Ion-conducting glass ceramic having garnet-like crystal structure

Patent metadata

Field	Value
Publication number	US-10483585-B2
Application number	US-201615215421-A
Country	US
Kind code	B2
Filing date	Jul 20, 2016
Priority date	Jan 22, 2014
Publication date	Nov 19, 2019
Grant date	Nov 19, 2019

Abstract

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.

First claim

What is claimed is:

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.-%.

Assignees

• Schott Ag

Inventors

• Schneider Meike
• Hochrein Oliver
• Schmidbauer Wolfgang
• Kunze Miriam

Classifications

• H01M2300/0077

  based on zirconium oxide · CPC title

• H01M2300/0071

  Oxides · CPC title

• H01M10/052

  Li-accumulators · CPC title

• C03C4/08

  for glass selectively absorbing radiation of specified wave lengths · CPC title

• C03C3/12

  Silica-free oxide glass compositions · CPC title