Electrochromic nickel oxide simultaneously doped with lithium and a metal dopant
View Patent ↗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.
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 x Ni(II) 1−y Ni(III) y M z O 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 x Ni(II) (1−y) Ni(III) (y) M(A) z O (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 x Ni(II) (1−y) Ni(III) (y) M(A) z O (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 x Ni(II) (1−y) Ni(III) (y) M(A) z O (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 x Ni(II) (1−y) Ni(III) (y) M(A) Z O (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 2.3 Ni(II) (0.5) Ni(III) (0.5) Y(III) 0.3 O 3.1 .
11. The electrochromic device of claim 1 , wherein said mixed oxide is Li 2.3 Ni(II) (0.5) Ni(III) (0.5) Zr(IV) 0.3 O 3.25 .
12. The electrochromic device of claim 1 , wherein said mixed oxide is Li 2.3 Ni(II) (0.5) Ni(III) (0.5) Hf(IV) 0.3 O 3.25 .
13. The electrochromic device of claim 1 , wherein said mixed oxide is Li 2.3 Ni(II) (0.5) Ni(III) (0.5) Zr(IV) 0.294 Hf(IV) 0.006 O 3.25 .
14. The electrochromic device of claim 1 , wherein said mixed oxide is Li 2.3 Ni(II) (0.5) Ni(III) (0.5) Ta(V) 0.3 O 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 μm −1 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 μm −1 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 x Ni(II) 1−y Ni(III) y M z O 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 x Ni(II) (1−y) Ni(III) (y) M(A) z O (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 x Ni(II) (1−y) Ni(III) (y) M(A) z O (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 x Ni(II) (1−y) Ni(III) (y) M(A) z O (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 x Ni(II) (1−y) Ni(III) (y) M(A) z O (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.