Aqueous electrolyte lithium sulfur batteries

• US 8,828,575 B2
• Filed: 11/14/2012
• Issued: 09/09/2014
• Est. Priority Date: 11/15/2011
• Status: Active Grant

• Current Assignee: PolyPlus Battery Company
• Original Assignee: PolyPlus Battery Company
• Inventors: Visco, Steven J., Nimon, Yevgeniy S., Katz, Bruce D., De Jonghe, Lutgard C., Goncharenko, Nikolay, Loginova, Valentina
• Primary Examiner(s): Ruddock, Ula C
• Assistant Examiner(s): Chmielecki, Scott J
• Application Number:
  US13/676,487
• Publication Number:
  US 20130141050A1
• Time in Patent Office: 664 Days
• Field of Search: 429/105
• US Class Current: 429/105
• CPC Class Codes: H01M 10/02 Details of electrodes H01M4/00; of non-active parts H01M50/00
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/26 Selection of materials as electrolytes
• CPC Class Codes: H01M 10/36 Accumulators not provided for in groups H01M10/05-H01M10/34
• CPC Class Codes: H01M 12/08 composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
• CPC Class Codes: H01M 2300/0014 Alkaline electrolytes
• CPC Class Codes: H01M 2300/0037 Mixture of solvents
• CPC Class Codes: H01M 4/136 Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• 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 4/38 of elements or alloys
• CPC Class Codes: H01M 4/382 Lithium H01M4/405 takes precedence
• CPC Class Codes: H01M 4/386 Silicon or alloys based on silicon
• CPC Class Codes: H01M 4/40 Alloys based on alkali metals
• CPC Class Codes: H01M 4/405 Alloys based on lithium
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/5815 Sulfides
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 4/661 Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: H01M 4/663 containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
• CPC Class Codes: H01M 4/667 in the form of layers, e.g. coatings
• CPC Class Codes: H01M 4/74 : Meshes or woven material; Expanded metal
• CPC Class Codes: H01M 4/806 : Nonwoven fibrous fabric containing only fibres
• CPC Class Codes: H01M 4/808 : Foamed, spongy materials
• CPC Class Codes: H01M 50/77 : with external circulating path
• CPC Class Codes: H01M 6/04 : Cells with aqueous electrolyte
• CPC Class Codes: H01M 8/188 : by recharging of redox couples containing fluids; Redox flow type batteries
• CPC Class Codes: H01M 8/20 : Indirect fuel cells, e.g. fuel cells with redox couple being irreversible H01M8/18 takes precedence
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y02T 10/70 : Energy storage systems for electromobility, e.g. batteries

Abstract

Provided are lithium sulfur battery cells that use water as an electrolyte solvent. In various embodiments the water solvent enhances one or more of the following cell attributes: energy density, power density and cycle life. Significant cost reduction can also be realized by using an aqueous electrolyte in combination with a sulfur cathode. For instance, in applications where cost per Watt-Hour (Wh) is paramount, such as grid storage and traction applications, the use of an aqueous electrolyte in combination with inexpensive sulfur as the cathode active material can be a key enabler for the utility and automotive industries, providing a cost effective and compact solution for load leveling, electric vehicles and renewable energy storage.

Claims

1. An aqueous lithium sulfur electrochemical cell comprising:

an anode structure comprising a lithium electroactive material;

a cathode comprising a solid electron transfer medium;

an aqueous electrolyte comprising at least 10% of a non-aqueous solvent in direct contact with the electron transfer medium; and

active sulfur species in direct contact with the aqueous electrolyte;

wherein the anode electroactive material is isolated from direct contact with the aqueous electrolyte whereby the anode electroactive material does not contact water of the aqueous electrolyte or the active sulfur species.

2. The aqueous lithium sulfur electrochemical cell of claim 1, wherein the nonaqueous solvent is a protic liquid.

3. The aqueous lithium sulfur electrochemical cell of claim 2, wherein the aqueous electrolyte comprises about 10-70% of the protic liquid.

4. The aqueous lithium sulfur electrochemical cell of claim 2, wherein the aqueous electrolyte comprises about 20-60% of the protic liquid.

5. The aqueous lithium sulfur electrochemical cell of claim 2, wherein the aqueous electrolyte has a composition such that it has a pH of at least 12, absent the protic liquid.

6. The aqueous lithium sulfur electrochemical cell of claim 1, wherein the active sulfur species concentration in the aqueous electrolyte is greater than 10 Molar.

7. The aqueous lithium sulfur electrochemical cell of claim 1, wherein the active sulfur species concentration in the aqueous electrolyte is greater than 15 Molar.

8. The aqueous lithium sulfur electrochemical cell of claim 2, wherein the protic liquid is an amine.

9. The aqueous lithium sulfur electrochemical cell of claim 2, wherein the protic liquid is an alcohol.

10. The aqueous lithium sulfur electrochemical cell of claim 1, wherein the ratio of active sulfur to active lithium dissolved in the aqueous electrolyte is greater than 5.

11. The aqueous lithium sulfur electrochemical cell of claim 10, wherein the ratio of active sulfur to active lithium dissolved in the aqueous electrolyte is greater than 5 prior to initial cell operation.

12. The aqueous lithium sulfur electrochemical cell of claim 1, wherein the cell is a secondary battery cell.

13. An aqueous lithium sulfur electrochemical cell comprising:

an anode structure comprising an electroactive material;

a cathode comprising a solid electron transfer medium;

an aqueous electrolyte in direct contact with the electron transfer medium, wherein the aqueous electrolyte comprises deoxygenated water; and

active sulfur species in direct contact with the aqueous electrolyte;

wherein the anode electroactive material is isolated from direct contact with the aqueous electrolyte whereby the anode electroactive material does not contact water of the aqueous electrolyte or the active sulfur species.

14. The aqueous lithium sulfur electrochemical cell of claim 13, wherein the concentration of molecular oxygen in the aqueous electrolyte is less than 1000 ppm.

15. The aqueous lithium sulfur electrochemical cell of claim 14 wherein the concentration of molecular oxygen in the aqueous electrolyte is less than 100 ppm.

16. The aqueous lithium sulfur electrochemical cell of claim 13, wherein the cell is a secondary battery cell.

17. An aqueous lithium sulfur electrochemical cell comprising:

an anode structure comprising an electroactive material;

a cathode comprising a solid electron transfer medium;

an aqueous electrolyte in direct contact with the electron transfer medium; and

active sulfur species in direct contact with the aqueous electrolyte;

wherein the anode electroactive material is isolated from direct contact with the aqueous electrolyte whereby the anode electroactive material does not contact water of the aqueous electrolyte or the active sulfur species; and

wherein the full charge capacity of the cell prior to initial cell operation is derived from dissolved active sulfur species in the aqueous electrolyte and solid phase lithium sulfide in contact with the aqueous electrolyte.

18. The aqueous lithium sulfur electrochemical cell of claim 17, wherein the anode is substantially devoid of active lithium.

19. The aqueous lithium sulfur electrochemical cell of claim 18, wherein the lithium electroactive material of the anode is an intercalation material.

20. The aqueous lithium sulfur electrochemical cell of claim 17, wherein the cell is a secondary battery cell.