Ion-conducting glass ceramic having garnet-like crystal structure

Patent metadata

Field	Value
Publication number	US-10899648-B2
Application number	US-201916596588-A
Country	US
Kind code	B2
Filing date	Oct 8, 2019
Priority date	Jan 22, 2014
Publication date	Jan 26, 2021
Grant date	Jan 26, 2021

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 method of producing a glass ceramic comprising a garnet-like main crystal phase, wherein the garnet-like main crystal phase has a 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, wherein 0≤x<3 and 0≤y<2, the method comprising the steps of:
providing starting materials for the glass ceramic;
melting and homogenizing the starting materials in an inductively heated Skull crucible to yield a glass melt; and
cooling the glass melt and temperature treating to generate the glass ceramic comprising the garnet-like main crystal phase with an amorphous proportion of at least 5% wt.-%.

2. The method of claim 1 , wherein the inductively heated Skull crucible has a plurality of metal tubes that are traversed by a coolant having slot-like intervals between the plurality of metal tubes, and further comprise having an induction coil surrounding the plurality of metal tubes.

3. The method of claim 2 , wherein the plurality of metal tubes are shorted with each other.

4. The method of claim 1 , wherein the glass ceramic comprises 10-25 wt.-% of Li 2 O.

5. The method of claim 1 , wherein the glass ceramic comprises in total 40-60 wt.-% of an oxide of at least one lanthanoid.

6. The method of claim 1 , wherein the glass ceramic comprises 10-25 wt.-% of Li 2 O and in total 40-60 wt.-% of an oxide of at least one lanthanoid.

7. The method of claim 1 , wherein 0≤x≤2 and 0≤y≤1.

8. The method of claim 1 , wherein the amorphous proportion has a maximum of 40 wt.-%.

9. The method of claim 1 , wherein the glass ceramic has an ion-conductivity of at least 5·10 −5 S/cm.

10. The method of claim 1 , wherein the glass ceramic comprises in total 40-60 wt.-% of La 2 O 3 .

11. The method of claim 1 , wherein the glass ceramic comprises 15-35 wt.-% of ZrO 2 .

12. The method of claim 1 , wherein the glass ceramic comprises 1-5 wt.-% of one oxide being selected from a 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 method of claim 12 , wherein the glass ceramic comprises 1-5 wt.-% of one oxide being selected from a 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.

14. The method of claim 1 , wherein the glass ceramic comprises 1-20 wt.-% of an oxide being selected from a group consisting of Ta 2 O 5 , Nb 2 O 5 , V 2 O 5 , P 2 O 5 , and mixtures thereof.

15. The method of claim 1 , wherein the glass ceramic comprises 1-5 wt.-% of an oxide being selected from a group consisting of TiO 2 , HfO 2 , SnO 2 , and mixtures thereof.

16. The method of claim 1 , wherein the glass ceramic comprises 1-10 wt.-% of at least of an oxide being selected from a group consisting of RO, ZnO, and mixtures thereof, wherein R is an alkaline earth ion.

17. A method of producing a glass ceramic comprising a garnet-like main crystal phase, wherein the 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 is a trivalent cation, M IV is a tetravalent cation, M V is a pentavalent cation, the method comprising the steps of:
providing starting materials for the glass ceramic;
melting and homogenizing the starting materials to yield a glass melt;
cooling the glass melt and temperature treating to generate the glass ceramic comprising the garnet-like main crystal phase with an amorphous proportion of at least 5% wt.-%.

18. The method of claim 1 , wherein 0≤x≤2 and 0≤y≤1.

19. The method of claim 1 , wherein the amorphous proportion has a maximum of 40 wt.-%.

20. A method of producing a glass ceramic comprising a garnet-like main crystal phase, wherein the 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 is a trivalent cation, M IV is a tetravalent cation, M V is a pentavalent cation, the method comprising the steps of:
providing starting materials for the glass ceramic;
melting and homogenizing the starting materials to yield a glass melt;
cooling the glass melt and temperature treating to generate the glass ceramic comprising the garnet-like main crystal phase with an amorphous proportion of at least 5% wt.-% and an ion-conductivity of at least 5·10 −5 S/cm.

Assignees

• Schott Ag

Inventors

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

Classifications

• C03C4/18

  for ion-sensitive glass · CPC title

• H01M2300/0077

  based on zirconium oxide · CPC title

• C03C3/12

  Silica-free oxide glass compositions · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M10/052

  Li-accumulators · CPC title