Ion-conducting glass ceramic having garnet-like crystal structure
A glass ceramic containing lithium-ions and having a garnet-like main crystal phase having an amorphous proportion of at least 5% is disclosed. The garnet-like main crystal phase preferably has the chemical formula Li 7+x−y M x II M 3−x III M 2−y IV M y V O 12 , wherein M II is a bivalent cation, M III is a trivalent cation, M IV is a tetravalent cation, M V is a pentavalent cation. The glass ceramic is prepared by a melting technology preferably within a Skull crucible and has an ion conductivity of at least 5·10 −5 S/cm, preferably of at least 1·10 −4 S/cm.
1. A lithium-ion conducting glass ceramic comprising a garnet-like main crystal phase having an amorphous proportion of at least 5 wt.-%, wherein said garnet-like main crystal phase has the chemical formula:
Li 7+x−y M x II M 3−x III M 2−y IV M y V O 12 ,
wherein M II is a bivalent cation, M III a trivalent cation, M Iv a tetravalent cation, and M V a pentavalent cation.
2. The glass ceramic of claim 1 , wherein 0≤x<3 and 0≤y<2.
3. The glass ceramic of claim 1 , wherein said glass ceramic is ceramicised from a starting glass comprising 10-25 wt.-% of Li 2 O.
4. The glass ceramic of claim 1 , comprising in total 40-60 wt.-% of an oxide of at least one lanthanoid.
5. The glass ceramic of claim 1 , wherein said glass ceramic comprises in total 40-60 wt.-% of an oxide of at least one lanthanoid and is ceramicised from a starting glass comprising 10-25 wt.-% of Li 2 O.
6. The glass ceramic of claim 1 , wherein 0≤x≤2 and 0≤y≤1.
7. The glass ceramic of claim 1 , wherein said amorphous proportion is a maximum of 40 wt.-%.
8. The glass ceramic of claim 1 , having an ion-conductivity of at least 5·10 −5 S/cm.
9. The glass ceramic of claim 1 , wherein said glass ceramic is ceramicised from a starting glass comprising in total 40-60 wt.-% of La 2 O 3 .
10. The glass ceramic of claim 1 , wherein said glass ceramic is ceramicised from a starting glass comprising 15-35 wt.-% of ZrO 2 .
11. The glass ceramic of claim 1 , wherein said glass ceramic is ceramicised from a starting glass comprising 1-5 wt.-% of one oxide being selected from the group consisting of Al 2 O 3 , Bi 2 O 3 , Ga 2 O 3 , Y 2 O 3 , Fe 2 O 3 , Cr 2 O 3 , In 2 O 3 , and mixtures thereof.
12. The glass ceramic of claim 11 , wherein said glass ceramic is ceramicised from a starting glass comprising 1-5 wt.-% of one oxide being selected from the group consisting of Al 2 O 3 , Bi 2 O 3 , Ga 2 O 3 , Y 2 O 3 , Fe 2 O 3 , Cr 2 O 3 , In 2 O 3 , and mixtures thereof.
13. The glass ceramic of claim 1 , wherein said glass ceramic is ceramicised from a starting glass comprising 1-20 wt.-% of an oxide being selected from the group consisting of Ta 2 O 5 , Nb 2 O 5 , V 2 O 5 , P 2 O 5 , and mixtures thereof.
14. The glass ceramic of claim 1 , wherein said glass ceramic is ceramicised from a starting glass comprising 1-5 wt.-% of an oxide being selected from the group consisting of TiO 2 , HfO 2 , SnO 2 , and mixtures thereof.
15. The glass ceramic of claim 1 , wherein said glass ceramic is ceramicised from a starting glass comprising 1-10 wt.-% of at least of an oxide being selected from the group consisting of RO, ZnO, and mixtures thereof, wherein R is an alkaline earth ion.
16. A battery comprising a glass ceramic according to claim 1 , wherein said battery is configured as a battery selected from the group consisting of a lithium-ion battery, an all-solid-state battery, a lithium-air battery, and a lithium-sulfur battery.
17. The battery of claim 16 , wherein said glass ceramic is configured as an electrolyte, as an electrolyte additive or as a component of a composite electrolyte.
18. A lithium-ion conducting glass ceramic comprising:
a garnet-like main crystal phase having an amorphous proportion of greater than 10 wt.-% and less than 40 wt.-%,
wherein said garnet-like main crystal phase has the chemical formula:
Li 7+x−y M x II M 3−x III M 2−y IV M y V O 12 ,
wherein 0≤x<3 and 0≤y<2,
wherein M is selected from the group consisting of La, Zr, Al, Ta, and Nb, and
wherein M II is a bivalent cation, M III a trivalent cation, M IV a tetravalent cation, and M V a pentavalent cation.
19. The glass ceramic of claim 18 , wherein 0≤x≤2 and 0≤y≤1.
20. The glass ceramic of claim 18 , comprising in total 40-60 wt.-% of an oxide of at least one lanthanoid.
21. The glass ceramic of claim 18 , wherein said amorphous proportion is a maximum of 40 wt.-%.
22. The glass ceramic of claim 18 , having an ion-conductivity of at least 5·10 −5 S/cm.
23. The glass ceramic of claim 18 , having an ion-conductivity of at least 1·10 −4 S/cm.
24. The glass ceramic of claim 18 , wherein the amorphous proportion is smaller than or equal to 30 wt.-%.