Lithium-sulfur secondary battery containing gradient electrolyte
View Patent ↗A rechargeable lithium-sulfur cell comprising a cathode, an anode, a separator electronically separating the two electrodes, a first electrolyte in contact with the cathode, and a second electrolyte in contact with the anode, wherein the first electrolyte contains a first concentration, C 1 , of a first lithium salt dissolved in a first solvent when the first electrolyte is brought in contact with the cathode, and the second electrolyte contains a second concentration, C 2 , of a second lithium salt dissolved in a second solvent when the second electrolyte is brought in contact with the anode, wherein C 1 is less than C 2 . The cell exhibits an exceptionally high specific energy and a long cycle life.
1. A rechargeable lithium-sulfur cell comprising a cathode having a sulfur-containing cathode active material, an anode having an anode active material, a separator electronically separating said anode and said cathode, a first electrolyte in contact with said cathode active material, and a second electrolyte in contact with said anode active material, wherein said first electrolyte contains a first concentration, C 1 , of a first lithium salt dissolved in a first liquid solvent, and said second electrolyte contains a second concentration, C 2 , of a second lithium salt dissolved in a second liquid solvent wherein said second concentration C 2 is greater than said first concentration C 1 by a factor of 2 or more, and said second concentration, C 2 , is no less than 4 molar (mole/L), wherein an amount of said second electrolyte is greater than an amount of said first electrolyte, wherein said first electrolyte is not in contact with said anode and said second electrolyte is not in contact with said cathode, wherein said first electrolyte is not mixed with said second electrolyte, and wherein said first electrolyte and said second electrolyte are selected from a polymer gel electrolyte, ionic liquid electrolyte, non-aqueous liquid electrolyte, or a combination thereof, and wherein said first lithium salt and said second lithium salt are selected from lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro-metasulfonate (LiCF 3 SO 3 ), bis-trifluoromethyl sulfonylimide lithium (LiN(CF3SO 2 ) 2 , lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 O 4 ), lithium nitrate (LiNO 3 ), Li-fluoroalkyl-phosphates (LiPF 3 (CF 2 CF 3 ) 3 ), lithium bisperfluoroethysulfonylimide (LiBETI), an ionic liquid salt, and combinations thereof.
2. The rechargeable lithium-sulfur cell of claim 1 wherein said first liquid solvent and said second liquid solvent have the same composition and/or said first lithium salt and said second lithium salt have the same composition.
3. The rechargeable lithium-sulfur cell of claim 1 wherein said second concentration, C 2 , is no less than 5 molar (mole/L).
4. The rechargeable lithium-sulfur cell of claim 1 wherein said second concentration, C 2 , is greater than 7 molar (mole/L).
5. The rechargeable lithium-sulfur cell of claim 1 wherein said first concentration, C 1 , is less than 2 molar (mole/L).
6. The rechargeable lithium-sulfur cell of claim 1 wherein said first concentration, C 1 , is no greater than 1 molar (mole/L).
7. The rechargeable lithium-sulfur cell of claim 1 wherein said first liquid solvent or said second liquid solvent is selected from ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), gamma.-butyrolactone (γ-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene or methyl acetate (MA), fluoroethylene carbonate (FEC), vinylene carbonate (VC), allyl ethyl carbonate (AEC), 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethylether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), sulfone, sulfolane, room temperature ionic liquid, or a combination thereof, wherein said room temperature ionic liquid is an ionic salt having a melting point no greater than 25° C.
8. The rechargeable lithium-sulfur cell of claim 1 wherein said first electrolyte or second electrolyte contains an ionic liquid.
9. The rechargeable lithium-sulfur cell of claim 1 , further comprising a layer of protective material disposed between said anode and said second electrolyte wherein said protective material is a lithium ion conductor.
10. The rechargeable lithium-sulfur cell of claim 9 , wherein said protective material consists of a solid electrolyte.
11. The rechargeable lithium-sulfur cell of claim 1 wherein said anode contains an anode active material selected from lithium metal, a lithium metal alloy, a mixture of lithium metal or lithium alloy with a lithium intercalation compound, a lithiated compound, lithiated titanium dioxide, lithium titanate, lithium manganate, a lithium transition metal oxide, Li 4 Ti 5 O 12 , or a combination thereof.
12. 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);
(b) 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;
(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;
(d) salts and hydroxides of Sn;
(e) carbon or graphite materials; and
combinations thereof.
13. The rechargeable lithium-sulfur cell of claim 1 wherein said first electrolyte is mixed with a cathode active material before or during the cell is made.
14. The rechargeable lithium-sulfur cell of claim 1 wherein said cathode comprises:
a) an integrated nano-structure of electrically conductive nanometer-scaled filaments that are interconnected to form a porous network of electron-conducting paths comprising pores with a size smaller than 100 nm, wherein said filaments have a transverse dimension less than 500 nm; and
b) powder or coating of sulfur, lithium-containing sulfide or lithium polysulfide disposed in said pores or deposited on a nano-scaled filament surface, wherein said sulfur, lithium-containing sulfide, or polysulfide is in contact with said first electrolyte, or dispersed or dissolved in said first solvent, and the sulfur- or sulfide-to-filament weight ratio is between 1/10 and 10/1 which is measured when said cell is in a fully discharged state.
15. The rechargeable lithium-sulfur cell of claim 14 wherein said filaments comprise an electrically conductive material selected from the group consisting of electro-spun nanofibers, vapor-grown carbon or graphite nanofibers, carbon or graphite whiskers, carbon nanotubes, carbon nanowires, nano graphene sheets or platelets, metal nanowires, metal-coated nanowires or nanofibers, conductive polymer-coated nanowires or nanofibers, and combinations thereof.
16. The rechargeable lithium-sulfur cell of claim 14 wherein said filaments comprise a fiber selected from the group consisting of an electrically conductive electro-spun polymer fiber, electro-spun polymer nanocomposite fiber comprising a conductive filler, nano carbon fiber obtained from carbonization of an electro-spun polymer fiber, electro-spun pitch fiber, and combinations thereof.
17. The rechargeable lithium-sulfur cell of claim 14 wherein said filaments comprise nano graphene sheets or platelets with a thickness less than 10 nm.
18. The rechargeable lithium-sulfur cell of claim 14 wherein said filaments comprise nano graphene sheets or platelets selected from single-layer or few-layer pristine graphene, reduced graphene oxide, graphene oxide, hydrogenated graphene, nitrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof, wherein few-layer is defined as 10 planes of hexagonal carbon atoms or less.
19. The rechargeable lithium-sulfur cell of claim 14 wherein said nano-filaments 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.
20. The rechargeable lithium-sulfur cell of claim 1 , wherein said anode contains a nano-structure comprising an integrated 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-structured anode provides nano-filament surface areas to support lithium metal when the cell is in a charged state.
21. A rechargeable lithium-sulfur cell comprising a cathode having a sulfur-containing cathode active material, an anode having an anode active material, a separator electronically separating said anode and said cathode, a first electrolyte in contact with said cathode active material, and a second electrolyte in contact with said anode active material, wherein said first electrolyte contains a first concentration, C 1 , of a first lithium salt dissolved in a first liquid solvent, and said second electrolyte contains a second concentration, C 2 , of a second lithium salt dissolved in a second liquid solvent and said first concentration and said second concentration are measured before said second electrolyte is brought in contact with said first electrolyte, wherein C 1 is less than C 2 , wherein said cathode comprises a porous composite active material consisting 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; 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 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 which is measured or calculated when said cell is in a fully charged state.
22. The rechargeable lithium-sulfur cell of claim 21 wherein said nano-scaled powder or coating has a diameter or thickness less than 10 nm.
23. The rechargeable lithium-sulfur cell of claim 21 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.
24. The rechargeable lithium-sulfur cell of claim 21 wherein the amount of the powder or coating of sulfur, sulfur compound, or lithium polysulfide is no less than 80% by weight.
25. The rechargeable lithium-sulfur cell of claim 21 wherein said exfoliated graphite worms have a graphite flake thickness less than 3 nm.
26. The rechargeable lithium-sulfur cell of claim 21 wherein said exfoliated graphite worms contain flakes that are single graphene planes.
27. The rechargeable lithium-sulfur cell of claim 21 wherein said conductive graphite flake network has a specific surface area greater than 500 m 2 /g.
28. The rechargeable lithium-sulfur cell of claim 1 wherein said cathode has an active material utilization rate no less than 90%.
29. The rechargeable lithium-sulfur cell as defined in claim 14 , wherein said cell is at a discharged state when said cell is made.
30. 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 in a charged state.