Electrolytes for lithium sulfur cells

• US 9,859,588 B2
• Filed: 06/06/2014
• Issued: 01/02/2018
• Est. Priority Date: 01/06/2004
• Status: Active Grant

• Current Assignee: Sion Power Corporation
• Original Assignee: Sion Power Corporation
• Inventors: Mikhaylik, Yuriy V.
• Primary Examiner(s): WEINER, LAURA S
• Application Number:
  US14/298,640
• Publication Number:
  US 20140287326A1
• Time in Patent Office: 1,306 Days
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0567 characterised by the additives
• CPC Class Codes: H01M 10/0568 characterised by the solutes
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 10/0587 of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
• 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 4/382 Lithium H01M4/405 takes precedence
• CPC Class Codes: H01M 4/581 Chalcogenides or intercalation compounds thereof
• CPC Class Codes: H01M 4/5815 Sulfides
• 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

Disclosed is an electrochemical cell comprising a lithium anode and a sulfur-containing cathode and a non-aqueous electrolyte. The cell exhibits high utilization of the electroactive sulfur-containing material of the cathode and a high charge-discharge efficiency.

Claims

1. An electrochemical cell comprising:

(a) a cathode comprising an electroactive sulfur-containing material;

(b) an anode comprising a first active anode layer comprising lithium and a multi-layered structure overlying a surface layer of said first anode active layer, wherein said multi-layer structure comprises three or more layers, wherein at least one of said three or more layers comprises a non-electronically conductive single ion conducting layer, wherein at least another one of said three or more layers comprises a polymer layer, and wherein the non-electrically conductive single ion conducting layer and the polymer layer alternate; and

(c) a nonaqueous electrolyte, wherein the electrolyte comprises;

(i) one or more nonaqueous solvents selected from the group consisting of acyclic ethers, cyclic ethers, polyethers, and sulfones;

(ii) one or more lithium salts; and

(iii) 0.02 mol/Kg solvent and about 2 mol/Kg solvent one or more N—

O additives selected from the group consisting of inorganic nitrates, organic nitrates, inorganic nitrites, organic nitrites, organic nitro compounds, pyridine N-oxide, alkylpyridine N-oxides, and tetramethyl piperidine N-oxyl (TEMPO),

wherein the electroactive sulfur-containing material comprises material selected from the group consisting of elemental sulfur and organic materials containing both sulfur atoms and carbon atoms and electrochemical activity involves breaking or forming of sulfur-sulfur covalent bonds, and

wherein the cell exhibits utilization greater than the utilization of another electrochemical cell comprising the cathode, the anode, and the nonaqueous electrolyte, without the one or more N—

O additives, and

wherein utilization is defined as a percent of elemental sulfur in the cathode that is utilized.

2. The electrochemical cell of claim 1, wherein the utilization of the electrochemical cell is about 20% to about 36% greater than the utilization of the another electrochemical cell under the same test conditions.

3. The electrochemical cell of claim 1, wherein the utilization of the electrochemical cell is about 20% to about 35% greater than the utilization of the another electrochemical cell under the same test conditions.

4. The electrochemical cell of claim 1, wherein a concentration of the one or more N—

O additives in the electrolyte is between about 0.2 mol/Kg solvent and about 1 mol/Kg solvent.

5. The electrochemical cell of claim 1, wherein a concentration of the one or more N—

O additives in the electrolyte is between about 0.1 mol/Kg solvent and about 1.5 mol/Kg solvent.

6. The electrochemical cell of claim 1, wherein the one or more N—

O additives comprise one or more of the lithium nitrates.

7. The electrochemical cell of claim 1, wherein the one or more N—

O additives comprise one or more inorganic nitrates, organic nitrates, inorganic nitrites, organic nitrites, and organic nitro compounds.

8. The electrochemical cell of claim 1, wherein the a non-electronically conductive single ion conducting layer is selected from the group consisting of inorganic polymeric materials, organic polymeric materials, mixed organic-inorganic polymeric materials, glass, and glassy materials.

9. The electrochemical cell of claim 1, wherein the a non-electronically conductive single ion conducting layer is selected from the group consisting of lithium silicates, lithium borates, lithium aluminates, lithium phosphates, lithium phosphorus oxynitrides, lithium silicosulfides, lithium germanosulfides, lithium lanthanum oxides, lithium titanium oxides, lithium borosulfides, lithium aluminosulfides, and lithium phosphosulfides, and combinations thereof.

10. The electrochemical cell of claim 1, wherein the polymer layer is selected from the group consisting of electrically conductive polymers, ionically conductive polymers, sulfonated polymers, and hydrocarbon polymers.

11. The electrochemical cell of claim 1, wherein the polymer layer is selected from the group consisting of poly(p-phenylene), polyacetylene, poly(phenylenevinylene), polyazulene, poly(perinaphthalene), polyacenes, poly(naphthalene-2,6-diyl), polyethylene oxides, sulfonated siloxane polymers, sulfonated polystyrene-ethylene-butylene polymers, sulfonated polystyrene polymers, ethylene-propylene polymers, and polystyrene polymers.