Solid electrolyte assembly having intermediate layer

Patent metadata

Field	Value
Publication number	US-12407012-B2
Application number	US-201917045921-A
Country	US
Kind code	B2
Filing date	Apr 16, 2019
Priority date	Apr 17, 2018
Publication date	Sep 2, 2025
Grant date	Sep 2, 2025

Abstract

A solid electrolyte assembly has an anode, a cathode, and a solid electrolyte layer located therebetween. An intermediate layer is provided between the anode or the cathode and the solid electrolyte layer. The intermediate layer is made of a cerium oxide containing lanthanum and a rare-earth element excluding lanthanum and cerium. The solid electrolyte layer contains an oxide of lanthanum. Preferably, the solid electrolyte layer contains a composite oxide of lanthanum and silicon. Also, preferably, the intermediate layer is made of a cerium oxide containing lanthanum and any one of samarium, gadolinium, yttrium, erbium, ytterbium, and dysprosium.

First claim

The invention claimed is:

1. A solid electrolyte assembly comprising:
an anode, a cathode, and a solid electrolyte located therebetween,
wherein an intermediate layer is provided between at least one of the anode and the cathode and the solid electrolyte,
the intermediate layer is made of a cerium oxide containing lanthanum and a rare-earth element Ln, and the rare-earth element Ln represents samarium or gadolinium,
an atom ratio Ln/Ce in the cerium oxide containing lanthanum and the rare-earth element Ln is in a range of 0.2 to 0.5,
an atom ratio La/Ce in the cerium oxide containing lanthanum and the rare-earth element Ln is in a range of 0.5 to 1.2,
the solid electrolyte contains an oxide of lanthanum, and
either the anode or the cathode is composed of an oxide, the oxide has a perovskite structure of ABO 3-δ having an A site and a B site, and a combination of the A site and the B site is one of:
(i) the A site consisting of lanthanum and strontium, and the B site consisting of iron, cobalt, and nickel;
(ii) the A site consisting of lanthanum and barium, and the B site consisting of iron;
(iii) the A site consisting of barium, and the B site consisting of iron and copper; and
(iv) the A site consisting of lanthanum and barium, and the B site consisting of iron and copper, and

wherein a value of a ratio P 1 /P 2 is 0.04 or greater and 0.095 or less, where the ratio P 1 /P 2 is a ratio of a primary particle size P 1 (nm) to a secondary particle size P 2 (nm), and the primary particle size P 1 and the secondary particle size P 2 are obtained through small-angle X-ray scattering measurement of the oxide having the perovskite structure, and
at least one of the anode and the cathode is made of a porous body.

2. The solid electrolyte assembly as set forth in claim 1 , wherein the solid electrolyte contains a composite oxide of lanthanum and silicon.

3. The solid electrolyte assembly as set forth in claim 2 , wherein each of the anode and the cathode is made of the porous body.

4. The solid electrolyte assembly as set forth in claim 1 ,
wherein the solid electrolyte contains a composite oxide represented by the general formula A 9.33+x [T 6.00-y M y ] O 26.0+z , where A represents one or two or more elements selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Be, Mg, Ca, Sr, and Ba, T represents an element including Si or Ge or both, and M represents one or two or more elements selected from the group consisting of Mg, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Ga, Y, Zr, Ta, Nb, B, Ge, Zn, Sn, W, and Mo, and where x represents a number that is −1.33 or greater and 1.50 or less, y represents a number that is 0.00 or greater and 3.00 or less, z represents a number that is −5.00 or greater and 5.20 or less, and a ratio of the number of moles of A to the number of moles of T is 1.33 or greater and 3.61 or less.

5. The solid electrolyte assembly as set forth in claim 4 , wherein each of the anode and the cathode is made of the porous body.

6. The solid electrolyte assembly as set forth in claim 1 ,
wherein the intermediate layer is provided between the anode and the solid electrolyte and between the cathode and the solid electrolyte.

7. The solid electrolyte assembly as set forth in claim 6 , wherein each of the anode and the cathode is made of the porous body.

8. The solid electrolyte assembly as set forth in claim 1 ,
wherein the oxide having the perovskite structure has an average particle size of 1000 nm or less,
the average particle size is obtained based on an image of particles of the oxide, and the image is taken by a scanning electron microscope, and
a value of a ratio C/D is 0.2 or greater, where D is a length of an outline of a particle of the oxide having the perovskite structure, and C is a length of a portion of the outline that overlaps an adjacent particle.

9. The solid electrolyte assembly as set forth in claim 8 , wherein each of the anode and the cathode is made of the porous body.

10. The solid electrolyte assembly as set forth in claim 1 ,
wherein the oxide having the perovskite structure has an average particle size of 1000 nm or less, and
the average particle size is obtained based on an image of particles of the oxide, and the image is taken by a scanning electron microscope.

11. The solid electrolyte assembly as set forth in claim 10 , wherein each of the anode and the cathode is made of the porous body.

12. The solid electrolyte assembly as set forth in claim 1 ,
wherein the perovskite structure of ABO 3-δ is represented by the general formula La 1-x A′ x BO 3-δ , where:
an A′ site is one of:
(v) the A′ site consisting of strontium; and
(vi) the A′ site consisting of barium; and

x represents a number that is 0.01 or greater and 0.80 or less.

13. The solid electrolyte assembly as set forth in claim 12 , wherein each of the anode and the cathode is made of the porous body.

14. The solid electrolyte assembly as set forth in claim 1 , wherein each of the anode and the cathode is made of the porous body.

Assignees

• Mitsui Mining & Smelting Co Ltd

Inventors

• Ide Shingo
• Shimanoe Kengo
• Watanabe Ken
• Suematsu Koichi

Classifications

• H01M4/9033

  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 title

• H01M2300/0074

  Ion conductive at high temperature · CPC title

• H01M2008/1293

  Fuel cells with solid oxide electrolytes · CPC title

• H01M8/1246

  the electrolyte consisting of oxides · CPC title

• H01M4/86

  Inert electrodes with catalytic activity, e.g. for fuel cells · CPC title