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

Patent metadata

Field	Value
Publication number	US-10840546-B2
Application number	US-201816179803-A
Country	US
Kind code	B2
Filing date	Nov 2, 2018
Priority date	Dec 2, 2014
Publication date	Nov 17, 2020
Grant date	Nov 17, 2020

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 electrode assembly, comprising:
i. a first 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; and
ii. an electroactive component layer having first and second major opposing surfaces, the electroactive component layer comprising electroactive material;
wherein the first major surface of the electroactive component layer is encapsulated by the first principal side surface of the solid electrolyte wall structure.

2. The standalone electrode assembly of claim 1 , wherein the electroactive component layer comprises lithium metal.

3. The standalone electrode assembly of claim 2 , wherein the electrode assembly is solid-state, and the first major surface of the electroactive component layer forms a solid-state interface in direct contact with the first principal side surface.

4. The standalone electrode assembly of claim 3 , wherein the solid-state assembly is a double-sided assembly comprising:
a second freestanding and vitreous solid electrolyte sheet of Li ion conducting sulfur-based glass having first and second principal opposing sides and associated surfaces; and
wherein the second major surface of the electroactive component layer is encapsulated in direct contact by the first principal side surface of the second vitreous solid electrolyte sheet.

5. The standalone electrode assembly of claim 4 , wherein the electrode assembly is sealed to prevent the electroactive material from coming into direct touching contact with constituents from the external environment.

6. The standalone electrode assembly of claim 5 , wherein the double-sided electrode assembly is edge sealed by a fusion seal or pinch seal between the first and second vitreous solid electrolyte sheets.

7. A method of making a Li electrode assembly, the method comprising:
i. providing 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; and
ii. applying a fresh surface of lithium metal directly onto the first principal side surface of the solid electrolyte wall structure.

8. The method of claim 7 , wherein the vitreous sheet of Li ion conducting sulfur-based glass has a uniform thickness of no more than 50 μm.

9. The method of claim 7 , wherein the vitreous sheet of Li ion conducting sulfur-based glass has a uniform thickness that is between 10 μm and less than 30 μm thick.

10. A lithium battery cell, comprising:
a positive electrode;
a negative electrode; and
a solid electrolyte separator disposed between the electrodes, wherein the solid electrolyte separator is 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.

11. The lithium battery cell of claim 10 , wherein the negative electrode comprises lithium metal layer.

12. The lithium battery cell of claim 11 , wherein the lithium metal layer thickness is between 5 and 30 μm.

13. The lithium battery cell of claim 12 , wherein the vitreous sheet of sulfur-based glass has a uniform thickness of no more than 50 μm.

14. The lithium battery cell of claim 13 , wherein the vitreous sheet of sulfur-based glass has a uniform thickness that is between 10 μm and less than 30 μm thick.

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

• Y02P70/50

  Manufacturing or production processes characterised by the final manufactured product · CPC title