Electrochromic nickel oxide simultaneously doped with lithium and a metal dopant

• US 8,687,261 B2
• Filed: 07/20/2012
• Issued: 04/01/2014
• Est. Priority Date: 07/21/2011
• Status: Active Grant

• Current Assignee: Alliance For Sustainable Energy LLC, Sage Electrochromics, Inc (Compagnie de Saint-Gobain SA)
• Original Assignee: Alliance For Sustainable Energy LLC, Sage Electrochromics, Inc (Compagnie de Saint-Gobain SA)
• Inventors: Gillaspie, Dane T., Weir, Douglas G.
• Primary Examiner(s): Dinh, Jack
• Application Number:
  US13/554,144
• Publication Number:
  US 20130182307A1
• Time in Patent Office: 620 Days
• Field of Search: 359265-275
• US Class Current: 359/265
• CPC Class Codes: C09K 9/00 Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
• CPC Class Codes: G02F 1/1524 Transition metal compounds
• CPC Class Codes: G02F 1/155 Electrodes

Abstract

An electrochromic device comprising a counter electrode layer comprised of lithium metal oxide which provides a high transmission in the fully intercalated state and which is capable of long-term stability, is disclosed. Methods of making an electrochromic device comprising such a counter electrode are also disclosed.

Claims

1. An electrochromic device comprising:

(a) a first electrode comprising one of a electrochromic layer or a counter electrode layer,

(b) a second electrode comprising other of said electrochromic layer or said counter electrode layer,

(c) an ion-conductor layer for conducting ions between said first and second electrodes,

(d) a first conductive layer, and

(e) a second conductive layer,

said first and second electrodes and said ion-conductor layer being sandwiched between said first and second conductive layers,

said counter electrode layer comprising at least one mixed oxide having a formula Li_xNi(II)<sub>1−

y</sub>Ni(III)_yM_zO_a, where M is a metal, and x is about 0 to about 10, y is about 0 to about 1, z is about 0 to about 10, and a is from about (0.5x+1+0.5y+z) to about (0.5x+1+0.5y+3.5z).

2. The electrochromic device of claim 1, wherein said mixed oxide has the formula Li_xNi(II)₍₁₋

y)Ni(III)_(y)M(A)_zO_{(1+0.5x+0.5y+1.5z)}, where A is the oxidation state of the metal M.

3. The electrochromic device of claim 2, wherein M(A) is selected from the group consisting of Al(III), Sc(III), Cr(III), Co(III), Y(III), Rh(III), In(III), La(III), Ce(III), Nd(III), and Sm(III).

4. The electrochromic device of claim 1, wherein said mixed oxide has the formula Li_xNi(II)₍₁₋

y)Ni(III)_(y)M(A)_zO_{(1+0.5x+0.5y+2z)}, where A is the oxidation state of the metal M.

5. The electrochromic device of claim 4, wherein M(A) is selected from the group consisting of Si(IV), Ti(IV), Mn(IV), Zr(IV), Sn(IV), Ce(IV), Hf(IV), Re(IV), and Ir(IV).

6. The electrochromic device of claim 1, wherein said mixed oxide has the formula Li_xNi(II)₍₁₋

y)Ni(III)_(y)M(A)_zO_{(1+0.5x+0.5y+2.5z)}, where A is the oxidation state of the metal M.

7. The electrochromic device of claim 6, wherein M(A) is selected from the group consisting of V(V), Nb(V), Sb(V), Ta(V), and Pa(V).

8. The electrochromic device of claim 1, wherein said mixed oxide has the formula Li_xNi(II)₍₁₋

y)Ni(III)_(y)M(A)_ZO_{(1+0.5x+0.5y+3z)}, where A is the oxidation state of the metal M.

9. The electrochromic device of claim 8, wherein M(A) is selected from the group consisting of Cr(VI), Se(VI), Mo(VI), Te(VI), and W(VI).

10. The electrochromic device of claim 1, wherein said mixed oxide is Li_2.3Ni(II)_(0.5)Ni(III)_(0.5)Y(III)_0.3O_3.1.

11. The electrochromic device of claim 1, wherein said mixed oxide is Li_2.3Ni(II)_(0.5)Ni(III)_(0.5)Zr(IV)_0.3O_3.25.

12. The electrochromic device of claim 1, wherein said mixed oxide is Li_2.3Ni(II)_(0.5)Ni(III)_(0.5)Hf(IV)_0.3O_3.25.

13. The electrochromic device of claim 1, wherein said mixed oxide is Li_2.3Ni(II)_(0.5)Ni(III)_(0.5)Zr(IV)_0.294Hf(IV)_0.006O_3.25.

14. The electrochromic device of claim 1, wherein said mixed oxide is Li_2.3Ni(II)_(0.5)Ni(III)_(0.5)Ta(V)_0.3O_3.4.

15. The electrochromic device of claim 1, wherein said mixed oxide is further doped with an additional metal or metal oxide.

16. The electrochromic device of claim 1, wherein said mixed oxide has an optical density in the dark state of at least about 10 μ

m<sup>−

1</sup> at an optical wavelength of about 450 nm.

17. The electrochromic device of claim 1, wherein said mixed oxide has a bleached state optical absorption of less than about 0.5 μ

m<sup>−

1</sup> at an optical wavelength of about 450 nm.

18. The electrochromic device of claim 1, wherein said mixed oxide has a refractive index of at least about 2.0.

19. The electrochromic device of claim 1, wherein a thickness of said counter electrode layer ranges from about 80 nm to about 500 nm.

20. The electrochromic device of claim 19, wherein said thickness ranges from about 100 nm to about 320 nm.

21. The electrochromic device of claim 1, wherein said mixed oxide is substantially amorphous.

22. The electrochromic device of claim 1, wherein said mixed oxide is prepared by d.c. magnetron reactive sputter deposition.

23. An insulated glazing unit comprising the electrochromic device of claim 1.

24. A method for the preparation of an electrochromic device comprising:

(a) providing a first conductive layer,

(b) depositing one of an electrochromic layer or a counter electrode layer on said first conductive layer, thereby providing a first deposited electrode,

(c) depositing an ion-conductor layer on said first deposited electrode,

(d) depositing the other of said electrochromic layer or said counter electrode layer on said ion-conductor layer, thereby providing a second deposited electrode,

(e) depositing a second conductive layer on said second deposited electrode,

wherein said counter electrode layer comprises a mixed oxide having a formula Li_xNi(II)<sub>1−

y</sub>Ni(III)_yM_zO_a, where M is a metal, and x is about 0 to about 10, y is about 0 to about 1, z is about 0 to about 10, and a is from about (0.5x+1+0.5y+z) to about (0.5x+1+0.5y+3.5z).

25. The method of claim 24, further comprising depositing lithium into one of said ion-conductor layer or said counter electrode layer.

26. The method of claim 24, wherein the mixed oxide has the formula Li_xNi(II)₍₁₋

y)Ni(III)_(y)M(A)_zO_{(1+0.5x+0.5y+1.5z)}, where A is the oxidation state of the metal M.

27. The method of claim 26, wherein M(A) is selected from the group consisting of Al(III), Sc(III), Cr(III), Co(III), Y(III), Rh(III), In(III), La(III), Ce(III), Nd(III), and Sm(III).

28. The method of claim 24, wherein the mixed oxide has the formula Li_xNi(II)₍₁₋

y)Ni(III)_(y)M(A)_zO_{(1+0.5x+0.5y+2z)}, where A is the oxidation state of the metal M.

29. The method of claim 28, wherein M(A) is selected from the group consisting of Si(IV), Ti(IV), Mn(IV), Zr(IV), Sn(IV), Ce(IV), Hf(IV), Re(IV), and Ir(IV).

30. The method of claim 24, wherein the mixed oxide has the formula Li_xNi(II)₍₁₋

y)Ni(III)_(y)M(A)_zO_{(1+0.5x+0.5y+2.5z)}, where A is the oxidation state of the metal M.

31. The method of claim 30, wherein M(A) is selected from the group consisting of V(V), Nb(V), Sb(V), Ta(V), and Pa(V).

32. The method of claim 24, wherein the mixed oxide has the formula Li_xNi(II)₍₁₋

y)Ni(III)_(y)M(A)_zO_{(1+0.5x+0.5y+3z)}, where A is the oxidation state of the metal M.

33. The method of claim 32, wherein M(A) is selected from the group consisting of Cr(VI), Se(VI), Mo(VI), Te(VI), and W(VI).

34. The method of claim 24, wherein said counter electrode is deposited by d.c. magnetron reactive sputtering.