Corrosion resistant ceramic materials

• US 5,538,810 A
• Filed: 06/07/1995
• Issued: 07/23/1996
• Est. Priority Date: 09/14/1990
• Status: Expired due to Term

• Current Assignee: Thomas D. Kaun
• Original Assignee: Thomas D. Kaun
• Inventors: Kaun, Thomas D.
• Primary Examiner(s): KALAFUT, STEPHEN J
• Application Number:
  US08/473,757
• Time in Patent Office: 412 Days
• Field of Search: 501/1, 501/140, 429/129, 429/247, 423/511
• US Class Current: 429/129
• 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 corrosion-resistant batten having alkali-metal conductivity, comprising:

a conductive member selected from the group consisting of a metallic material, a ceramic material, and combinations thereof;

a negative electrode selected from the group consisting of alkali metals, alkaline earth metals, and alloys thereof, said electrode in a substantially conductive relationship to said member;

a single phase sulfide-containing ceramic separator having at least three chemical elements and selected from the group consisting of a sulfide and a sulfide/selenide composite, and including an alkali metal ion conductive material selected from the group consisting of an oxide, nitride, carbide, and sulfide, said separator in a substantially conductive relationship to said negative electrode; and

a positive electrode selected from the group consisting of metal oxides, sulfides, nitrides, and carbides intercalated with alkali metal ions, said electrode including a non-intercalated material selected from the group consisting of metal oxide, sulfide, nitride, and carbide ceramics, in a substantially conductive relationship to said separator.

2. The battery 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, Ga₂ S₃, BaS, ZrS₂ and SrS.

3. The battery as defined in claim 1 wherein said alkali metal is lithium.

4. The battery as defined in claim 3 wherein:

said negative electrode is a lithium alloy; and

said positive electrode is a lithiated metal oxide including a metal sulfide ceramic.

5. The battery as defined in claim 4 wherein said alkali metal ion conductive material comprises from about zero to 50 wt %.

6. The battery as defined in claim 1 wherein said sulfide-containing ceramic material is selected from the group consisting of CaAl₂ S₄, CaAl₂ SIS₇, CaK₂ NaS₃, MgAl₂ S₄, KAlS₂, LiAlS₂, YAlS₃, CaYAl₃ S₇, BaAl₂ S₄, LaAlS₃, CeAlS₃, Li₂ CaS₂, Li₂ CaYAlS₅, CaY₂ S₄ and Li₄ Al₂ SiS₇.

7. The battery as defined in claim 1 wherein said sulfide-containing ceramic consists of a sulfide comprising greater than fifty percent of said ceramic and having a heat of formation more negative than about -75 Kcal/mole.

8. The battery as defined in claim 1 wherein said member is a bipolar plate in a substantially conductive relationship to a second positive electrode arranged and configured in a series circuit with said negative electrode.

9. A corrosion-resistant battery having one of alkali-metal and alkaline earth-metal conductivity, comprising:

a conductive member selected from the group consisting of a metallic material, a ceramic material, and combinations thereof;

a negative electrode selected from the group consisting of alkali metals, alkaline earth metals, and alloys thereof, said electrode in a substantially conductive relationship with said member;

a ceramic, wherein said ceramic is a single phase sulfide-containing material having at least three chemical elements, wherein one of said elements is sulfur or selenium, said ceramic including a metal ion conductive material selected from the group consisting of an oxide, nitride, carbon, carbide, and sulfide, said ceramic in a substantially conductive relationship with said negative electrode; and

a positive electrode selected from the group consisting of metal oxides, sulfides, nitrides, and carbides intercalated with one of alkali and alkaline earth-metal ions, said electrode including a non-intercalated material selected from the group consisting of metal oxide, sulfide, nitride, and carbide ceramics, in a substantially conductive relationship with said sulfide-containing ceramic.

10. The battery of claim 9 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, Ga₂ S₃, BaS, ZrS₂, SrS, Al₂ Se₃, Li₂ Se and GeSe.

11. The battery of claim 9 wherein said alkali metal is lithium.

12. The battery of claim 11 wherein:

said negative electrode is a lithium alloy; and

said positive electrode is a lithiated metal oxide including a metal sulfide ceramic.

13. The battery of claim 12 wherein said alkali metal ion conductive material comprises up to about 50 wt %.

14. The battery of claim 9 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, CaYAl₃ S₇, LiCaAlS₃, BaAl₂ S₄, LaAlS₃, CeAlS₃, LiAlSeS, Li₂ CaS₂, Li₂ CaYAlS₅, CaY₂ S₄, and Li₄ Al₂ SiS₇ and Ca₂ Al₂ Se₃ S.

15. The battery of claim 9 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.

16. The battery of claim 9 wherein said member is a bipolar plate in a substantially conductive relationship with a second positive electrode arranged and configured in a series circuit with said negative electrode.

17. The battery of claim 9 wherein said bipolar plate is an electrically-conducting sulfide-containing ceramic.

18. A corrosion-resistant battery having alkali-metal conductivity, comprising:

a conductive member selected from the group consisting of a metallic material, a ceramic material, and combinations thereof;

a negative electrode selected from the group consisting of alkali metals, alkaline earth metals, and alloys thereof, said electrode in a substantially conductive relationship to said member;

a single phase sulfide-containing ceramic separator having at least three chemical elements, wherein one of said elements is sulfur, said separator including an alkali metal ion conductive material selected from the group consisting of an oxide, nitride, carbide, and sulfide, said separator in a substantially conductive relationship to said negative electrode; and

a positive electrode selected from the group consisting of metal oxides, sulfides, nitrides, and carbides intercalated with alkali metal ions, said electrode including a non-intercalated material selected from the group consisting of metal oxide, sulfide, nitride, and carbide ceramics, in a substantially conductive relationship to said separator.

19. The battery as defined in claim 18 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, Al₂ Se₃, Li₂ Se, GeSe, Ga₂ S₃, BaS, ZrS₂ and SrS.

20. The battery as defined in claim 18 wherein said alkali metal is lithium.

21. The battery as defined in claim 20 wherein:

said negative electrode is a lithium alloy; and

said positive electrode is a lithiated metal oxide including a metal sulfide ceramic.

22. The battery as defined in claim 21 wherein said alkali metal ion conductive material comprises up to about 50 wt %.

23. The battery as defined in claim 18 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, CaYAl₃ S₇, BaAl₂ S₄, LaAlS₃, CeA₁ S₃, LiAlSeS, Li₂ CaS₂, Li₂ CaYAlS₅, Ca₂ Al₂ Se₃ S, CaY₂ S₄ and Li₄ Al₂ SiS₇.

24. The battery as defined in claim 18 wherein said 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.

25. The battery as defined in claim 18 wherein said member is a bipolar plate in a substantially conductive relationship to a second positive electrode arranged and configured in a series circuit with said negative electrode.

26. The battery as defined in claim 18 wherein said bipolar plate is an electrically-conductive sulfide-containing ceramic.