Corrosion resistant ceramic materials

• US 5,455,206 A
• Filed: 03/10/1993
• Issued: 10/03/1995
• Est. Priority Date: 09/14/1990
• Status: Expired due to Term

• Current Assignee: U Chicago Argonne, LLC
• Original Assignee: ARCH Development Corporation (University of Chicago)
• Inventors: Kaun, Thomas D.
• Primary Examiner(s): Bell, Mark L.
• Assistant Examiner(s): KOSLOW, CAROL M
• Application Number:
  US08/028,782
• Time in Patent Office: 937 Days
• Field of Search: 501/1, 501/40, 423/263, 423/269, 423/561.1, 423/566.2, 423/566.3, 423/562, 252/387, 428/698, 429/191
• US Class Current: 501/1
• CPC Class Codes: C04B 2235/6567 Treatment time
• CPC Class Codes: C04B 2237/08 Non-oxidic interlayers
• CPC Class Codes: C04B 2237/09 wherein the active component for bonding is not the largest fraction of the interlayer
• CPC Class Codes: C04B 2237/343 Alumina or aluminates
• CPC Class Codes: C04B 2237/36 Non-oxidic
• CPC Class Codes: C04B 2237/403 Refractory metals
• CPC Class Codes: C04B 2237/406 Iron, e.g. steel
• CPC Class Codes: C04B 35/547 based on sulfides or selenides or tellurides
• CPC Class Codes: C04B 35/653 Processes involving a melting step
• CPC Class Codes: C04B 37/005 consisting of glass or ceramic material
• CPC Class Codes: C04B 37/025 consisting of glass or ceramic material
• CPC Class Codes: H01M 10/39 working at high temperature
• CPC Class Codes: H01M 10/3918 characterised by the electrolyte
• CPC Class Codes: H01M 10/399 Cells with molten salts
• CPC Class Codes: H01M 4/664 Ceramic materials
• CPC Class Codes: H01M 50/191 Inorganic material
• CPC Class Codes: H01M 50/198 characterised by physical properties, e.g. adhesiveness or hardness
• CPC Class Codes: H01M 50/434 Ceramics
• CPC Class Codes: H01M 50/44 Fibrous material
• CPC Class Codes: H01M 50/489 Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
• CPC Class Codes: H01M 50/497 : Ionic conductivity
• CPC Class Codes: H01M 6/185 : with oxides, hydroxides or oxysalts as solid electrolytes
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries

Abstract

Ceramic materials which exhibit stability in severely-corrosive environments having high alkali-metal activity, high sulfur/sulfide activity and/or molten halides at temperatures of 200°-550° C. or organic salt (including SO₂ and SO₂ Cl₂) at temperatures of 25°-200° C. These sulfide ceramics form stoichiometric (single-phase) compounds with sulfides of Ca, Li, Na, K, Al, Mg, Si, Y, La, Ce, Ga, Ba, Zr and Sr and show melting-points that are sufficiently low and have excellent wettability with many metals (Fe, Ni, Mo) to easily form metal/ceramic seals. Ceramic compositions are also formulated to adequately match thermal expansion coefficient of adjacent metal components.

Claims

1. A nonaqueous corrosion resistant composite comprising:

a crystalline single phase sulfide-containing ceramic material having at least three chemical elements, wherein one of said elements is sulfur; and

a material selected from the group consisting of a metallic material, a second ceramic material, and combinations thereof, and sealingly bonded to said single phase sulfide-containing ceramic material.

2. The composite as defined in claim 1 wherein said single phase sulfide-containing ceramic material is selected from the group consisting of mixtures of at least two of the compounds Li₂ S, Na₂ S₂, K₂ S, CaS, Al₂ S₃, SiS₂, MgS, Y₂ S₃, Ce₂ S₃, La₂ S₃, CeS, Na₂ S, Na₂ S₃, La₂ S, Ga₂ S₃, BaS, ZrS₂ and SrS.

3. The composite as defined in claim 2 further including at least one of an oxide, nitride, carbon, carbide, metal and metal sulfide filler material.

4. The composite as defined in claim 3 wherein said filler material comprises an ionically conductive material.

5. The composite as defined in claim 3 wherein said filler material comprises up to about 50 wt %.

6. The composite as defined in claim 5 wherein said filler material is an oxide comprising at least one of CaO, MgO, Al₂ O₃ and B₂ O₃.Al₂ O₃.

7. The composite as defined in claim 1 wherein said sulfide-containing ceramic material is selected from the group consisting of CaAl₂ S₄, Ca₂ Al₂ SiS₇, CaK₂ NaS₃, MgAl₂ S₄, KAlS₂, LiAlS₂, YAlS₃, CaYAl ₃ S₇, BaAl₂ S₄, LaAlS₃, CeAlS ₃, LiAlSeS, Li₂ CaS₂, Li₂ CaYAlS₅, CaY₂ S₄ and Li₄ Al₂ SiS₇.

8. The composite as defined in claim 2 wherein said single phase sulfide-containing ceramic consists of a sulfide comprising greater than fifty mole percent of said ceramic and having a heat of formation more negative than about -75 Kcal/mole.

9. The composite as defined in claim 8 wherein said single phase sulfide-containing ceramic has a melting point below about 1200°

C.

10. A ceramic composition, comprising:

a crystalline single phase sulfide-containing material having at least four chemical elements, wherein one of said elements is sulfur.

11. The composition as defined in claim 10 further including at least one of an oxide, nitride, carbon, carbide, metal and metal sulfide filler material.

12. The composition as defined in claim 11 wherein said filler material comprises an ionically conductive material.

13. The composition as defined in claim 11 wherein said filler material comprises up to about 50 wt %.

14. The composition as defined in claim 13 wherein said filler material is an oxide comprising at least one of CaO, MgO, Al₂ O₃ and B₂ O₃.Al₂ O₃.

15. The composition as defined in claim 10 wherein said sulfide-containing material is selected from the group consisting of Ca₂ Al₂ SiS₇, CaK₂ NaS₃, CaK₂ NaS₃, Li₄ Al₂ SiS₇, LiCaAlS₃, CaYAl₃ S₇, LiAlSeS, Li₂ CaYAlS₅ and Li₄ Al₂ SiS₇.

16. The composition as defined in claim 10 wherein said single phase sulfide-containing material consists essentially of a sulfide comprising greater than fifty mole percent of said material and having a heat of formation more negative than about -75 Kcal/mole.

17. The composition as defined in claim 16 wherein said single phase sulfide-containing material has a melting point below about 1200°

C.

22. The composition as defined in claim 10 wherein said filler material is an oxide comprising at least one of CaO, MgO, Al₂ O₃ and B₂ O₃.Al₂ O₃.

18. A ceramic material, comprising:

a crystalline single phase sulfide-containing ceramic having at least three chemical elements and wherein one of said elements is sulfur, said sulfide-containing ceramic having an associated resulting coefficient of thermal expansion; and

a material selected from the group consisting of a metallic material, a second ceramic material and combinations thereof, and bonded to said single phase sulfide-containing ceramic and having an associated coefficient of thermal expansion substantially the same as said ceramic material.

19. A ceramic composition, comprising:

a crystalline single phase sulfide-containing material having at least three chemical elements wherein one of said elements is sulfur; and

at least one of an oxide, nitride, carbon, carbide, metal, and metal sulfide filler material, said filler material bonded with said sulfide-containing material.

20. The composite as defined in claim 19 wherein said single phase sulfide-containing ceramic material is selected from the group consisting of mixtures of at least two of the compounds Li₂ S, Na₂ S₂, K₂ S, CaS, Al₂ S₃, SiS₂, MgS, Y₂ S₃, Ce₂ S₃, La₂ S₃, CeS, Na₂ S, Na₂ S₃, La₂,S, Ga₂ S₃, BaS, ZrS₂ and SrS.

21. The composition as defined in claim 20 wherein said filler material comprises an ionically conductive material.

23. The composition as defined in claim 19 wherein said sulfide-containing material is selected from the group consisting of CaAl₂ S₄, CaAl₂ SiS₇, CaK₂ NaS₃, MgAl₂ S₄, KAlS₂, LiAlS₂, YAlS₃, CaYAl₃ S₇, LiCaAlS₃, BaAl₂ S₄, LaAlS₃, CeAlS₃, LiAlSeS, Li₂ CaS₂, Li₂ CaYAlS₅, CaY₂ S₄ and Li₄ Al₂ SiS₇.

24. The composition as defined in claim 20 wherein said sulfide-containing material consists essentially of a single phase sulfide comprising greater than fifty mole percent of said material and having a heat of formation more negative than about -75 Kcal/mole.

25. The composition as defined in claim 20 wherein said single phase sulfide-containing material has a melting point below about 1200°

C.