Bonded hydrogen conducting solid electrolytes

• US 4,724,191 A
• Filed: 05/12/1986
• Issued: 02/09/1988
• Est. Priority Date: 06/28/1985
• Status: Expired due to Term

• Current Assignee: Minister of Finance Incorporated
• Original Assignee: Her Majesty The Queen In Right of Canada As Represented By The Minister of National Defence
• Inventors: Ahmad, Aftab, Kuriakose, Areekattuthazhayil K., Canaday, Jon D., Wheat, Thomas A., Hanson, Albert J.
• Primary Examiner(s): Silbaugh, Jan H.
• Assistant Examiner(s): McCarthy, Neil M.
• Application Number:
  US06/866,855
• Time in Patent Office: 638 Days
• Field of Search: 264/104, 264/122, 429/189, 429/191, 429/192, 429/193, 501/153
• US Class Current: 429/316
• CPC Class Codes: C04B 2235/3201 Alkali metal oxides or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3224 Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
• CPC Class Codes: C04B 2235/3225 Yttrium oxide or oxide-forming salts thereof
• CPC Class Codes: C04B 35/16 based on silicates other than clay zircon C04B35/48
• CPC Class Codes: C04B 35/6306 Binders based on phosphoric acids or phosphates
• CPC Class Codes: C25B 13/04 characterised by the material
• CPC Class Codes: G01N 27/4074 for detection of gases other than oxygen
• CPC Class Codes: H01M 6/185 with oxides, hydroxides or oxysalts as solid electrolytes
• CPC Class Codes: H01M 8/1016 characterised by the electrolyte material H01M8/12 takes precedence
• CPC Class Codes: Y02E 60/50 Fuel cells
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

Hydronium bonded polycrystalline shaped articles may be produced by the simple expedient of selecting a hydronium containing powder prepared by one of a plurality of prior art methods and then intermingling the hydronium powder with ortho-phosphoric acid to obtain a viscous mixture (resembling the consistency of toothpaste). The mixture is then formed into a predetermined shape, for example a disc or tube, and the shaped polycrystalline ceramic is allowed to cure. Curing may take place at an elevated temperature below 100° C. for approximately 3 hours either as a step subsequent to forming, or as part of the forming step in 30 minutes at 120° C. The result is bonded hydrogen conducting - hydronium, H₃ O+, solid rigid structure with a smooth finish copying the mold from which it was shaped. Specifically, the hydronium containing powders are selected from the group of poly antimonic acid and precursor powders generally known as Nasicons and preferably being selected from the group of powders consisting of sodium β/β"-alumina, sodium/potassium β/β"-alumina, sodium zirpsios, Gasicon and Yasicon.

Claims

1. A method of chemically bonding hydronium ion conducting solid electrolyte powder into dense polycrystalline shaped bodies comprising the steps of:

(a) selecting a hydronium containing powder and a bonding agent selected from the group of bonding agents consisting of hydronium conducting organic polymers and phosphates;

(b) intermingling the hydronium powder with the bonding agent to obtain a mixture;

(c) forming the mixture into a predetermined shape;

(d) curing the predetermined shape so as to create a dense polycrystalline shaped hydronium conducting ceramic body, in which the bonding agent does not affect the hydronium ion conductivity significantly.

8. The method as claimed in claim 1, 2 or 3, wherein the selecting step (a) a material is selected from the group of materials consisting of

2. A method of chemically bonding hydronium ion conducting powder into dense polycrystalline shaped bodies comprising the steps of:

(a) selecting a hydronium containing powder;

(b) intermingling the hydronium powder with orthophosphoric acid bonding agent to obtain a mixture;

(c) molding the mixture into a predetermined shape;

(d) curing the predetermined shape so as to create a dense polycrystalline shaped hydronium ceramic body, in which the bonding agent does not affect the hydronium ion conductivity significantly.

3. The method as claimed in claim 2, wherein the intermingling step (b) includes intermingling the hydronium powder with ortho phosphoric acid and water to obtain a paste like mixture.

4. The method as claimed in claim 2, wherein the hydronium containing powder is selected from the group of powders converted into hydronium powder from precursor powders consisting of sodium β

/β

"-alumina, sodium/potassium β

/β

"-alumina, sodium zirpsios, Gasicon, Yasicon and poly antimonic acid.

5. The method as claimed in claim 3, wherein the hydronium containing powder is selected from the group of powders converted into hydronium powder from precursor powders consisting of sodium β

/β

"-alumina, sodium/potassium β

/β

"-alumina, sodium zirpsios, Gasicon, Yasicon and poly antimonic acid.

6. The method as claimed in claim 2, 3, or 4, wherein the amount of ortho phosphoric acid in gravimetric ratio with the hydronium powder is between 15%-30% by weight of the mixture.

7. The method as claimed in claim 5, wherein the amount of ortho phosphoric acid in gravimetric ratio with the hydronium powder is between 15%-30% by weight of the mixture.

9. A hydronium ion conducting bonded polycrystalline solid, snow white in colour, very difficult to break by hand and with good resistance to breaking, shattering and cracking and having a conductivity at 100°

C. between 1.4×

10^-4 (ohm cm)^-1 and 6.0×

10^-4 (ohm cm)^-1 wherein 50% to 90% by weight is hydronium conducting powder, the balance an ionic bonding agent.

10. The bonded polycrystalline solid as claimed in claim 9, wherein the ionic bonding agent is a hydrogen phosphate.

11. The bonded polycrystalline solid as claimed in claim 9, wherein the hydronium conducting powder is H₃ O⁺ -β

/β

"-Al₂ O₃ and the balance is alumina hydrogen phosphate.

12. The bonded polycrystalline solid as claimed in claim 9, wherein the hydronium conducting powder is hydronium Zirpsio and the balance is zirconium hydrogen phosphate.

13. The bonded polycrystalline solid as claimed in claim 9, wherein the hydronium conducting powder is selected from the group of materials consisting of hydronium Gasicon, hydronium Yasicon and the balance is selected from the group of materials consisting of Gadolinium acid phosphate and Yttrium acid phosphate.

14. The bonded polycrystalline solid as claimed in claim 9, wherein a presursor powder for the hydronium conducting powder is poly antimonic acid and the balance is antimonic hydrogen phosphate.

15. The bonded polycrystalline solid as claimed in claim 9, wherein the ionic bonding agent is a polymer.