IP Library › Granted Patent US 12,298,643
Granted Patent B2
US 12,298,643 · App. 18/051,309 · Granted May 13, 2025

Electrochromic nickel oxide simultaneously doped with lithium and a metal dopant

Inventors: Dane T. Gillaspie (Golden, CO); Douglas G. Weir (Northfield, MN)
Assignees: SAGE ELECTROCHROMICS, INC.; ALLIANCE FOR SUSTAINABLE ENERGY, LLC
G02F1/1524C09K9/00G02F1/155
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,298,643
App. No.
18/051,309
Granted
May 13, 2025
Kind
B2
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 (23)

1. An electrochromic device comprising:

a first electrode comprising one of an electrochromic layer or a counter electrode layer,

a second electrode comprising other of the electrochromic layer or the counter electrode layer, wherein:

the counter electrode layer comprises at least one mixed oxide having a formula Li x Ni y M z O a , where M is a metal selected from the group consisting of zirconium, hafnium, tantalum, niobium, tungsten, vanadium, molybdenum, manganese, lanthanum, cerium, and any combination thereof; x and z independently range from greater than 0 to about 10; y is greater than 0 and about 1; and a range from (0.5x+1+0.5y+z) to about (0.5x+ 1+0.5y+3.5z).

2. The electrochromic device of claim 1 , wherein M is selected from the group consisting of Zr(IV), Hf(IV), Nb(V), Ta(V), Mo(VI), W(VI), and any combination thereof.

3. The electrochromic device of claim 2 , wherein Ni y comprises a mixture of Ni(II) 1-y and Ni(III) y .

4. The electrochromic device of claim 3 , wherein x ranges from 0.5 to 3.

5. The electrochromic device of claim 4 , wherein y ranges from about 0.1 to 1.

6. The electrochromic device of claim 5 , wherein a ranges from about 0 to 45.

7. The electrochromic device of claim 1 , wherein the counter electrode layer has a dark state optical density of no more than 20 μm −1 at an optical wavelength of 450 nm.

8. The electrochromic device of claim 1 , wherein the counter electrode layer has a dark state optical density of between 5 μm −1 and 20 μm −1 at an optical wavelength of 450 nm.

9. The electrochromic device of claim 1 , wherein the counter electrode layer has a dark state optical density of between 8 μm −1 and 12 μm −1 at an optical wavelength of 450 nm.

10. The electrochromic device of claim 1 , wherein the counter electrode layer has a mixed electronic and ionic conductivity from 10 −11 Scm −1 to 10 −6 Scm −1 .

11. The electrochromic device of claim 1 , wherein the counter electrode layer has a mixed electronic and ionic conductivity from 10 −10 Scm −1 to 10 −6 Scm −1 .

12. The electrochromic device of claim 1 , wherein the counter electrode layer has a lithium charge capacity between 10 mC/cm 2 to 100 mC/cm 2 .

13. The electrochromic device of claim 1 , the counter electrode layer has a refractive index from 1.7 to 2.5.

14. The electrochromic device of claim 1 , wherein the counter electrode layer has a band gap energy from 2.5 eV to 6 eV.

15. The electrochromic device of claim 1 , wherein M is in the most favorable oxidation state of the metal.

16. The electrochromic device of claim 1 , wherein the thickness of the counter electrode layer is in a range from about 80 nm to about 500 nm.

17. The electrochromic device of claim 1 , wherein x ranges from about 1.5 to about 3.

18. The electrochromic device of claim 1 , wherein y ranges from about 0.4 to about 0.95.

19. The electrochromic device of claim 1 , wherein z ranges from about 0.15 to about 1.

20. The electrochromic device of claim 1 , wherein x ranges from about 1.81 to about 2.5, y ranges from about 0.6 to about 0.9, and z ranges from about 0.2 to about 0.5.

Assignments (2)
CHANGE OF NAME Recorded Dec 16, 2025
From: ALLIANCE FOR SUSTAINABLE ENERGY, LLC
To: ALLIANCE FOR ENERGY INNOVATION, LLC
Reel/Frame 073993/0276 →
CONFIRMATORY LICENSE Recorded Jun 5, 2023
From: NATIONAL RENEWABLE ENERGY LABORATORY
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 063853/0340 →
Continuity (6)
Continuation 16689799 · Nov 20, 2019
Continuation 15479942 · Apr 5, 2017
Continuation 14031573 · Sep 19, 2013
Continuation 13554144 · Jul 20, 2012
Provisional Application 61510381 · Jul 21, 2011
Related Publication 20230168557A1 · Jun 1, 2023
References Cited (64)
US 5277986A · Cronin et al. · 1994 [cited by applicant]
US 5699192A · Van Dine et al. · 1997 [cited by applicant]
US 6094292A · Goldner · 2000 [cited by examiner]
US 6277523B1 · Giron · 2001 [cited by examiner]
US 6859297B2 · Lee et al. · 2005 [cited by applicant]
US 9651845B2 · Gillaspie et al. · 2017 [cited by applicant]
US 20010031403A1 · Giron · 2001 [cited by applicant]
US 20030174377A1 · Reynolds · 2003 [cited by examiner]
US 20030227663A1 · Agrawal et al. · 2003 [cited by applicant]
US 20040150867A1 · Lee et al. · 2004 [cited by applicant]
US 20040155263A1 · Giron · 2004 [cited by applicant]
US 20050100788A1 · Sada et al. · 2005 [cited by applicant]
US 20050277014A1 · Ku et al. · 2005 [cited by applicant]
US 20060028730A1 · Varaprasad et al. · 2006 [cited by applicant]
US 20060209383A1 · Burdis · 2006 [cited by examiner]
US 20070160907A1 · Jang et al. · 2007 [cited by applicant]
US 20080169185A1 · Burdis et al. · 2008 [cited by applicant]
US 20090057137A1 · Pitts · 2009 [cited by examiner]
US 20100007937A1 · Widjaja et al. · 2010 [cited by applicant]
US 20100014145A1 · Jang · 2010 [cited by examiner]
US 20100243427A1 · Kozlowski et al. · 2010 [cited by applicant]
US 20110151283A1 · Gillaspie et al. · 2011 [cited by applicant]
US 20140043666A1 · Weir et al. · 2014 [cited by applicant]
CN 1466794A · 2004 [cited by applicant]
CN 1699273A · 2005 [cited by applicant]
CN 1969408A · 2007 [cited by applicant]
CN 101441938A · 2009 [cited by applicant]
JP H1030181A · 1998 [cited by applicant]
JP 2006235632A · 2006 [cited by applicant]
JP 2009522613A · 2009 [cited by applicant]
JP 2012523019A · 2012 [cited by applicant]
KR 20010070985A · 2001 [cited by applicant]
KR 100526640B1 · 2006 [cited by applicant]
KR 20070062720A · 2007 [cited by applicant]
WO 2009029111A1 · 2009 [cited by applicant]
WO 2014025876A2 · 2014 [cited by applicant]
Passerini, S. et al., “The Intercalation of Lithium in Nickel Oxide and its Electrochromic Properties”, Journal of the Electrochemical Society, ECS, vol. 137, No. 10, Oct. 1, 1990, pp. 3297-3300. [cited by applicant]
Dong, Yan et al., “Microstructure and Dielectric Properties of LiTiNiO Thin Films”, Key Engineering Materials, vol. 336-338, 2007, pp. 2635-2638. [cited by applicant]
Svegl, F. et al., “Electrochromic Properties of Lithiated Co-Oxide (LixCo02) and Ni-Oxide (LixNi02) Thin Films Prepared by the Sol-Gel Route”, Solar Energy, Pergamon Press, Oxford, GB, vol. 68, No. 6, Jan. 1, 2000, pp. … [cited by applicant]
Wu, J.B. et al., “Analysis of AC Electrical Properties of (Li and Ti)-doped NiO”, Materials Science and Engineering B, vol. 99, 2003, pp. 294-297. [cited by applicant]
Lu, Z. et al., “Understanding the Anomalous Capacity of Li/Li[NixLi (1/3-2x/3)Mn(2/3-x/3]O2 Cells Using in Situ X-Ray Diffraction and Electrochemical Studies” Journal of the Electrochemical Society, vol. 149, 2002, pp. … [cited by applicant]
Pouillerie, C. et al., “Effect of Magnesium Substitution on the Cycling Behavior of Lithium Nickel Cobalt Oxide”, Journal of Power Sources, vol. 96, 2001, pp. 293-302. [cited by applicant]
Kim, J. et al., “A Comparative Study on the Substitution of Divalent, Trivalent and Tetravalent Metal lons in LiNi1-xMx02 (M= Cu2+, A13+ and Ti4+)”, Journal of Power Sources, vol. 104, 2002, pp. 33-39. [cited by applicant]
Lee, S. et al., “Electrochromic Behavior of Ni—W Oxide Electrodes”, Solar Energy Materials and Solar Cells 39 (1995), pp. 155-166. [cited by applicant]
Lee, S. et al., “A New Lithium Based Counter Electrochromic Material for Fast Optical Response”, Electrochemical Society Proceedings, vol. 96-24, pp. 191-205, San Antonio, TX (1996). [cited by applicant]
Lee, S. et al., “Characterization of Ni—W Oxide Thin Film Electrodes”, Solid State Ionics 109 (1998), pp. 303-310. [cited by applicant]
Lee, S. et al., “Electrochromic Mechanism in a-WO3-y Thin Films”, Applied Physics Letters, American Institute of Physics, vol. 74, No. 2, Jan. 11, 1999, pp. 242-244. [cited by applicant]
Lee, S. et al., “Raman Spectroscopic Studies of Ni—W Oxide Thin Films”, Solid State Ionics 140, 2001, pp. 135-139. [cited by applicant]
Scrosati, B., “1st International Meeting on Electrochromism (IME-1), Murano-Venice, Oct. 19-21, 1994”, Solar Energy Materials and Solar Cells 39 (1995), pp. 111-113. [cited by applicant]
Gillaspie, D. et al., “Nanocomposite Counter Electrode Materials for Electrochromic Windows,” Journal of the Electrochemical Society, vol. 157, No. 3, Jan. 20, 2010, pp. H328-H331. [cited by applicant]
Gillaspie, D. T. et al., “Metal-Oxide Films For Electrochromic Applications: Present Technology and Future Directions,” Journal of Materials Chemistry, vol. 20, No. 43, 2010, pp. 9585-9592. [cited by applicant]
Tateishi, K. et al., “LiMn2O4: A Spinel-Related Low-Temperature Modification,” Acta Crystallographica Section E, Structure Reports Online, vol. 60, No. 2, 2004, pp. i18-i21. [cited by applicant]
Lim, SunHye et al., “PVP-Assisted ZrO2 Coating on LiMn2O4 Spinel Cathode Nanoparticles Prepared by MnO2 Nanowire Templates,” Electrochemistry Communications, Elsevier, vol. 10, 2008, pp. 1478-1481. [cited by applicant]
Monk, Paul M. S. et al., “Electrochromism: Fundamentals and Appplications,” dated 1995, VCH, Federal Republic of Germany, XP002718689, pp. 59-92. [cited by applicant]
Monk, Paul M. S. et al., “Electrochromic Tungsten Oxide: Doping with Two or Three Other Metal Oxides,” Journal of Materials Chemistry, vol. 4, No. 7, 1994, pp. 1071-1074. [cited by applicant]
“Sputtering,” Wikipedia, the free encyclopedia; Feb. 7, 2006; 4 pages; http://en.wikipedia.org/wiki/Sputtering. [cited by applicant]
International Search Report and Written Opinion for Application No. PCT/US2013/053934, dated Apr. 23, 2014, 28 pages. [cited by applicant]
International Search Report issued in Application No. PCT/US2012/047569 dated Sep. 19, 2012, 3 pages. [cited by applicant]
European Search Report issued in Application No. EP06003692 dated May 9, 2006, 2 pages. [cited by applicant]
Answer, Affirmative Defenses, and Counterclaims of Defendant /Counterclaimant View, Inc., filed Feb. 11, 2013, Case C-12-06441 (SYI), 52 pages. [cited by applicant]
Complaint for Patent Infringement and Injunctive Relief, filed Dec. 20, 2012, Case C-12-6441, 37 pages. [cited by applicant]
Defendant-Counterclaimant View, Inc.'s Answer to Plaintiff and Counterclaim-Defendant Sage Electrochromics, Inc.'s Counterclaims, filed Apr. 15, 2013, Case C-12-6441 (JST) ,4 pages. [cited by applicant]
First Amended Answer, Affirmative Defenses, and Counterclaims of Defendant-Counterclaimant View, Inc., filed Mar. 4, 2013, Case C-12-06441 (JST), 120 pages. [cited by applicant]
Plaintiff and Counterclaim-Defendant Sage Electrochromics, Inc.'s Answer to Defendant and Counterclaimant View, Inc.'s First Amended Counterclaims, Affirmative Defenses, and Counterclaims, Case C-12-06441 (JST), filed M… [cited by applicant]