Vitreous solid electrolyte sheets of Li ion conducting sulfur-based glass and associated structures, cells and methods

Patent metadata

Field	Value
Publication number	US-10164289-B2
Application number	US-201514954812-A
Country	US
Kind code	B2
Filing date	Nov 30, 2015
Priority date	Dec 2, 2014
Publication date	Dec 25, 2018
Grant date	Dec 25, 2018

Abstract

A lithium ion-conductive solid electrolyte including a freestanding inorganic vitreous sheet of sulfide-based lithium ion conducting glass is capable of high performance in a lithium metal battery by providing a high degree of lithium ion conductivity while being highly resistant to the initiation and/or propagation of lithium dendrites. Such an electrolyte is also itself manufacturable, and readily adaptable for battery cell and cell component manufacture, in a cost-effective, scalable manner.

First claim

The invention claimed is:

1. A standalone Li ion conductive solid electrolyte separator comprising:
a freestanding substantially amorphous solid electrolyte wall structure that is dense, inorganic and highly conductive of Li ions, the wall structure comprising:
i) a continuous Li ion conducting inorganic amorphous material phase with room temperature Li ion conductivity ≥10 −5 S/cm;
ii) first and second opposing principal sides and associated surfaces; and
iii) a microstructure devoid of contiguous crystalline grain boundaries and powder particle boundaries extending between the opposing principal side surfaces;

wherein the inorganic amorphous material phase is a Li ion conducting sulfur-based glass having,
S (sulfur) and Li (lithium) as constituent elements of the glass; and
at least one more constituent element of the glass selected from the group consisting of P (phosphorous), B (boron), Ge (germanium), and Si (silicon);

wherein the wall structure is a freestanding vitreous sheet of the Li ion conducting sulfur-based glass; and
wherein the vitreous sheet has substantially parallel lengthwise edges.

2. The standalone Li ion conductive solid electrolyte separator of claim 1 , wherein the area of the vitreous sheet is at least 100 cm 2 .

3. The standalone Li ion conductive solid electrolyte separator of claim 1 , wherein the length of the vitreous sheet is at least 25 cm.

4. The standalone Li ion conductive solid electrolyte separator of claim 1 , wherein the vitreous sheet has length (l) to width (w) area aspect ratio (l/w) of no less than 10, and the sheet width (w) is no less 1 cm.

5. The standalone Li ion conductive solid electrolyte separator of claim 1 , wherein the first principal side comprises a liquid-like surface.

6. The standalone Li ion conductive solid electrolyte separator of claim 5 , wherein the liquid-like first principal side surface lacks flaws having a flaw depth extension (Γ) of more than 5 μm.

7. The standalone Li ion conductive solid electrolyte separator of claim 6 , wherein the liquid-like first principal side surface lacks flaws having a flaw depth extension (Γ) greater than 1% of the sheet thickness.

8. The standalone Li ion conductive solid electrolyte separator of claim 5 , wherein the liquid-like first principal side surface is characterizable as having a threshold current density greater than 1 mA/cm 2 .

9. The standalone Li ion conductive solid electrolyte separator of claim 8 , wherein the threshold current density is greater than 2 mA/cm 2 .

10. The standalone lithium ion conductive solid electrolyte separator of claim 5 , wherein the liquid-like first principal side surface has average surface roughness Ra≤0.05 um.

11. The standalone lithium ion conductive solid electrolyte separator of claim 5 , wherein the liquid-like first principal side surface has average surface waviness Wa≤5 μm.

12. The standalone Li ion conductive solid electrolyte separator of claim 5 , wherein the first principal side surface is untouched by an abrasive solid surface.

13. The standalone Li ion conductive solid electrolyte separator of claim 12 , wherein the second principal side surface is untouched by an abrasive solid surface.

14. The standalone Li ion conductive solid electrolyte separator of claim 1 , wherein the first and second principal side surfaces of the vitreous sheet, in its virgin state as a solid, are untouched by a foreign solid body surface.

15. The standalone Li ion conductive solid electrolyte separator of claim 14 , wherein the vitreous sheet, in its virgin state as a solid, has a uniform thickness no greater than 100 μm thick.

16. The standalone Li ion conductive solid electrolyte separator of claim 1 , wherein the first and second principal sides of the vitreous sheet are essentially free of surface microvoids.

17. The standalone Li ion conductive solid electrolyte separator of claim 1 , wherein the vitreous sheet is essentially free of internal micropores.

18. The standalone Li ion conductive solid electrolyte separator of claim 1 , wherein the first principal side surface of the vitreous sheet of sulfur-based glass is chemically compatible in direct contact with Li metal.

19. The standalone lithium ion conductive solid electrolyte separator of claim 18 , wherein the vitreous sheet has ASR of no more than 200 Ω-cm 2 , as measured using non-blocking lithium metal electrodes in direct contact with the first and second principal opposing side surfaces.

20. The standalone lithium ion conductive solid electrolyte separator of claim 19 , wherein the sulfur-based glass comprises B (boron) as a constituent element and is substantially devoid of P (phosphorous).

21. The standalone Li ion conductive solid electrolyte separator of claim 1 , wherein the sulfur-based glass is of the type selected from the group consisting of Li 2 S—YS n , Li 2 S—YS n —YO n , and combinations thereof; wherein Y is selected from the group consisting of Ge, Si, As, B, or P; and n=2, 3/2 or 5/2.

22. The standalone Li ion conductive solid electrolyte separator of claim 1 , wherein the sulfur-based glass comprises Li 2 S as a glass modifier and one or more glass formers selected from the group consisting of P 2 S 5 , P 2 O 5 , SiS 2 , SiO 2 , B 2 S 3 and B 2 O 3 .

23. The standalone Li ion conductive solid electrolyte separator of claim 1 , further comprising electrically insulating edge-protector elements, which interface with the substantially parallel lengthwise edges of the vitreous sheet.

24. The standalone Li ion conductive solid electrolyte component of claim 1 , wherein the vitreous sheet is in the form of a continuous web of sulfur-based glass having length >100 cm.

25. The standalone Li ion conductive solid electrolyte component of claim 24 , wherein the continuous web is in the form of a coil.

26. A standalone Li ion conductive solid electrolyte separator comprising:
a freestanding substantially amorphous solid electrolyte wall structure that is dense, inorganic and highly conductive of Li ions, the wall structure comprising:
i) a continuous Li ion conducting inorganic amorphous material phase with room temperature Li ion conductivity ≥10 −5 S/cm;
ii) first and second opposing principal sides and associated surfaces; and
iii) a microstructure devoid of contiguous crystalline grain boundaries and powder particle
boundaries extending between the opposing principal side surfaces;

wherein the inorganic amorphous material phase is a Li ion conducting sulfur-based glass having,
S (sulfur) and Li (lithium) as constituent elements of the glass; and
at least one more constituent element of the glass selected from the group consisting of P (phosphorous), B (boron), Ge (germanium), and Si (silicon);

wherein the wall structure is a freestanding vitreous sheet of the Li ion conducting sulfur-based glass; and
wherein the vitreous sheet of sulfur-based glass has a uniform thickness of no more than 100 μm.

27. A standalone Li ion conductive solid electrolyte separator comprising:
a freestanding substantially amorphous solid electrolyte wall structure that is dense, inorganic and highly conductive of Li ions, the wall structure comprising:
i) a continuous Li ion conducting inorganic amorphous material phase with room temperature Li ion conductivity ≥10 −5 S/cm;
ii) first and second opposing principal sides and associated surfaces; and
iii) a microstructure

Assignees

• Polyplus Battery Co Inc

Inventors

• Visco Steven J
• Nimon Yevgeniy S
• De Jonghe Lutgard C
• Katz Bruce D
• Nimon Vitaliy

Classifications

• H01M50/497

  Ionic conductivity · CPC title

• H01M50/489

  Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties · CPC title

• H01M50/437

  Glass · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M10/052 Primary

  Li-accumulators · CPC title