Scandia-stabilized zirconia powder for solid oxide fuel cells, method for producing same, scandia-stabilized zirconia sintered body for solid oxide fuel cells, method for producing said scandia-stabilized zirconia sintered body for solid oxide fuel cells, and solid oxide fuel cell

Patent metadata

Field	Value
Publication number	US-11462760-B2
Application number	US-201716625908-A
Country	US
Kind code	B2
Filing date	Jun 30, 2017
Priority date	Jun 30, 2017
Publication date	Oct 4, 2022
Grant date	Oct 4, 2022

Abstract

The present invention provides a scandia-stabilized zirconia powder for solid oxide fuel cells or a scandia-stabilized zirconia sintered body for solid oxide fuel cells, each having high crystal structure stability, low grain-boundary resistivity, and high ionic conductivity; and the production methods of these. The scandia-stabilized zirconia powder for solid oxide fuel cells comprises a compound represented by formula (1): (ZrO2)1-x-a(Sc2O3)x(Al2O3)a. In formula (1), 0.09≤x≤0.11 and 0.002≤a<0.01 are satisfied. The scandia-stabilized zirconia powder has a rhombohedral phase crystal structure. The sintered body of the scandia-stabilized zirconia powder has a cubic phase crystal structure. The sintered body of the scandia-stabilized zirconia powder has a grain-boundary resistivity of 12 Ω·cm or less at 550° C.

First claim

The invention claimed is:

1. A scandia-stabilized zirconia powder for solid oxide fuel cells, comprising
ZrO 2 , Sc 2 O 3 , Al 2 O 3 ,
wherein
the Sc 2 O 3 is dissolved in the ZrO 2 ,
a molar ratio of the ZrO 2 , the Sc 2 O 3 , and the Al 2 O 3 in the scandia-stabilized zirconia powder is (ZrO 2 ) 1-x-a : (Sc 2 O 3 ) x : (Al 2 O 3 ) a , in which x is 0.097≤x≤0.103 and a is 0.002≤a<0.01,
the scandia-stabilized zirconia powder having a rhombohedral phase crystal structure,
the scandia-stabilized zirconia powder is effective for producing a sintered body that consists of a cubic phase crystal structure, and that has a grain-boundary resistivity of 12 Ω·cm or less at 550° C., and
the sintered body is produced by applying a pressure of 1.0 t/cm 2 to the scandia-stabilized zirconia powder, and sintering the scandia-stabilized zirconia powder at 1450° C. for 2 hours.

2. The scandia-stabilized zirconia powder according to claim 1 , wherein the sintered body has a grain-boundary resistivity of 60 Ω·cm or less at 500° C.

3. The scandia-stabilized zirconia powder according to claim 1 , wherein the sintered body has a grain-boundary resistivity of 200 Ω·cm or less at 450° C.

4. The scandia-stabilized zirconia powder according to claim 1 , wherein the sintered body has a grain-boundary resistivity of 1000 Ω·cm or less at 400° C.

5. The scandia-stabilized zirconia powder according to claim 1 , wherein the crystal structure of the sintered body does not change even after heat treatment at 600° C. for 1000 hours.

6. A scandia-stabilized zirconia sintered body for solid oxide fuel cells, comprising a compound represented by the following formula (1):
(ZrO 2 ) 1-x-a (Sc 2 O 3 ) x (Al 2 O 3 ) a   (1)

wherein x is 0.097≤x≤0.103, and a is 0.002≤a<0.01, and
wherein the sintered body consists of a cubic phase crystal structure, and has a grain-boundary resistivity of 12 Ω·cm or less at 550° C., and is obtainable by sintering the scandia-stabilized zirconia powder according to claim 1 by applying a pressure of 1.0 t/cm 2 to the scandia-stabilized zirconia powder, and sintering the scandia-stabilized zirconia powder at 1450° C. for 2 hours.

7. The scandia-stabilized zirconia sintered body according to claim 6 , wherein the sintered body has a grain-boundary resistivity of 60 Ω·cm or less at 500° C.

8. The scandia-stabilized zirconia sintered body according to claim 6 , wherein the sintered body has a grain-boundary resistivity of 200 Ω·cm or less at 450° C.

9. The scandia-stabilized zirconia sintered body according to claim 6 , wherein the sintered body has a grain-boundary resistivity of 1000 Ω·cm or less at 400° C.

10. The scandia-stabilized zirconia sintered body according to claim 6 , wherein the crystal structure does not change even after heat treatment at 600° C. for 1000 hours.

11. A method for producing the scandia-stabilized zirconia powder according to claim 1 , the method comprising the following steps 1 to 3:
step 1: mixing a raw material containing a zirconium salt and a raw material containing a scandium salt, and then performing neutralization to obtain a scandium-zirconium composite hydroxide;
step 2: calcining the resulting hydroxide to obtain an oxide; and
step 3: adding alumina to the resulting oxide,
wherein an amount of each of the zirconium salt-containing raw material, the scandium salt-containing raw material, and the alumina is adjusted to a range such that a molar ratio of the zirconium salt, the scandium salt, and the alumina is (ZrO 2 ) 1-x-a : (Sc 2 O 3 ) x : (Al 2 O 3 ) a , in which x is 0.097≤x≤0.103 and a is 0.002≤a<0.01.

12. A method for producing the scandia-stabilized zirconia sintered body according to claim 6 , the method comprising the following steps 1 to 4:
step 1: mixing a raw material containing a zirconium salt and a raw material containing a scandium salt, and then performing neutralization to obtain a scandium-zirconium composite hydroxide;
step 2: calcining the resulting hydroxide to obtain an oxide;
step 3: adding alumina to the resulting oxide; and
step 4: sintering the alumina-containing oxide obtained in step 3, of 1.0 t/cm 2 to the alumina-containing, oxide obtained in step 3, and sintering the alumina-containing oxide at 1450° C. for 2 hours,
wherein an amount of each of the zirconium salt-containing raw material, the scandium salt-containing raw material, and the alumina is adjusted to a range such that a molar ratio of the zirconium salt, the scandium salt, and the alumina is (ZrO 2 ) 1-x-a : (Sc 2 O 3 ) x : (Al 2 O 3 ) a , in which x is 0.097≤x≤0.103 and a is 0.002≤a<0.01.

13. A solid oxide fuel cell comprising the scandia-stabilized zirconia sintered body according to claim 6 as a constituent element.

Assignees

• Daiichi Kigenso Kagaku Kogyo

Inventors

• Tamazaki Fuminori

Classifications

• C04B35/4885

  with aluminium oxide · CPC title

• C01G25/00

  Compounds of zirconium · CPC title

• C04B2235/762

  Cubic symmetry, e.g. beta-SiC · CPC title

• C04B35/62685

  characterised by the order of addition of constituents or additives · CPC title

• C04B35/62645

  Thermal treatment of powders or mixtures thereof other than sintering · CPC title