Solid electrolyte and lithium ion battery with cubic garnet type crystalline and amorphous areas
A solid electrolyte which reduces grain boundary resistance and exhibits a high total ion conductivity is provided. The solid electrolyte includes a first area which has a cubic garnet type crystalline and a second area which is amorphous, around the first area, in which each of the first area and the second area contains a composite oxide represented by formula (1) or (2) as a forming material, and an abundance ratio of metal atoms each having an ionic radius of 78 pm or more gradually increases from the first area to the second area. Li 7+x La 3−x Zr 2 A x O 12 (1) [In formula (1), A is at least one selected from the group consisting of Mg, Ca, Sr, and Ba. In addition, x is 0.1 or more and 0.6 or less.] Li 7 La 3−x Zr 2 B x O 12 (2) [In formula (2), B is at least one selected from the group consisting of Sc and Y. In addition, x is 0.1 or more and 0.6 or less.]
1. A solid electrolyte comprising: a first area which has a cubic garnet type crystalline structure; and a second area which is amorphous around the first area, wherein:
each of the first area and the second area contains a complex oxide represented by formula (1) or (2) as a forming material;
Li 7+x La 3−x Zr 2 A x O 12 (1)
in formula (1), A is at least one selected from the group consisting of magnesium, calcium, strontium, and barium, and x is 0.1 or more and 0.6 or less;
Li 7 La 3−x Zr 2 B x O 12 (2)
in formula (2), B is at least one selected from the group consisting of scandium and yttrium, and x is 0.1 or more and 0.6 or less; and
an abundance ratio of metal atoms each having an ionic radius of 78 pm or more gradually increases from the first area to the second area;
wherein the solid electrolyte is manufactured by a method that comprises: obtaining a gel by removing a solvent from a precursor solution in which a lithium compound, a lanthanum compound, a zirconium compound, and a compound comprising the metal atoms are dissolved in the solvent; and heat-treating the gel to form a composite containing the first and second areas.
2. The solid electrolyte according to claim 1 , wherein a composite containing the first area and the second area has a plurality of voids, a third area which is amorphous is formed in the plurality of voids, and the third area contains an element different from the second area.
3. The solid electrolyte according to claim 1 , wherein the metal atoms are any one of niobium, antimony, and tantalum.
4. The solid electrolyte according to claim 2 , wherein the third area contains at least lithium, boron, and oxygen as elements.
5. The solid electrolyte according to claim 4 , wherein the third area contains lithium borate.
6. A lithium ion battery comprising: a positive electrode; a negative electrode; and a solid electrolyte layer which is sandwiched between the positive electrode and the negative electrode, wherein the solid electrolyte layer contains the solid electrolyte according to claim 1 .
7. The solid electrolyte according to claim 1 , wherein the solid electrolyte is non-sintered.
8. A solid electrolyte comprising: a first area which has a cubic garnet type crystalline structure; and a second area which is amorphous around the first area, wherein:
each of the first area and the second area contains a complex oxide represented by formula (1) or (2) as a forming material;
Li 7+x La 3−x Zr 2 A x O 12 (1)
in formula (1), A is at least one selected from the group consisting of magnesium, calcium, strontium, and barium, and x is 0.1 or more and 0.6 or less;
Li 7+x La 3−x Zr 2 B x O 12 (2)
in formula (2), B is at least one selected from the group consisting of scandium and yttrium, and x is 0.1 or more and 0.6 or less;
an abundance ratio of metal atoms each having an ionic radius of 78 pm or more gradually increases from the first area to the second area; and the metal atoms comprise antimony;
wherein the solid electrolyte is manufactured by a method that comprises: obtaining a gel by removing a solvent from a precursor solution in which a lithium compound, a lanthanum compound, a zirconium compound, and a compound comprising the metal atoms are dissolved in the solvent; and heat-treating the gel to form a composite containing the first and second areas.
9. The solid electrolyte according to claim 8 , wherein the metal atoms further comprise any one of niobium and tantalum.