Process for preparing multi-layer electrochromic stacks

• US 10,061,177 B2
• Filed: 07/22/2015
• Issued: 08/28/2018
• Est. Priority Date: 07/23/2014
• Status: Active Grant

• Current Assignee: Halio Incorporated
• Original Assignee: Kinestral Technologies, Inc.
• Inventors: Choi, Hye Jin, Bailey, Mark, Bass, John David, Von Kugelgen, Stephen Winthrop, Lachman, Eric, Turner, Howard W., Giaquinta, Daniel Mark
• Primary Examiner(s): Gross, Carson
• Application Number:
  US14/806,545
• Publication Number:
  US 20160026055A1
• Time in Patent Office: 1,133 Days
• CPC Class Codes: B05D 1/005 Spin coating
• CPC Class Codes: B05D 3/0486 Operating the coating or treatment in a controlled atmosphere
• CPC Class Codes: B32B 17/10513 Electrochromic layer
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C03C 17/25 by deposition from the liquid phase
• CPC Class Codes: C03C 2217/21 Oxides
• CPC Class Codes: C23C 18/1254 Sol or sol-gel processing
• CPC Class Codes: G02F 1/1523 comprising inorganic material
• CPC Class Codes: G02F 1/1524 Transition metal compounds
• CPC Class Codes: G02F 1/155 Electrodes
• CPC Class Codes: G02F 2001/1555 Counter electrode

Abstract

Process for forming a multi-layer electrochromic structure, the process comprising depositing a film of a liquid mixture onto a surface of a substrate, and treating the deposited film to form an anodic electrochromic layer, the liquid mixture comprising a continuous phase and a dispersed phase, the dispersed phase comprising metal oxide particles, metal alkoxide particles, metal alkoxide oligomers, gels or particles, or a combination thereof having a number average size of at least 5 nm.

Claims

1. A process for preparing a multi-layer electrochromic structure, the process comprising the steps of:

(a) forming an electrode, the formation of the electrode comprising depositing a film of a first liquid mixture onto an electrode substrate to form a first deposited film and thermally treating the first deposited film to form an electrode electrochromic layer having an electrochemical state and a surface;

(b) forming a counter-electrode electrochromic layer by a series of steps comprising depositing a film of a second liquid mixture onto a counter-electrode substrate to form a second deposited film and thermally treating the second deposited film to form a counter-electrode electrochromic layer comprising an inorganic electrochromic material on the counter-electrode substrate, wherein the counter-electrode electrochromic layer comprises an exposed surface and an electrochemical state, the electrochemical state of the counter-electrode electrochromic layer being matched to the electrochemical state of the thermally treated electrode; and

(c) forming a laminate of the electrode electrochromic layer, the counter-electrode electrochromic layer and an ion conductor layer, the ion conductor layer being sandwiched between the exposed surfaces of the electrode electrochromic layer and the counter-electrode electrochromic layer.

2. The process of claim 1, wherein the ion conductor layer comprises polymerizable monomers.

3. The process of claim 1 wherein the electrode layer is an anodic electrochromic layer adapted to cycle between bleached states having a transmissivity of at least 70% and darkened states having a transmissivity less than 30%.

4. The process of claim 1 wherein the second liquid mixture is deposited on the counter-electrode substrate by dip coating, spin coating, die coating, or spray coating.

5. The process of claim 1 wherein the first liquid mixture is deposited by a wet-coating technique other than electrolytic deposition.

6. The process of claim 1 wherein the counter-electrode electrochromic layer is optically passive.

7. The process of claim 1 wherein the first liquid mixture, the second liquid mixture or each of the first and the second liquid mixtures comprise a continuous phase and a dispersed species wherein the dispersed species has a number average size selected from the group consisting of at least 10 nm, at least 25 nm, at least 50 nm, at least 75 nm, and at least 100 nm.

8. The process of claim 7 wherein the dispersed species comprises discrete particles.

9. The process of claim 7 wherein the first or the second liquid mixture is a colloidal dispersion.

10. The process of claim 7 wherein the process further comprises combining at least one hydrolysable source material in a solvent system, and hydrolyzing the hydrolysable source material to form the first or the second liquid mixture.

11. The process of claim 10 wherein the hydrolysable source material comprises a hydrolysable lithium source material, a hydrolysable nickel source material or hydrolysable bleached state stabilizing element source material.

12. The process of claim 11 wherein the hydrolysable lithium source material, the hydrolysable nickel source material or the hydrolysable bleached state stabilizing element source material is a metal alkoxide comprising lithium, nickel and/or the bleached state stabilizing element.

13. The process of claim 10 wherein the hydrolysable source material is hydrolyzed by adding water to the first or second liquid mixture.

14. The process of claim 10 wherein the hydrolysable source material is hydrolyzed by water generated in situ in the first or second liquid mixture.

15. The process of claim 1 wherein the first deposited film has an average thickness of about 100 nm to about 700 nm.

16. The process of claim 1 wherein the electrode substrate or the counter-electrode substrate comprises a transparent conductive layer and a glass, plastic, metal, or metal-coated glass or plastic layer, and the surface of the substrate onto which the first or the second liquid mixture is deposited is a surface of the transparent conductive layer.

17. The process of claim 1 wherein the process further comprises passing the first or second liquid mixture through a 0.2 micron filter before the first or second liquid mixture is deposited onto the surface of the electrode substrate or the counter-electrode substrate.

18. The process of claim 1 wherein the first deposited film or the second deposited film is thermally treated at an annealing temperature of at least 200°

C. and for an annealing time in the range of several minutes to several hours to form the electrode electrochromic layer or the counter-electrode electrochromic layer.

19. The process of claim 1 wherein the electrode electrochromic layer, the counter-electrode electrochromic layer, or both the electrode electrochromic layer and the counter-electrode electrochromic layer comprises at least 0.05 wt % carbon.

20. The process of claim 1 wherein the electrode electrochromic layer, the counter-electrode electrochromic layer, or both the electrode electrochromic layer and the counter-electrode electrochromic layer comprises at least 0.5 wt % carbon.

21. The process of claim 1 wherein the electrode electrochromic layer is an anodic electrochromic layer having a bleached state voltage of at least 2V.

22. The process of claim 1 wherein the electrode electrochromic layer is an anodic electrochromic layer characterized by a largest d-spacing of at least 2.5 Á

.