Metal sulfide anolytes for electrochemical cells

• US 10,116,003 B2
• Filed: 02/01/2016
• Issued: 10/30/2018
• Est. Priority Date: 02/03/2015
• Status: Active Grant

• Current Assignee: Quantumscape Battery Incorporated
• Original Assignee: Quantumscape Corporation
• Inventors: Mayer, Marie, Han, Joseph
• Primary Examiner(s): Kelly, Cynthia H
• Assistant Examiner(s): Wills, Monique M
• Application Number:
  US15/526,702
• Publication Number:
  US 20170324113A1
• Time in Patent Office: 1,002 Days
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 10/058 Construction or manufacture
• CPC Class Codes: H01M 4/0447 of complete cells or cells stacks
• CPC Class Codes: H01M 4/1395 of electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/1397 of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/405 Alloys based on lithium
• CPC Class Codes: H01M 4/5815 Sulfides
• CPC Class Codes: H01M 4/661 Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: H01M 4/667 in the form of layers, e.g. coatings
• CPC Class Codes: H01M 50/46 Separators, membranes or diaphragms characterised by their combination with electrodes
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

Provided are negative electrode assemblies containing lithium sulfide anolyte layers, electrochemical cells including these assemblies, and methods of forming thereof. An anolyte layer may be disposed over a metal layer of a current collector and may be used to separate the current collector from the rest of the electrolyte. The metal layer may include copper or any other suitable metal that forms in situ a metal sulfide during fabrication of the electrode assembly. Specifically, a sulfur containing layer, such as a solid electrolyte, is formed on the metal layer. Sulfur from this layer reacts with the metal of the current collector and forms a metal sulfide layer. When lithium is later added to the metal sulfide layer, a lithium sulfide anolyte layer is formed while the metal layer is recovered. Most, if not all operations may, be performed in situ during fabrication of electrochemical cells.

Claims

1. A negative electrode assembly for a rechargeable electrochemical cell, the negative electrode assembly comprising:

a current collector layer comprising a metal selected from the group consisting of copper, nickel, iron, lithium, aluminum, magnesium, indium, tungsten, molybdenum, alloys thereof, multilayers thereof, and combinations thereof; and

an anolyte layer comprising a lithium sulfide compound disposed over the current collector metal layer and having a thickness between 1 nm and 100 nm;

wherein the anolyte layer directly contacts a sulfide-containing solid electrolyte layer; and

a lithium metal layer disposed between the current collector metal layer and the anolyte layer.

2. The negative electrode assembly of claim 1, wherein the anolyte layer consists essentially of the lithium sulfide compound.

3. The negative electrode assembly of claim 1, wherein the anolyte layer directly contacts the current collector metal layer.

4. The negative electrode assembly of claim 1, wherein a combined average concentration of lithium and sulfur in the anolyte layer is greater than a combined average concentration of lithium and sulfur in the sulfide-containing solid electrolyte layer.

5. The negative electrode assembly of claim 1, wherein an average concentration of lithium in the anolyte layer is greater than an average concentration of lithium in the sulfide-containing solid electrolyte layer.

6. The negative electrode assembly of claim 4, wherein the average concentration is determined based on the molar amounts of the lithium and sulfur.

7. The negative electrode assembly of claim 1, wherein a combined average concentration of lithium and sulfur in the anolyte layer is at least 90 atomic %.

8. The negative electrode assembly of claim 1, wherein the anolyte layer further comprises the metal of the current collector metal layer.

9. The negative electrode assembly of claim 8, wherein the metal of the current collector metal layer present in the anolyte layer is copper.

10. The negative electrode assembly of claim 8, wherein the metal of the current collector metal layer present in the anolyte layer is iron.

11. The negative electrode assembly of claim 8, wherein the metal of the current collector metal layer present in the anolyte layer is nickel.

12. The negative electrode assembly of claim 1, wherein the sulfide-containing solid electrolyte layer further comprises at least one element selected from the group consisting of lithium, phosphorous, silicon, germanium, antimony, arsenic, and tin.

13. The negative electrode assembly of claim 12, wherein the sulfide-containing solid electrolyte layer further comprises a combination of at least two or more members selected from the group consisting of lithium, phosphorous, silicon, germanium, antimony, arsenic, and tin.

14. The negative electrode assembly of claim 12, wherein an average concentration of the at least one of phosphorous, silicon, germanium, antimony, arsenic, or tin in the sulfide-containing solid electrolyte layer is greater than that in the anolyte layer.

15. The negative electrode assembly of claim 1, wherein a thickness of the anolyte layer is about 5 nanometers or about 100 nanometers.

16. The negative electrode assembly of claim 1, wherein the lithium sulfide of the anolyte layer is represented by LiS_x, and wherein 0<

x≤

2.

17. The negative electrode assembly of claim 1, wherein the lithium sulfide of the anolyte layer is represented by Li₂S.

18. The negative electrode assembly of claim 1, wherein the lithium sulfide of the anolyte layer is represented by Li_1.944S.

19. The negative electrode assembly of claim 1, wherein the sulfide-containing solid electrolyte layer comprises a sulfide selected from the group consisting of evaporated lithium phosphorous sulfide, lithium phosphorous sulfide (LPS), evaporated lithium silicon sulfide, lithium silicon sulfide (LSS), evaporated lithium silicon tin phosphorous sulfide, lithium silicon tin phosphorous sulfide (LSTPS), evaporated lithium tin sulfide, lithium tin sulfide (LTS), evaporated lithium arsenic tin sulfide, lithium arsenic tin sulfide (LATS), evaporated lithium germanium phosphorous sulfide, lithium germanium phosphorous sulfide (LGPS), evaporated lithium phosphorous sulfide doped with oxygen, lithium phosphorous sulfide doped with oxygen (LPSO), evaporated lithium silicon tin phosphorous sulfide doped with oxygen, lithium silicon tin phosphorous sulfide doped with oxygen (LSTPSO), and a polymer-sulfide composite.

20. The negative electrode assembly of claim 1, wherein the sulfide-containing solid electrolyte layer comprises a sulfide selected from the group consisting of evaporated lithium phosphorous sulfide and lithium phosphorous sulfide (LPS).

21. The negative electrode assembly of claim 1, wherein the sulfide-containing solid electrolyte layer comprises a sulfide selected from the group consisting of evaporated lithium phosphorous sulfide doped with oxygen and lithium phosphorous sulfide doped with oxygen (LPSO).

22. The negative electrode assembly of claim 1, wherein the sulfide-containing solid electrolyte layer comprises a sulfide selected from the group consisting of evaporated lithium arsenic tin sulfide and lithium arsenic tin sulfide (LATS).

23. The negative electrode assembly of claim 1, wherein the current collector metal layer is a part of a bilayer current collector comprising a base layer having a metal different from the metal of the current collector metal layer.

24. The negative electrode assembly of claim 23, wherein the metal of the current collector metal layer comprises copper.

25. The negative electrode assembly of claim 23, wherein the metal of the base layer comprises nickel, iron, lithium, aluminum, magnesium, indium, alloys thereof, multilayers thereof, or combinations thereof.

26. The negative electrode assembly of claim 23, wherein the metal of the base layer comprises nickel.

27. The negative electrode assembly of claim 24, wherein the copper of the current collector metal layer is substantially free from oxygen.

28. The negative electrode assembly of claim 1, wherein a thickness of the lithium metal layer is between about 1 μ

m to about 100 μ

m.

29. The negative electrode assembly of claim 1, wherein a thickness of the lithium metal layer is about 50 μ

m.

30. A battery comprising:

a positive electrode; and

a negative electrode,

the negative electrode comprising a current collector metal layer comprising a metal selected from the group consisting of copper, nickel, iron, lithium, aluminum, magnesium, indium, tungsten, molybdenum, alloys thereof, multilayers thereof, and combinations thereof;

a sulfide-containing solid electrolyte layer disposed between the positive electrode and the negative electrode and providing ionic communication between the positive electrode and the negative electrode,

the sulfide-containing solid electrolyte comprising an anolyte layer disposed over the current collector metal layer,

wherein the anolyte layer comprises a lithium sulfide compound and has a thickness between about 10 nm and 1 μ

m, and

a lithium metal layer disposed between the current collector metal layer and the anolyte layer.