Sintered body and method for manufacturing thereof
The sintered body has an average particle size in the range of 0.1 μm or more and 5 μm or less, includes gamet-type oxide base material particles having at least Li, La, and Zr, has 8% by volume or more of voids, and has an ionic conductivity of 1.0×10 −5 S/cm or more at temperature of 25° C.
1. A method for manufacturing a sintered body comprising:
a precursor manufacturing step for synthesizing a precursor powder, which is not sintered, by mixing lithium hydroxide with a base material powder made of a garnet-type oxide having an average particle size in a range of 0.1 μm to 5 μm and including at least Li, La, and Zr and by firing an obtained power; and
a molding and sintering step for molding the precursor powder as it is, or adding a pore-forming material to the precursor powder and molding, and for sintering an obtained molded body at a temperature of 900° C. or less to obtain a sintered body having a void of 8% by volume or more.
2. The method for manufacturing the sintered body according to claim 1 m, wherein:
in the precursor manufacturing step, the base material powder having a basic composition of Li 7.0+x−y (La 3−x , A x ) (Zr 2−y , T y )O 12 is used;
A is at least one of Sr and Ca;
T is at least one of Nb and Ta,
an equation of 0<x≤1.0 and an equation of 0<y<0.75 are satisfied.
3. The method for manufacturing the sintered body according to claim 1 , wherein:
a lithium number in the lithium hydroxide is defined as Lh;
a lithium number in the garnet type oxide is defined as Lg;
a ration of Lh with respect to Lg is defined as Lh/Lg; and
in the precursor manufacturing step, the lithium hydroxide is mixed in a range of Lh/Lg of 0.05 or more and 0.35 or less.
4. The method for manufacturing the sintered body according to claim 1 , wherein:
in the precursor manufacturing step, a mixed powder is fired at a temperature of 650° C. or higher and 800° C. or lower.
5. The method for manufacturing the sintered body according to claim 1 , wherein:
in the molding and sintering step, lithium borate is further added and molded.
6. The method for manufacturing the sintered body according to claim 1 , wherein:
in the molding and sintering step, the molded body is sintered at a temperature of 800° C. or higher and 900° C. or lower.
7. The method for manufacturing the sintered body according to claim 1 , wherein:
in the molding and sintering step, the pore-forming material is added to the precursor powder to mold and sinter, and the sintered body having the void in a range of 10% by volume or more and 50% by volume or less and having an ion conductivity of 1.0×10 −4 S/cm at 25° C. is obtained.
8. The method for manufacturing the sintered body according to claim 1 , wherein:
in the molding and sintering step, the precursor powder is molded and sintered without adding the pore-forming material, and the sintered body having the void of 20% by volume or less and having an ion conductivity of 1.0×10 −5 S/cm at 25° C. is obtained.
9. The method for manufacturing the sintered body according to claim 1 , wherein:
in the molding and sintering step, the sintered body including aluminum oxide in an amount of 0.08 mol or more and 0.12 mol or less with respect to 1 mol of the garnet-type oxide is obtained.
10. The method for manufacturing the sintered body according to claim 1 , wherein:
an ion conductivity of the sintered body at 25° C. is 1.0×10 −5 S/cm or more.
11. The method for manufacturing the sintered body according to claim 10 , wherein:
the base material particle has a basic composition of Li 7.0+x−y (La 3−x , A x ) (Zr 2−y , T y )O 12 ;
A is at least one of Sr and Ca;
T is at least one of Nb and Ta; and
an equation of 0<x≤1.0 and an equation of 0<y<0.75 are satisfied.
12. The method for manufacturing the sintered body according to claim 10 , wherein:
lithium borate is included in a grain boundary of the base material particle.
13. The method for manufacturing the sintered body according to claim 10 , wherein
the void is in a range of 10% by volume or more and 50% by volume or less.
14. The method for manufacturing the sintered body according to claim 10 , wherein
the void is in a range of 20% by volume or less; and
an ion conductivity of the sintered body at 25° C. is 1.0×10 −4 S/cm or more.