Porous sintered bodies and solid oxide fuel cells using such porous sintered bodies as air electrodes

• US 5,489,483 A
• Filed: 08/29/1994
• Issued: 02/06/1996
• Est. Priority Date: 09/03/1993
• Status: Expired due to Term

• Current Assignee: NGK Insulators Limited
• Original Assignee: NGK Insulators Limited
• Inventors: Mori, Kazuyo, Soma, Takao, Kawasaki, Shinji, Takahashi, Tomonori, Yamada, Hirotake
• Primary Examiner(s): Skapars, Anthony
• Application Number:
  US08/297,096
• Time in Patent Office: 526 Days
• Field of Search: 429/45, 429/40, 429/30, 429/33, 429/218, 429/27
• US Class Current: 429/489
• CPC Class Codes: B01J 23/002 Mixed oxides other than spinels, e.g. perovskite
• CPC Class Codes: B01J 23/34 Manganese
• CPC Class Codes: B01J 2523/00 Constitutive chemical elements of heterogeneous catalysts
• CPC Class Codes: B01J 2523/17 Copper
• CPC Class Codes: B01J 2523/22 Magnesium
• CPC Class Codes: B01J 2523/23 Calcium
• CPC Class Codes: B01J 2523/24 Strontium
• CPC Class Codes: B01J 2523/27 Zinc
• CPC Class Codes: B01J 2523/31 Aluminium
• CPC Class Codes: B01J 2523/36 Yttrium
• CPC Class Codes: B01J 2523/3706 Lanthanum
• CPC Class Codes: B01J 2523/3718 Praseodymium
• CPC Class Codes: B01J 2523/3725 Neodymium
• CPC Class Codes: B01J 2523/3737 Samarium
• CPC Class Codes: B01J 2523/3762 Dysprosium
• CPC Class Codes: B01J 2523/67 Chromium
• CPC Class Codes: B01J 2523/72 Manganese
• CPC Class Codes: B01J 2523/845 Cobalt
• CPC Class Codes: B01J 2523/847 Nickel
• CPC Class Codes: C04B 35/01 based on oxide ceramics
• CPC Class Codes: C04B 38/00 : Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof treating slag with gases or gas generating material C04B5/06 ; expanded graphite C04B35/536
• CPC Class Codes: H01M 4/9016 : Oxides, hydroxides or oxygenated metallic salts
• CPC Class Codes: H01M 4/9033 : Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
• CPC Class Codes: Y02E 60/50 : Fuel cells

Abstract

A porous sintered body is composed of a perovskite-type composite oxide, wherein A-site of the composite oxide are occupied by one or more kinds of first metallic elements selected from the group consisting of calcium and strontium, one or more kinds of second metal elements selected from the group consisting of rare earth elements and yttrium excluding lanthanum and cerium, and lanthanum, the above one or more kinds of the first metallic elements amount to 5 to 70 mol % of the A-sites, and manganese is contained in B-sites of the composite oxide.

Claims

1. A porous sintered body comprising a perovskite composite oxide, wherein A-sites of said composite oxide are occupied by (i) at least one first metallic element selected from the group consisting of calcium and strontium, (ii) at least one second metallic element selected from, the group consisting of scandium, yttrium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium, and (iii) lanthanum, wherein said at least one first metallic element amounts to 5 to 70 mol % of said A-sites, and manganese is contained in B-sites of said composite oxide.

2. The porous sintered body set forth in claim 1, wherein said at least one second metallic element is selected from the group consisting of praseodymium, neodymium, samarium, dysprosium, gadolinium and yttrium.

3. The porous sintered body set forth in claim 1, wherein at least one second metallic element amounts to 1 to 80 mol % of said A-sites.

4. The porous sintered body set forth in claim 2, wherein said at least one second metallic element amounts to 1 to 80 mol % of said A-sites.

5. The porous sintered body set forth in claim 1 wherein a part of said B-sites are occupied by at least one third metallic element selected from the group consisting of aluminum, cobalt, magnesium and nickel, and the remainder of the B-sites are occupied by manganese.

6. The porous sintered body set forth in claim 1, wherein a part of said B-sites are occupied by at least one third metallic element selected from the group consisting of chromium, copper, iron, titanium and zinc, and the remainder of the B-sites are occupied by manganese.

7. The porous sintered body set forth in claim 1, wherein a part of said B-sites are occupied by at least one third metallic element selected from the group consisting of aluminum, cobalt, magnesium, nickel, chromium, copper, iron, titanium and zinc, and the remainder of the B-sites are occupied by manganese.

8. The porous sintered body set forth in claim 1, wherein said B-sites are occupied by manganese.

9. The porous sintered body set forth in claim 1, wherein the average coefficient of thermal expansion of the sintered body in a range from 25°

C. to 1000°

C. is not less than 10.2×

10^-6 K^-1 and not more than 10.8×

10^-6 K^-1.

10. The porous sintered body set forth in claim 5, wherein the average coefficient of thermal expansion of the sintered body in a range from 25°

C. to 1000°

C. is not less than 10.2×

10^-6 K^-1 and not more than 10.8×

10^-6 K^-1.

11. The porous sintered body set forth in claim 6, wherein the average coefficient of thermal expansion of the sintered body in a range from 25°

C. to 1000°

C. is not less than 10.2×

10^-6 K^-1 and not more than 10.8×

10^-6 K^-1.

12. The porous sintered body set forth in claim 7, wherein the average coefficient of thermal expansion of the sintered body in a range from 25°

C. to 1000°

C. is not less than 10.2×

10⁶ K^-1 and not more than 10.8×

10^-6 K^-1.

13. The porous sintered body set forth in claim 8, wherein the average coefficient of thermal expansion of the sintered body in a range from 25°

C. to 1000°

C. is not less than 10.2×

10^-6 K^-1 and not more than 10.8×

10^-6 K^-1.

14. The porous sintered body set forth in claim 1, wherein thermal shrinkage of the porous sintered body caused by heat cycling between room temperature and 1000°

C. is not more than 0.01% per one heat cycle.

15. The porous sintered body set forth in claim 5, wherein thermal shrinkage of the porous sintered body caused by heat cycling between room temperature and 1000°

C. is not more than 0.01% per one heat cycle.

16. The porous sintered body set forth in claim 6, wherein thermal shrinkage of the porous sintered body caused by heat cycling between room temperature and 1000°

C. is not more than 0.01% per one heat cycle.

17. The porous sintered body set forth in claim 7, wherein thermal shrinkage of the porous sintered body caused by heat cycling between room temperature and 1000°

.C is not more than 0.01% per one heat cycle.

18. The porous sintered body set forth in claim 8, wherein thermal shrinkage of the porous sintered body caused by heat cycling between room temperature and 1000°

C. is not more than 0.01% per one heat cycle.

19. The porous sintered body set forth in claim 1, wherein porosity of the porous sintered body is not less than 5% and not more than 40%.

20. A solid oxide fuel cell, comprising an air electrode made of said porous sintered body set forth in claim 5.

21. A solid oxide fuel cell, comprising an air electrode made of said porous sintered body set forth in claim 6.

22. A solid oxide fuel cell, comprising an air electrode made of said porous sintered body set forth in claim 7.

23. A solid oxide fuel cell, comprising an air electrode made of said porous sintered body set forth in claim 8.

24. The solid oxide fuel cell set forth in claim 20, wherein said air electrode supports the fuel cell.

25. The solid oxide fuel cell set forth in claim 21, wherein said air electrode supports the fuel cell.

26. The solid oxide fuel cell set forth in claim 22, wherein said air electrode supports the fuel cell.

27. The solid oxide fuel cell set forth in claim 23, wherein said air electrode supports the fuel cell.

28. The solid oxide fuel cell set forth in claim 24, wherein said air electrode has a cylindrical shape.

29. The porous sintered body set forth in claim 2, wherein a part of said B-sites are occupied by at least one third metallic element selected from the group consisting of aluminum, cobalt, magnesiumand nickel, and the remainder of the B-sites are occupied by manganese.

30. The porous sintered body set forth in claim 3, wherein a part of said B-sites are occupied by at least one third metallic element selected from the group consisting of aluminum, cobalt, magnesiumand nickel, and the remainder of the B-sites are occupied by manganese.

31. The porous sintered body set forth in claim 4, wherein a part of said B-sites are occupied by at least one third metallic element selected from the group consisting of aluminum, cobalt, magnesium and nickel, and the remainder of the B-sites are occupied by manganese.

32. The porous sintered body set forth in claim 2, wherein a part of said B-sites are occupied by at least one third metallic element selected from the group consisting of chromium, copper, iron, titanium and zinc, and the remainder of the B-sites are occupied by manganese.

33. The porous sintered body set forth in claim 3, wherein a part of said B-sites are occupied by at least one third metallic element selected from the group consisting of chromium, copper, iron, titanium and zinc, and the remainder of the B-sites are occupied by manganese.

34. The porous sintered body set forth in claim 4, wherein a part of said B-sites are occupied by at least one third metallic element selected from the group consisting of chromium, copper, iron, titanium and zinc, and the remainder of the B-sites are occupied by manganese.

35. The porous sintered body set forth in claim 2, wherein a part of said B-sites are occupied by at least one third metallic element selected from the group consisting of aluminum, cobalt, magnesium, nickel, chromium, copper, iron, titanium and zinc, and the remainder of the B-sites are occupied by manganese.

36. The porous sintered body set forth in claim 3, wherein a part of said B-sites are occupied by at least one third metallic element selected from the group consisting of aluminum, cobalt, magnesium, nickel, chromium, copper, iron, titanium and zinc, and the remainder of the B-sites are occupied by manganese.

37. The porous sintered body set forth in claim 4, wherein a part of said B-sites are occupied by at least one third metallic element selected from the group consisting of aluminum, cobalt, magnesium, nickel, chromium, copper, iron, titanium and zinc, and the remainder of the B-sites are occupied by manganese.

38. The porous sintered body set forth in claim 2, wherein said B-sites are occupied by manganese.

39. The porous sintered body set forth in claim 3, wherein said B-sites are occupied by manganese.

40. The porous sintered body set forth in claim 4, wherein said B-sites are occupied by manganese.

41. The porous sintered body set forth in claim 2, wherein the average coefficient of thermal expansion of the sintered body in a range from 25°

C. to 1000°

C. is not less than 10.2×

10^-6 K^-1 and not more than 10.8×

10^-6 K^-1.

42. The porous sintered body set forth in claim 3, wherein the average coefficient of thermal expansion of the sintered body in a range from 25°

C. to 1000°

C. is not less than 10.2×

10^-6 K^-1 and not more than 10.8×

10^-6 K^-1.

43. The porous sintered body set forth in claim 4, wherein the average coefficient of thermal expansion of the sintered body in a range from 25°

C. to 1000°

C. is not less than 10.2×

10^-6 K^-1 and not more than 10.8×

10^-1 K^-1.

44. The porous sintered body set forth in claim 2, wherein thermal shrinkage of the porous sintered body caused by heat cycling between room temperature and 1000°

C. is not more than 0.01% per one heat cycle.

45. The porous sintered body set forth in claim 3, wherein thermal shrinkage of the porous sintered body caused by heat cycling between room temperature and 1000°

C. is not more than 0.01% per one heat cycle.

46. The porous sintered body set forth in claim 4, wherein thermal shrinkage of the porous sintered body caused by heat cycling between room temperature and 1000°

C. is not more than 0.01% per one heat cycle.

47. The porous sintered body set forth in claim 2, wherein porosity of the porous sintered body is not less than 5% and not more than 40%.

48. The porous sintered body set forth in claim 3, wherein porosity of the porous sintered body is not less than 5% and not more than 40%.

49. The porous sintered body set forth in claim 4, wherein porosity of the porous sintered body is not less than 5% and not more than 40%.

50. A solid oxide fuel cell, comprising an air electrode made of said porous sintered body set forth in claim 1.

51. A solid oxide fuel cell, comprising an air electrode made of said porous sintered body set forth in claim 2.

52. A solid oxide fuel cell, comprising an air electrode made of said porous sintered body set forth in claim 3.

53. A solid oxide fuel cell, comprising an air electrode made of said porous sintered body set forth in claim 4.