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

Patent metadata

Field	Value
Publication number	US-10950897-B2
Application number	US-201916653077-A
Country	US
Kind code	B2
Filing date	Oct 15, 2019
Priority date	Jun 30, 2017
Publication date	Mar 16, 2021
Grant date	Mar 16, 2021

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. An alkali metal-sulfur cell having a quasi-solid electrode, said cell comprising:
(a) a quasi-solid cathode containing deformable and electrically conductive cathode material comprising a combination of a quantity of a cathode active material, a quantity of an electrolyte, and a conductive additive, 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, contains 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, wherein said quasi-solid cathode contains said 3D network of electron-conducting pathways such that the cathode maintains an electrical conductivity no less than 10 −6 S/cm; and
(b) an anode.

2. The cell 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 cell of claim 1 , wherein said quasi-solid cathode has a thickness no less than 200 μM.

4. The cell 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.

5. The cell of claim 1 , wherein said quasi-solid cathode has an electrical conductivity from 10 −3 S/cm to 10 S/cm.

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

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

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

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

10. The cell of claim 1 , wherein said cell has a gravimetric energy density greater than 200 Wh/kg.

11. The cell of claim 1 , wherein said anode contains a deformable and electrically conductive material which includes a quantity of an anode active material, a quantity of an electrolyte, and a conductive additive, 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, wherein said 3D network of electron-conducting pathways is uninterrupted such that the anode maintains an electrical conductivity no less than 10 −6 S/cm.

12. The cell of claim 1 , wherein the solvent for said electrolyte is selected from water, an organic solvent, an ionic liquid, or a mixture of an organic solvent and an ionic liquid.

13. The cell 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.

14. The cell of claim 13 , 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.

15. The cell of claim 1 , wherein said alkali metal-sulfur cell is a sodium-ion sulfur cell, and said anode contains an anode active material containing an alkali intercalation compound selected from petroleum coke, carbon black, amorphous carbon, activated carbon, hard carbon, soft carbon, templated carbon, hollow carbon nanowires, hollow carbon sphere, titanates, NaTi 2 (PO 4 ) 3 , Na 2 Ti 3 O 7 , Na 2 C 8 H 4 O 4 , Na 2 TP, Na x TiO 2 (x=0.2 to 1.0), Na 2 C 8 H 4 O 4 , carboxylate based materials, C 8 H 4 Na 2 O 4 , C 8 H 6 O 4 , C 8 H 5 NaO 4 , C 8 Na 2 F 4 O 4 , C 10 H 2 Na 4 O 8 , C 14 H 4 O 6 , C 14 H 4 Na 4 O 8 , or a combination thereof.

16. The cell of claim 1 , wherein said alkali metal-sulfur cell is a sodium-ion sulfur cell, and said active material is an anode active material selected from the group consisting of:
a) particles of sodium metal or a sodium 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) sodium-doped silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), cobalt (Co), nickel (Ni), manganese (Mn), cadmium (Cd), and mixtures thereof;
d) sodium-containing alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and their mixtures;
e) sodium-containing oxides, carbides, nitrides, sulfides, phosphides, selenides, tellurides, or antimonides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd, and mixtures or composites thereof;
f) sodium salts;
g) graphene sheets pre-loaded with sodium ions; and combinations thereof.

17. The cell of claim 1 , wherein said anode is a quasi-solid polymer-free anode which has a thickness no less than 200 μm.

18. The cell of claim 1 , wherein said cathode active material constitutes an electrode active material mass loading greater than 25 mg/cm 2 .

19. The cell of claim 1 , wherein said cathode active material constitutes an electrode active material mass loading greater than 45 mg/cm 2 .

20. An alkali metal-sulfur cell having a quasi-solid electrode, said cell comprising:
(a) a deformable and electrically conductive cathode material comprising a combination of a quantity of a cathode active material, a quantity of a quasi-solid electrolyte, and a conductive additive, 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

Assignees

• Global Graphene Group Inc

Inventors

• Zhamu Aruna
• Jang Bor Z

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• 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

• H01M4/0402

  Methods of deposition of the material · CPC title

• H01G11/40

  Fibres · CPC title