Electrochromic lithium nickel group 4 mixed metal oxides
View Patent ↗Multi-layer devices comprising a layer of an electrochromic lithium nickel oxide composition on a first substrate, the lithium nickel oxide composition comprising lithium, nickel and a Group 4 metal selected from titanium, zirconium, hafnium and a combination thereof.
1. A multi-layer electrochromic device comprising a layer of a lithium nickel oxide composition on a first substrate, the lithium nickel oxide composition comprising lithium, nickel, and at least one-metal selected from the group consisting of titanium, zirconium, and hafnimn, the lithium nickel oxide composition being characterized by a largest d-spacing of at least 2.5 A ; and wherein the lithium nickel oxide composition exhibits long range ordering as measured by the presence of at least one reflection peak in the XRD pattern below 26 degrees (20) when measured with copper Ka radiation.
2. The multi-layer electrochromic device of claim 1 wherein the lithium nickel oxide composition comprises titanium.
3. The multi-layer electrochromic device of claim 1 wherein (i) the atomic ratio of lithium to the combined amount of nickel and titanium in the lithium nickel oxide composition is at least 0.4:1, respectively, and (ii) the atomic ratio of the amount of titanium to the combined amount of nickel and titanium in the lithium nickel oxide composition is about 0.025:1 to about 0.8:1, respectively.
4. The multi-layer electrochromic device of claim 3 wherein the atomic ratio of lithium to the combined amount of nickel and titanium in the lithium nickel oxide composition is in the range about 0.75:1 to about 3:1, respectively.
5. The multi-layer electrochromic device of claim 3 wherein the atomic ratio of titanium to the combined amount of nickel and titanium in the lithium nickel oxide composition is in the range of about 0.1:1 and about 0.6:1, respectively.
6. The multi-layer electrochromic device of claim 1 wherein the lithium nickel oxide composition comprises zirconium.
7. The multi-layer electrochromic device of claim 1 wherein the atomic ratio of lithium to the combined amount of nickel and zirconium in the lithium nickel oxide composition is at least 0.4:1, respectively, and (ii) the atomic ratio of the amount of zirconium to the combined amount of nickel and zirconium in the lithium nickel oxide composition is about 0.025:1 to about 0.8:1, respectively.
8. The multi-layer electrochromic device of claim 7 wherein the atomic ratio of lithium to the combined amount of nickel and zirconium in the lithium nickel oxide composition is in the range of about 0.75:1 to about 3:1, respectively.
9. The multi-layer electrochromic device of claim 7 wherein the atomic ratio of zirconium to the combined amount of nickel and zirconium in the lithium nickel oxide composition is in the range of about 0.1:1 and about 0.6:1, respectively.
10. The multi-layer electrochromic device of claim 1 wherein the lithium nickel oxide composition comprises hafnium.
11. The multi-layer electrochromic device of claim 10 wherein the atomic ratio of lithium to the combined amount of nickel and hafnium in the lithium nickel oxide composition is at least 0.4:1, respectively, and (ii) the atomic ratio of the amount of hafnium to the combined amount of nickel and hafnium in the lithium nickel oxide composition is about 0.025:1 to about 0.8:1, respectively.
12. The multi-layer electrochromic device of claim 11 wherein the atomic ratio of lithium to the combined amount of nickel and hafnium in the lithium nickel oxide composition is in the range of about 0.75:1 to about 3:1, respectively.
13. The multi-layer electrochromic device of claim 11 wherein the atomic ratio of hafnium to the combined amount of nickel and hafnium in the lithium nickel oxide composition is in the range of about 0.1:1 and about 0.6:1, respectively.
14. The multi-layer electrochromic device of claim 1 wherein (i) the atomic ratio of lithium to the combined amount of nickel, titanium, zirconium and hafnium in the lithium nickel oxide composition is at least 0.4:1, respectively, and (ii) the atomic ratio of the combined amount of titanium, zirconium and hafnium to the combined amount of nickel, titanium, zirconium and hafnium in the lithium nickel oxide composition is about 0.025:1 to about 0.8:1, respectively.
15. The multi-layer electrochromic device of claim 14 wherein the atomic ratio of lithium to the combined amount of nickel, titanium, zirconium and hafnium in the lithium nickel oxide composition is in the range about 0.75:1 to about 3:1, respectively.
16. The multi-layer electrochromic device of claim 14 wherein the atomic ratio of the combined amount of titanium, zirconium and hafnium to the combined amount of nickel, titanium, zirconium and hafnium in the lithium nickel oxide composition is in the range of about 0.1:1 and about 0.6:1, respectively.
17. The multi-layer electrochromic device of claim 1 wherein (i) the lithium nickel oxide composition comprises at least one bleached state stabilizing element selected from the group consisting of Y, V, Nb, Ta, Mo, W, B, Al, Ga, In, Si, Ge, Sn, P, and Sb, (ii) the atomic ratio of lithium to the combined amount of nickel, titanium, zirconium, hafnium and the bleached state stabilizing element(s) in the lithium nickel oxide composition is at least 0.4:1, respectively, and (iii) the atomic ratio of the combined amount of titanium, zirconium, hafnium and the bleached state stabilizing element(s) to the combined amount of nickel, titanium, zirconium, hafnium and the bleached state stabilizing elements in the lithium nickel oxide composition is about 0.025:1 to about 0.8:1, respectively.
18. The multi-layer electrochromic device of claim 17 wherein the atomic ratio of lithium to the combined amount of nickel, titanium, zirconium, hafnium and the bleached state stabilizing element(s) in the lithium nickel oxide composition is in the range about 015:1 to about 3:1, respectively.
19. The multi-layer electrochromic device of claim 17 wherein the atomic ratio of the combined amount of titanium, zirconium, hafnium and the bleached state stabilizing elements to the combined amount of nickel, titanium, zirconium, hafnium and the bleached state stabilizing element(s) in the lithium nickel oxide composition is in the range of about 0.1:1 and about 0.6:1, respectively.
20. The multi-layer electrochromic device of claim 1 wherein the lithium nickel oxide composition layer has an average thickness between 25 nm and 2,000 nm.
21. The multi-layer electrochromic device of claim 1 wherein the first substrate comprises glass, plastic, metal, or metal-coated glass or plastic.
22. The multi-layer electrochromic device of claim 1 wherein the multi-layer device further comprises a first transparent conductive oxide layer and the first transparent conductive oxide layer is between the lithium nickel oxide composition layer and the first substrate.
23. The multi-layer electrochromic device of claim 1 wherein the lithium nickel oxide composition comprises at least 0.05 wt. % carbon.
24. The multi-layer electrochromic device of claim 1 wherein the lithium nickel oxide composition has a bleached state voltage of at least 2V.
25. A multi-layer electrochromic device of claim 1 wherein the multi-layer device further comprises a second substrate, a first electrically conductive layer, a second electrically conductive layer, a cathode layer, and an ion conductor layer, wherein the first electrically conductive layer is between the first substrate and the lithium nickel oxide layer, the lithium nickel oxide layer is between the first electrically conductive layer and the ion conductor layer, the second electrically conductive layer is between the cathode layer and the second substrate, the cathode layer is between the second electrically conductive layer and the ion conductor layer, and the ion conductor layer is between the cathode layer and the lithium nickel oxide anode layer.
26. A multi-layer electrochromic device comprising:
a first substrate;
a first electrically conductive layer;
a layer of a lithium nickel oxide composition, the lithium nickel oxide composition comprising lithium, nickel, and at least one metal selected from the group consisting of titanium, zirconium, and hafnium, the lithium nickel oxide composition being characterized by a largest d-spacing of at least 2.5 Å and at least one reflection peak in the XRD pattern below 26 degrees (20) when measured with copper Kα radiation;
an ion conductor layer;
a cathode layer;
a second electrically conductive layer; and
a second substrate,
wherein the first electrically conductive layer is between the first substrate and the layer of lithium nickel oxide composition, the layer of lithium nickel oxide composition is between the first electrically conductive layer and the ion conductor layer, the second electrically conductive layer is between the cathode layer and the second substrate, the cathode layer is between the second electrically conductive layer and the ion conductor layer, and the ion conductor layer is between the cathode layer and the lithium nickel oxide anode layer.
27. A multi-layer electrochromic device comprising:
a first substrate;
a first electrically conductive layer;
a layer of a lithium nickel oxide composition, the lithium nickel oxide composition comprising lithium, nickel, and at least one metal selected from the group consisting of titanium, zirconium, and hafnium, wherein (i) the atomic ratio of lithium to the combined amount of nickel, titanium, zirconium, and hafnium in the lithium nickel oxide composition is at least 0.4:1, respectively, and (ii) the atomic ratio of the amount of the combined amount of titanium, zirconium, and hafnium to the combined amount of nickel, titanium, zirconium, and hafnium in the lithium nickel oxide composition is about 0.025:1 to about 0.8:1, respectively, wherein the lithium nickel oxide composition is characterized by a largest d-spacing of at least 2.5 Å;
an ion conductor layer;
a cathode layer;
a second electrically conductive layer; and
a second substrate.