IP Library › Granted Patent US 12,199,326
Granted Patent B2
US 12,199,326 · App. 16/868,005 · Granted Jan 14, 2025

Fabrication processes for metal-supported proton conducting solid oxide electrochemical devices

Inventors: Michael Tucker (Piedmont, CA); Ruofan Wang (Berkeley, CA)
Assignee: The Regents of the University of California
H01M8/1226H01M4/8885H01M4/9033H01M4/9066H01M2008/1293
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Quick Facts
Patent No.
US 12,199,326
App. No.
16/868,005
Granted
Jan 14, 2025
Kind
B2
Abstract

This disclosure provides systems, methods, and apparatus related to metal-supported proton conducting solid oxide electrochemical devices. In one aspect, a method includes forming an electrode on a metal support of a device with a first proton-conducting ceramic. The metal support comprises an iron-chromium alloy. The first proton-conducting ceramic is in a powder form. An electrolyte layer is formed on the electrode and on the metal support of the device with a second proton-conducting ceramic. The second proton-conducting ceramic is in a powder form. The device is thermally treated at about 1200° C. to 1550° C.

Claims (39)

1. A method comprising:

(a) forming a first electrode on a metal support of a device with a first proton-conducting ceramic, the metal support comprising an iron-chromium alloy, and the first proton-conducting ceramic being in a powder form, wherein the first electrode comprises:

a first layer of a first lattice structure, comprising ytterbium substituting approximately 10% of a first type of lattice site of the first lattice structure, and

a second layer having substantially no ytterbium substituted lattice sites, with approximately 70% of the first type of lattice site of the second layer occupied by zirconium;

(b) forming an electrolyte layer on the first electrode and on the metal support of the device with a second proton-conducting ceramic, and the second proton-conducting ceramic being in a powder form;

(c) forming a second electrode on the electrolyte layer;

(d) thermally treating the device, comprising the first electrode, the metal support, and the electrolyte layer, at about 1200° C. to 1550° C.; and

(e) providing an electrical connection between the second electrode and the metal support, wherein the electrical connection comprises one of:

an electrical load, or

a power supply.

2. The method of claim 1 , wherein the metal support comprises a ferritic stainless steel.

3. The method of claim 1 , wherein the device is thermally treated at about 1300° C. to 1450° C.

4. The method of claim 1 , wherein operation (c) is performed in a reducing atmosphere.

5. The method of claim 1 , further comprising:

prior to operation (a), forming a barrier layer on the metal support.

6. The method of claim 5 , wherein the barrier layer is selected from a group consisting of yttrium-stabilized zirconia, doped ceria, lanthanum calcium niobate, and samarium cerium yttrium zirconate.

7. The method of claim 1 , wherein the first proton-conducting ceramic and the second proton-conducting ceramic comprise barium cerium yttrium zirconate.

8. The method of claim 1 , wherein operation (d) is performed in a reducing atmosphere, and wherein the first electrode, the electrolyte layer, or both the first electrode and the electrolyte layer include a sintering aid, selected from a group consisting of lithium hydride, lithium fluoride, lithium carbonate, lithium oxide, and manganese oxide.

9. The method of claim 1 , wherein the first proton-conducting ceramic and the second proton-conducting ceramic are the same proton-conducting ceramic.

10. The method of claim 1 , wherein the second proton conducting ceramic comprises material selected from a group consisting of lanthanum calcium niobate, barium cerium yttrium zirconate, and samarium cerium yttrium zirconate.

11. The method of claim 1 , wherein the metal support comprises a low-silicon stainless steel including less than about 0.5 weight percent silicon.

12. The method of claim 1 , wherein a thickness of the first electrode is about 10 microns to 100 microns.

13. The method of claim 1 , further comprising:

depositing a getter material on the first electrode or the metal support, wherein the getter material comprises lanthanum oxide, strontium oxide, or barium oxide.

14. The method of claim 1 , further comprising:

after operation (d), depositing a material on the first electrode, wherein the material is selected from a group consisting of a catalyst, a proton conductor, and an electronic conductor.

15. The method of claim 1 , wherein the device is selected from a group consisting of a metal supported solid oxide fuel cell (MS-SOFC), a metal supported solid oxide electrolysis cell, a metal supported solid oxide electrochemical reactor, a metal supported solid oxide oxygen generator, a metal supported solid oxide electrochemical hydrogen generator, and a metal supported solid oxide electrochemical hydrogen compressor.

16. A method comprising:

(a) forming a first electrode on a metal support of a device with barium cerium yttrium zirconate, the metal support comprising a low-silicon steel including less than about 0.5 weight percent silicon, and the barium cerium yttrium zirconate being in a powder form, wherein the first electrode comprises:

a first layer of a first lattice structure, comprising ytterbium substituting approximately 10% of a first type of lattice site of the first lattice structure, and

a second layer having substantially no ytterbium substituted lattice sites, having 70% of the first type of lattice site occupied by zirconium;

(b) forming an electrolyte layer on the first electrode and on the metal support of the device with the barium cerium yttrium zirconate;

(c) sintering the device, comprising the first electrode, the metal support, and the electrolyte layer, at about 1200° C. to 1550° C. in a reducing atmosphere;

(d) forming a second electrode on the electrolyte layer; and

(e) providing an electrical connection between the second electrode and the metal support.

17. The method of claim 1 , wherein forming the second electrode on the electrolyte layer is performed prior to thermally treating the device, and wherein thermally treating the device comprises treating the first electrode, the metal support, the electrolyte layer, and the second electrode.

18. The method of claim 1 , wherein forming the second electrode on the electrolyte layer is performed subsequent to thermally treating the device.

19. The method of claim 18 , wherein the method further comprises performing an additional thermal treatment operation of the device, comprising thermally treating the first electrode, the metal support, the electrolyte layer, and the second electrode.

20. The method of claim 7 , wherein the first layer is composed of BZCYYb1711, and the second layer is comprised of BZCY721.

Assignments (2)
CONFIRMATORY LICENSE Recorded Dec 16, 2020
From: UNIVERSITY OF CALIF-LAWRENC BERKELEY LAB
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 054666/0380 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 12, 2020
From: TUCKER, MICHAEL; WANG, RUOFAN
To: THE REGENTS OF THE UNIVERSITY OF CALIFORNIA
Reel/Frame 052637/0594 →
Continuity (2)
Provisional Application 62846233 · May 10, 2019
Related Publication 20200358122A1 · Nov 12, 2020
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