Method of producing shape-conformable alkali metal-sulfur battery having a deformable and conductive quasi-solid electrode

Patent metadata

Field	Value
Publication number	US-10454141-B2
Application number	US-201715638854-A
Country	US
Kind code	B2
Filing date	Jun 30, 2017
Priority date	Jun 30, 2017
Publication date	Oct 22, 2019
Grant date	Oct 22, 2019

Abstract

Provided is a method of preparing an alkali-sulfur cell comprising: (a) combining a quantity of an active material, a quantity of an electrolyte containing an alkali salt dissolved in a solvent, and a conductive additive to form a deformable and electrically conductive electrode material, wherein the conductive additive, containing conductive filaments, forms a 3D network of electron-conducting pathways; (b) forming the electrode material into a quasi-solid electrode (the first electrode), wherein the forming step includes deforming the electrode material into an electrode shape without interrupting the 3D network of electron-conducting pathways such that the electrode maintains an electrical conductivity no less than 10−6 S/cm; (c) forming a second electrode (the second electrode may be a quasi-solid electrode as well); and (d) forming an alkali-sulfur cell by combining the quasi-solid electrode and the second electrode having an ion-conducting separator disposed between the two electrodes.

First claim

We claim:

1. A method of producing an alkali metal-sulfur cell having a quasi-solid electrode, the method comprising:
(a) combining a quantity of a cathode active material, a quantity of an electrolyte, and a conductive additive to form a deformable and electrically conductive cathode material, wherein said cathode active material contains a sulfur-containing material selected from sulfur, a metal-sulfur compound, a sulfur-carbon composite, a sulfur-graphene composite, a sulfur-graphite composite, an organic sulfur compound, a sulfur-polymer composite, or a combination thereof, and wherein said conductive additive, containing conductive filaments, forms a 3D network of electron-conducting pathways and said electrolyte contains an alkali salt dissolved in a solvent and no ion-conducting polymer dissolved or dispersed in said solvent;
(b) forming the cathode material into a quasi-solid cathode, wherein said forming includes deforming the cathode material into an electrode shape without interrupting said 3D network of electron-conducting pathways such that the cathode maintains an electrical conductivity no less than 10 −6 S/cm;
(c) forming an anode; and
(d) forming an alkali metal-sulfur cell by combining the quasi-solid cathode and the anode.

2. The method of claim 1 , wherein said quasi-solid cathode contains from 30% to 95% by volume of said cathode active material, 5% to 40% by volume of said electrolyte, and 0.01% to 30% by volume of said conductive additive.

3. The method of claim 1 , wherein said conductive filaments are selected from carbon fibers, graphite fibers, carbon nanofibers, graphite nanofibers, carbon nanotubes, needle coke, carbon whiskers, conductive polymer fibers, conductive material-coated fibers, metal nanowires, metal fibers, metal wires, graphene sheets, expanded graphite platelets, a combination thereof, or a combination thereof with non-filamentary conductive particles.

4. The method of claim 1 , wherein said electrode maintains an electrical conductivity from 10 −3 S/cm to 10 S/cm.

5. The method of claim 1 , wherein said quasi-solid cathode contains from 0.1% to 20% by volume of a conductive additive.

6. The method of claim 1 , wherein said quasi-solid cathode contains from 1% to 10% by volume of a conductive additive.

7. The method of claim 1 , wherein the quantity of the cathode active material is from 40% to 90% by volume of the cathode material.

8. The method of claim 1 , wherein the quantity of the active material is about 50% to about 85% by volume of the cathode material.

9. The method of claim 1 , wherein said step of combining includes dispersing said conductive filaments into a liquid solvent to form a homogeneous suspension prior to adding said cathode active material in said suspension and prior to dissolving said alkali metal salt in said liquid solvent of said suspension.

10. A method of producing an alkali metal-sulfur cell having a quasi-solid electrode, the method comprising:
(a) combining a quantity of a cathode active material, a quantity of an electrolyte, and a conductive additive to form a deformable and electrically conductive cathode material, wherein said cathode active material contains a sulfur-containing material selected from sulfur, a metal-sulfur compound, a sulfur-carbon composite, a sulfur-graphene composite, a sulfur-graphite composite, an organic sulfur compound, a sulfur-polymer composite, or a combination thereof, and wherein said conductive additive, containing conductive filaments, forms a 3D network of electron-conducting pathways and said electrolyte contains an alkali salt dissolved in a solvent and no ion-conducting polymer dissolved or dispersed in said solvent;
(b) forming the cathode material into a quasi-solid cathode, wherein said forming includes deforming the cathode material into an electrode shape without interrupting said 3D network of electron-conducting pathways such that the cathode maintains an electrical conductivity no less than 10 −6 S/cm;
(c) forming an anode; and
(d) forming an alkali metal-sulfur cell by combining the quasi-solid cathode and the anode;
wherein said steps of combining and forming the cathode material into a quasi-solid cathode include dissolving a lithium salt or sodium salt in a liquid solvent to form an electrolyte having a first salt concentration and subsequently removing a portion of said liquid solvent to increase the salt concentration to obtain a quasi-solid electrolyte having a second salt concentration higher than the first concentration and higher than 2.5 M.

11. The method of claim 10 , wherein said removing does not cause precipitation or crystallization of said salt, and said electrolyte is in a supersaturated state.

12. The method of claim 10 , wherein said liquid solvent contains a mixture of at least a first liquid solvent and a second liquid solvent and the first liquid solvent is more volatile than the second liquid solvent and wherein said removing a portion of said liquid solvent includes removing said first liquid solvent.

13. The method of claim 1 , wherein said step of forming the anode includes (A) combining a quantity of an anode active material, a quantity of an electrolyte, and a conductive additive to form a deformable and electrically conductive anode material, wherein said conductive additive, containing conductive filaments, forms a 3D network of electron-conducting pathways and said electrolyte contains an alkali salt dissolved or dispersed in a solvent; and (B) forming the deformable and conductive anode material into a quasi-solid anode, wherein said forming includes deforming the deformable and conductive anode material into an electrode shape without interrupting said 3D network of electron-conducting pathways such that the anode maintains an electrical conductivity no less than 10 −6 S/cm.

14. The method of claim 1 , wherein said solvent is selected from water, an organic solvent, an ionic liquid, or a mixture of an organic solvent and an ionic liquid.

15. The method of claim 1 , wherein said alkali metal-sulfur cell is a lithium-ion sulfur cell and said anode contains an anode active material selected from the group consisting of:
(a) particles of lithium metal or a lithium metal alloy;
(b) natural graphite particles, artificial graphite particles, mesocarbon microbeads (MCMB), carbon particles, needle coke, carbon nanotubes, carbon nanofibers, carbon fibers, and graphite fibers;
(c) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), nickel (Ni), cobalt (Co), manganese (Mn), titanium (Ti), iron (Fe), and cadmium (Cd);
(d) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with other elements, wherein said alloys or compounds are stoichiometric or non-stoichiometric;
(e) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd, and their mixtures or composites;
(f) prelithiated versions thereof;
(g) prelithiated graphene sheets; and
combinations thereof.

16. The method of claim 15 , wherein said prelithiated graphene sheets are selected from prelithiated versions of pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, a physically or chemically activated or etched version thereof, or a combination thereof.

17. The method of claim 1 , wherein said alkali metal-sulf

Assignees

• Nanotek Instruments Inc
• Global Graphene Group Inc

Inventors

• Zhamu Aruna
• Jang Bor Z

Classifications

• H01M10/0564

  the electrolyte being constituted of organic materials only · CPC title

• H01M10/054

  Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M2300/0085

  Immobilising or gelification of electrolyte · CPC title

• H01M4/139

  Processes of manufacture · CPC title