nickel tantalum oxide layer has a Ni:

Ta ratio of between about 95;

5 and about 5;

95.

21. The electrochemical device of claim 19, wherein said nickel tantalum oxide layer and said tungsten oxide layer combination exhibit a broadband optical complimentary behavior, an ionic species complimentary behavior, and a coloration efficiency complimentary behavior.

22. An electrode containing a lithium metal injected metal oxide film layer, said metal oxide film layer being formed on a transparent glass substrate with a transparent layer of a conductive tin oxide interposed between said metal oxide film layer and said transparent glass substrate, and wherein said metal oxide film is formed by reactive oxygen ion sputtering from a target containing both tantalum and nickel, wherein said metal oxide film is subjected to a lithium metal injection process, said metal oxide film being characterized by the following properties:

an atomic ratio of Tantalum;

Nickel of between about 5;

95 and about 95;

5;

an absence of any long range crystal structure as determined by XRD;

electrochromic behavior such that said metal oxide film undergoes electrochromic coloring when connected to a cathode of an emf source having sufficient potential to drive said coloring and electrochromic bleaching when connected to the anode of an emf source having sufficient potential to drive said bleaching; and

an electrochromic coloration efficiency of greater than 5 cm²/C measured at about 400 nm.

23. The electrode of claim 22 further comprising an atomic tantalum:

nickel ratio of between about 5;

95 and about 60;

40.

24. The electrode of claim 22 wherein the conductive tin oxide is indium tin oxide.