Rechargeable lithium-sulfur battery having a high capacity and long cycle life
View Patent ↗A rechargeable lithium-sulfur cell comprising an anode, a separator and/or electrolyte, and a sulfur cathode, wherein the cathode comprises (a) exfoliated graphite worms that are interconnected to form a porous, conductive graphite flake network comprising pores having a size smaller than 100 nm; and (b) nano-scaled powder or coating of sulfur, sulfur compound, or lithium polysulfide disposed in the pores or coated on graphite flake surfaces wherein the powder or coating has a dimension less than 100 nm. The exfoliated graphite worm amount is in the range of 1% to 90% by weight and the amount of powder or coating is in the range of 99% to 10% by weight based on the total weight of exfoliated graphite worms and sulfur (sulfur compound or lithium polysulfide) combined. The cell exhibits an exceptionally high specific energy and a long cycle life.
1. A rechargeable lithium-sulfur cell comprising an anode, a separator and/or electrolyte, and a porous composite sulfur cathode, wherein said porous composite cathode consists of:
a) exfoliated graphite worms that are interconnected to form a porous, conductive graphite flake network comprising pores having a size smaller than 100 nm, wherein said exfoliated graphite worm is a network of interconnected exfoliated graphite flakes with pores between said exfoliated graphite flakes: and
b) nano-scaled powder or coating of sulfur, sulfur compound, or lithium polysulfide disposed in said pores or coated on a graphite flake surface wherein said powder or coating is in contact with said electrolyte and has a dimension less than 100 nm;
wherein the porous composite cathode has a pore size from 2 nm to 50 nm and the exfoliated graphite worm amount is in a range of 1% to 90 % by weight and an amount of powder or coating is in a range of 99% to 10% by weight based on a total weight of exfoliated graphite worms and sulfur, sulfur compound, or lithium polysulfide combined which is measured or calculated when said cell is in a fully charged state.
2. The rechargeable lithium-sulfur cell of claim 1 wherein said nano-scaled powder or coating has a diameter or thickness less than 20 nm.
3. The rechargeable lithium-sulfur cell of claim 1 wherein said nano-scaled powder or coating has a diameter or thickness less than 10 nm.
4. The rechargeable lithium-sulfur cell of claim 1 wherein said pores have a size from 2 nm to 10 nm to accommodate electrolyte therein after said nano-scaled powder or coating of sulfur, sulfur compound, or lithium polysulfide is disposed in said pores or coated on said graphite flake surface.
5. The rechargeable lithium-sulfur cell of claim 1 wherein the amount of the powder or coating of sulfur, sulfur compound, or lithium polysulfide is in the range of 70% to 95% by weight.
6. The rechargeable lithium-sulfur cell of claim 1 wherein the amount of the powder or coating of sulfur, sulfur compound, or lithium polysulfide is no less than 80% by weight.
7. The rechargeable lithium-sulfur cell of claim 1 wherein said exfoliated graphite worms have a graphite flake thickness less than 10 nm.
8. The rechargeable lithium-sulfur cell of claim 1 wherein said exfoliated graphite worms have a graphite flake thickness less than 3 nm.
9. The rechargeable lithium-sulfur cell of claim 1 wherein said exfoliated graphite worms contain flakes that are single graphene planes.
10. The rechargeable lithium-sulfur cell of claim 1 wherein said conductive graphite flake network has a specific surface area greater than 300 m 2 /g.
11. The rechargeable lithium-sulfur cell of claim 1 wherein said conductive graphite flake network has a specific surface area greater than 500 m 2 /g.
12. The rechargeable lithium-sulfur cell of claim 1 wherein said cathode has an active material utilization rate no less than 80%.
13. The rechargeable lithium-sulfur cell of claim 1 wherein said cathode has an active material utilization rate no less than 90%.
14. The rechargeable lithium-sulfur cell of claim 1 wherein said cathode has an active material utilization rate no less than 95%.
15. The rechargeable lithium-sulfur cell of claim 1 wherein said cell is a lithium metal-sulfur cell containing a lithium metal, lithium metal alloy, or lithium compound as an anode active material.
16. The rechargeable lithium-sulfur cell of claim 1 wherein said cell is a lithium ion-sulfur cell and said anode contains an anode active material selected from the group consisting of:
(a) 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), and lithiated versions thereof;
(b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with other elements, and lithiated versions thereof, wherein said alloys or compounds are stoichiometric or non-stoichiometric;
(c) 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, and lithiated versions thereof;
(d) salts and hydroxides of Sn and lithiated versions thereof;
(e) carbon or graphite materials and prelithiated versions thereof; and combinations thereof.
17. The rechargeable lithium-sulfur cell of claim 16 wherein said carbon or graphite materials are selected from the group consisting of natural graphite particles, synthetic graphite particles, needle cokes, electro-spun nano fibers, vapor-grown carbon or graphite nano fibers, carbon or graphite whiskers, carbon nano-tubes, carbon nanowires, sheets and platelets of pristine graphene, graphene oxide, reduced graphene oxide, doped graphene or graphene oxide, and chemically functionalized graphene, and combinations thereof.
18. The rechargeable lithium-sulfur cell of claim 1 wherein said cathode active material contains multiple secondary particles each composed of multiple primary particles of said exfoliated graphite worms and said nano-scaled powder or coating of sulfur, sulfur compound, or lithium polysulfide.
19. The rechargeable lithium-sulfur cell of claim 18 wherein said multiple secondary particles are bonded by a binder material selected from a resin, a conductive polymer, coal tar pitch, petroleum pitch, meso-phase pitch, coke, or a derivative thereof to form said cathode.
20. The rechargeable lithium-sulfur cell of claim 1 , further comprising a cathode current collector selected from aluminum foil, carbon- or graphene-coated aluminum foil, stainless steel foil or web, carbon- or graphene-coated steel foil or web, carbon or graphite paper, carbon or graphite fiber fabric, flexible graphite foil, graphene paper or film, or a combination thereof.
21. The rechargeable lithium-sulfur cell of claim 1 , further comprising an anode current collector selected from copper foil or web, carbon- or graphene-coated copper foil or web, stainless steel foil or web, carbon- or graphene-coated steel foil or web, titanium foil or web, carbon- or graphene-coated titanium foil or web carbon or graphite paper, carbon or graphite fiber fabric, flexible graphite foil, graphene paper or film, or a combination thereof.
22. The rechargeable lithium-sulfur cell of claim 1 wherein said anode contains a nano-structure of electrically conductive nanometer-scaled filaments that are interconnected to form a porous network of electron-conducting paths comprising interconnected pores, wherein said filaments have a transverse dimension less than 500 nm and wherein said nano-structure provides an amount of nano-filament surface areas to support lithium metal when the cell is in a charged state.
23. The rechargeable lithium-sulfur cell as defined in claim 22 , wherein said cell is at a discharged state when said cell is made.
24. The rechargeable lithium-sulfur cell of claim 1 , wherein said cathode comprises sulfur, sulfur-containing molecule, sulfur-containing compound, sulfur-carbon polymer, or a combination thereof when the cell is made or is in a charged state.
25. The rechargeable lithium-sulfur cell of claim 1 , wherein said electrolyte is selected from the group consisting of polymer electrolyte, polymer gel electrolyte, solid-state electrolyte, composite electrolyte, ionic liquid electrolyte, non-aqueous liquid electrolyte, soft matter phase electrolyte, and combinations thereof.
26. The rechargeable lithium-sulfur cell of claim 1 , wherein said electrolyte is selected from the group of solid-state electrolytes consisting of solid ionic conductors based on a LiM 2 (PO 4 ) 3 structure, where M is a metal, lithium aluminum germanium phosphates represented by Li 1−x Al x Ge 2−x PO 4 ) 3 , where x=0.1-0.9, glass-ceramic solid electrolytes, and combinations thereof.
27. The rechargeable lithium-sulfur cell of claim 1 , wherein said cathode provides a reversible specific capacity of no less than 800 mAh per gram based on the total weight of exfoliated graphite worms and sulfur, sulfur compound, or lithium polysulfide combined.
28. The rechargeable lithium-sulfur cell of claim 1 , wherein said cell provides a reversible specific capacity of no less than 1,000 mAh per gram based on the total weight of exfoliated graphite worms and sulfur, sulfur compound, or lithium polysulfide combined.
29. The rechargeable lithium-sulfur cell of claim 1 , wherein said cell provides a specific energy of no less than 600 Wh/Kg based on a total cell weight including anode, cathode, electrolyte, separator, and current collector weights combined.
30. The rechargeable lithium-sulfur cell of claim 1 , wherein said cell provides a specific energy of no less than 800 Wh/Kg based on a total cell weight including anode, cathode, electrolyte, separator, and current collector weights combined.
31. A process for producing a rechargeable lithium-sulfur cell of claim 1 , comprising:
a) preparing a mass of exfoliated graphite worms containing graphite flakes having a thickness less than 100 nm that are interconnected to form a porous network of electron-conducting paths;
b) depositing a nano-scaled coating of sulfur or sulfur compound onto a surface of said graphite flakes to obtain a cathode containing a coated graphite worm meso-porous structure, wherein the nano-scaled coating has a thickness less than 100 nm; and
c) combining said cathode with an anode, electrolyte or an electrolyte-separator assembly, an optional anode current collector, and an optional cathode current collector to form said lithium-sulfur cell.
32. The process for producing a rechargeable lithium-sulfur cell of claim 31 , wherein said exfoliated graphite worms are obtained with a controlled-volume exfoliation method.
33. A process for producing a rechargeable lithium-sulfur cell of claim 1 , comprising:
a) preparing a porous structure of exfoliated graphite worms that are interconnected to form a porous network of electron-conducting paths;
b) immersing said porous structure as a first electrode in a lithium polysulfide-containing electrolyte, immersing a lithium metal or lithium-containing conductor as a second electrode in said electrolyte, and imposing a current onto said first and second electrodes to electrochemically produce a lithium polysulfide-coated meso-porous structure for use as a cathode; and
c) Combining said cathode with an anode, electrolyte or an electrolyte-separator assembly, an optional anode current collector, and an optional cathode current collector to form said lithium-sulfur cell.