Compact, light-weight, solid-oxide electrochemical converter

• US 4,629,537 A
• Filed: 05/17/1985
• Issued: 12/16/1986
• Est. Priority Date: 05/17/1985
• Status: Expired due to Term

• Current Assignee: Michael S. Hsu
• Original Assignee: Michael S. Hsu
• Inventors: Hsu, Michael S.
• Primary Examiner(s): Valentine, Donald R.
• Application Number:
  US06/735,441
• Time in Patent Office: 578 Days
• Field of Search: 204/253-258, 204/267-270, 204/290 R, 204/15, 204/38 S, 427/115, 429/30, 429/32, 429/33, 429/38, 429/39
• US Class Current: 429/535
• CPC Class Codes: C25B 9/19 with diaphragms
• CPC Class Codes: C25B 9/65 Means for supplying current; Electrode connections; Electric inter-cell connections
• CPC Class Codes: C25B 9/70 Assemblies comprising two or more cells
• CPC Class Codes: H01M 2008/1293 Fuel cells with solid oxide electrolytes
• CPC Class Codes: H01M 2300/0074 Ion conductive at high temperature
• CPC Class Codes: H01M 8/0208 Alloys
• CPC Class Codes: H01M 8/0215 Glass; Ceramic materials
• CPC Class Codes: H01M 8/0254 corrugated or undulated
• CPC Class Codes: H01M 8/026 characterised by grooves, e.g. their pitch or depth
• CPC Class Codes: H01M 8/04014 Heat exchange using gaseous fluids; Heat exchange by combustion of reactants
• CPC Class Codes: H01M 8/0643 Gasification of solid fuel
• CPC Class Codes: H01M 8/1231 with both reactants being gaseous or vaporised
• CPC Class Codes: H01M 8/2404 Processes or apparatus for grouping fuel cells
• CPC Class Codes: H01M 8/2432 Grouping of unit cells of planar configuration
• CPC Class Codes: H01M 8/2495 of fuel cells of different types
• CPC Class Codes: Y02E 60/50 Fuel cells
• CPC Class Codes: Y10T 428/12354 Nonplanar, uniform-thickness material having symmetrical channel shape or reverse fold [e.g., making acute angle, etc.]
• CPC Class Codes: Y10T 428/12361 having aperture or cut
• CPC Class Codes: Y10T 428/2457 Parallel ribs and/or grooves

Abstract

A compact, light-weight solid-oxide electrochemical converter can be achieved using thin plates of electrolyte and interconnector. Impermeable, straight, thin plates of solid-oxide electrolyte are fabricated by high energy plasma spray methods under controlled temperature conditions. Thin sheets of nickel or platinum alloys can be used to form the interconnector. A protective coating is preferred on the contact points to provide electrical continuity when nickel alloys are employed. Stamping or electrodeposition techniques can be used to form corrugated patterns for reactant distribution over the surfaces of each electrolyte plate.

Claims

1. A method of constructing an electrochemical converter, the method comprising:

(a) forming a set of solid-oxide electrolyte plates by suspending a powder comprising zirconia stabilized with at least one material chosen from the group of magnesia, calcia and yttria in a gas, passing the suspension through an arc discharge of at least 30 kilowatts to generate a plasma spray and deposit a thin layer upon a substrate, uniformly cooling the deposited layer, repeating the deposition process until plates of about 50 to about 750 microns in thickness are deposited, and then removing the plates from the substrate;

(b) coating said electrolyte plates with a fuel electrode material on one surface of each plate and an oxidizer electrode material on a second surface of each plate;

(c) forming a set of interconnector plates having corrugated metal structures, comprising at least one metal chosen from the group of platinum and nickel alloys, the metal plate having a thickness ranging from about 25 to about 250 microns in the case of platinum alloys and having thickness ranging from about 100 to about 1000 microns in the case of nickel alloy, the corrugated structure defining groove networks for the passage of gases and ridges for gas seals and electrical contact with the electrode coatings of the electrolyte plates; and

(d) assembling the converter by stacking alternating layers of the electrolyte and interconnector plates together.

2. The method of claim 1 wherein the step of forming the electrolyte plates further includes employing an arc discharge having a voltage of at least 30 volts and a current of at least 800 amperes to generate the plasma spray.

3. The method of claim 1 wherein the step of forming the electrolyte plates further includes employing a powder having a mean particle size ranging from about 40 microns to about 100 microns.

4. The method of claim 1 wherein the step of forming the electrolyte plates further includes interrupting the deposition of the plasma when the substrate temperature exceeds a predetermined limit, and reinitiating deposition when the substrate temperature cools by about 20 degrees Celsius.

5. The method of claim 1 wherein the step of forming the electrolyte plates further includes passing a coolant through the substrate during the formation process.

6. The method of claim 1 wherein the step of forming the electrolyte plates further comprises passing a nonreactive gaseous coolant over the plate between the deposition of each layer.

7. The method of claim 1 wherein the step of forming the electrolyte plates further includes generating a plasma spray rate having a transport rate of about 2 to about 8 pounds per hour.

8. The method of claim 1 wherein the method further comprises preheating the substrate prior to the initial deposition.

9. The method of claim 1 wherein the step of coating the electrolyte plates further comprises coating one surface with a perkovite material to form an oxidizer electrode and coating a second surface with a cermet material to form a fuel electrode.

10. The method of claim 9 wherein the step of coating further comprises forming the coatings by flame or slurry deposition techniques.

11. A method of forming a solid oxide electrolyte plate, the method comprising:

(a) suspending a powder comprising zirconia and at least one stabilizing oxide chosen from the group of magnesia, calcia and yttria in a gas,

(b) passing the suspension through an arc discharge of at least 30 kilowatts to generate a plasma spray and deposit a thin layer upon a substrate,

(c) uniformly cooling the deposited layer,

(d) repeating the deposition process until a plates of about 50 to about 750 microns in thickness are deposited, and

(e) then removing the plate from the substrate;

12. The method of claim 11 wherein the method further includes employing an arc discharge having a voltage of at least 30 volts and a current of at least 800 amperes to generate the plasma spray.

13. The method of claim 11 wherein the method further includes employing a powder having a mean particle size ranging from about 40 microns to about 100 microns.

14. The method of claim 11 wherein the method further includes interrupting the deposition of the plasma when the substrate temperature exceeds a predetermined limit and reinitiating deposition when the substrate temperature cools by about 20 degrees Celsius.

15. The method of claim 11 wherein the method further includes passing a coolant through the substrate during the formation process.

16. The method of claim 11 wherein the method further comprises passing a nonreactive gaseous coolant over the plate between the deposition of each layer.

17. The method of claim 11 wherein the method further includes generating a plasma spray rate having a transport rate of about 2 to about 8 pounds per hour.

18. The method of claim 11 wherein the method further comprises preheating the substrate prior to the initial deposition.

19. The method of claim 11 wherein the method further comprises coating one surface with a perkovite material to form an oxidizer electrode and coating a second surface with a cermet material to form a fuel electrode.

20. The method of claim 19 wherein the method further comprises forming the coatings by flame or slurry deposition techniques.

21. A method of forming an interconnector plate for use in an electrochemical convertor, the interconnector plate serving to provide electrical connection between an oxidizer electrode of a first electrolyte disposed on one side of the interconnector plate and a fuel electrode of a second electrolyte disposed on the other side of the interconnector plate, the plate also serving to isolate and distribute separate reactant gases over the oxidizer and fuel electrodes of the first and second electrolytes, the method comprising

(a) forming a flat plate from a metal chosen from the group of platinum and nickel alloys the thickness of the plate ranging from about 25 to about 250 microns in the case of platinum alloys and from about 100 to about 1000 microns in the case of nickel alloys;

(b) defining a corrugated pattern of ridges and grooves on one side of the plate to permit the isolation and distribution of a first reactant gas on the one side;

(c) defining a complementary corrugated pattern of ridges and grooves on the other side of the plate to permit the isolation and distribution of a second reactant gas on the other side; and

(d) providing holes for introduction of the first reactant gas onto the one side and for the introduction of the second reactant gas onto the other side.

22. The method of claim 21 wherein the corrugated patterns are defined by stamping.

23. The method of claim 21 wherein the corrugated patterns are defined by electrodeposition.

24. The method of claim 21 wherein the method further comprises coating the ridges which provide contact points to adjacent electrodes with a non-oxidizing metal when the interconnector plate is formed from a nickel alloy.

25. An electrochemical converter comprising:

(a) a set of solid-oxide electrolyte plates formed by suspending a powder comprising zirconia stabilized with at least one material chosen from the group of magnesia, calcia and yttria in a gas, passing the suspension through an arc discharge of at least 30 kilowatts to generate a plasma spray and deposit a thin layer upon a substrate, uniformly cooling the deposited layer, repeating the deposition process until plates of about 50 to about 750 microns in thickness are deposited, removing the plates from the substrate; and

then coating said electrolyte plates with a fuel electrode material on one surface of each plate and an oxidizer electrode material on a second surface of each plate; and

(b) a set of interconnector plates having corrugated metal structures, comprising at least one metal chosen from the group of platinum and nickel alloys, the metal plate having a thickness ranging from about 25 to about 250 microns in the case of platinum alloys and having thickness ranging from about 100 to about 1000 microns in the case of nickel alloy, the corrugated structure defining groove networks for the passage of gases and ridges for gas seals and electrical contact with the electrode coatings of the electrolyte plates;

wherein the converter is assembled by stacking alternating layers of the electrolyte and interconnector plates together.

26. A solid oxide electrolyte plate for use in a electrochemical converter formed by suspending a powder comprising zirconia and at least one stabilizing oxide chosen from the group of magnesia, calcia and yttria in a gas, passing the suspension through an arc discharge of at least 30 kilowatts to generate a plasma spray and deposit a thin layer upon a substrate, uniformly cooling the deposited layer, repeating the deposition process until a plates of about 50 to about 750 microns in thickness are deposited, and then removing the plate from the substrate.

27. An interconnector plate for use in an electrochemical converter, the interconnector plate serving to provide electrical connection between an oxidizer electrode of a first electrolyte disposed on one side of the interconnector plate and a fuel electrode of a second electrolyte disposed on the other side of the interconnector plate, the plate also serving to isolate and distribute separate reactant gases over the oxidizer and fuel electrodes of the first and second electrolytes, the interconnector plates being formed as a flat plate from a metal chosen from the group of platinum and nickel alloys, the thickness fo the plate ranging from about 25 to about 250 microns in the case of platinum alloys and from about 100 to about 1000 microns in the caes of nickel alloys;

the plate having a corrugated pattern of ridges and grooves on one side thereof to permit the isolation and distribution of a first reactant gas on the one side and a complementary corrugated pattern of ridges and grooves on the other side of the plate to permit the isolation and distribution of a second reactant gas on the other side; and

holes for introduction of the first reactant gas onto the one side and for the introduction of the second reactant gas onto the other side.