Alkali metal-sulfur secondary battery containing a hybrid anode

1. A rechargeable alkali metal-sulfur cell selected from lithium-sulfur cell, sodium-sulfur cell, or potassium-sulfur cell, said alkali metal-sulfur cell comprising:

(A) an anode comprising (i) an anode active material layer composed of fine particles of a first anode active material having an average particle size from 1 nm to 10 μm, an optional conductive additive, and an optional binder that bonds said fine particles and said conductive additive together to form said anode active material layer of structural integrity and, prior to assembly of said cell, (ii) a layer of an alkali metal or alkali metal alloy having greater than 50% by weight of lithium, sodium, or potassium therein, wherein said layer of alkali metal or alkali metal alloy is in physical contact with said anode active material layer and provides from 1% to 120% of a required alkali metal storage capacity of said anode;

(B) a cathode comprising a cathode active material layer and an optional cathode current collector supporting said cathode active material layer, wherein said cathode active material layer contains a sulfur-containing material selected from a sulfur-carbon hybrid, sulfur-graphite hybrid, sulfur-graphene hybrid, conducting polymer-sulfur hybrid, metal sulfide, a sulfur compound, elemental sulfur, or a combination thereof; and

(C) an electrolyte in ionic contact with said anode active material layer and said cathode active material layer and an optional porous separator layer electronically isolating the anode from the cathode;

wherein lithium, sodium, or potassium ions or atoms from said alkali metal or alkali metal alloy diffuse into said first anode active material particles to form lithiated, sodiated, or potassiated anode particles after said battery is assembled and said anode is brought into contact with said electrolyte.

2. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said sulfur-carbon hybrid, sulfur-graphite hybrid, sulfur-graphene hybrid, or conducting polymer-sulfur hybrid is a mixture, blend, composite, chemically or physically bonded entity of sulfur or sulfide with a carbon, graphite, graphene, or conducting polymer material.

3. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said anode active material layer or the layer of alkali metal or alkali metal alloy further contains an amount of electrolyte.

4. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said first anode active material particles have an average particle size from 1 nm to 1 μm.

5. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said first anode active material particles have an average particle size from 1 nm to 100 nm.

6. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said first anode active material is selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), 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, or Cd, and their mixtures or composites; and (d) combinations thereof.

7. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said lithiated anode particles comprise a lithiated silicon represented by a chemical formula of Li 4 Si, Li 4.4 Si, or Li x Si, wherein 0.02≤x≤4.4.

8. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said metal sulfide contains M x S y , wherein x is an integer from 1 to 3 and y is an integer from 1 to 10, and M is a metal element selected from an alkali metal, an alkaline metal selected from Mg or Ca, a transition metal, a metal from groups 13 to 17 of the periodic table, or a combination thereof.

9. The rechargeable alkali metal-sulfur cell of claim 8 , wherein said metal element M is selected from Li, Na, K, Mg, Zn, Cu, Ti, Ni, Co, Fe, or Al.

10. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said metal sulfide contains Li 2 S 1 , Li 2 S 2 , Li 2 S 3 , Li 2 S 4 , Li 2 S 5 , Li 2 S 6 , Li 2 S 7 , Li 2 S 8 , Li 2 S 9 , Li 2 S 10 , Na 2 S 1 , Na 2 S 2 , Na 2 S 3 , Na 2 S 4 , Na 2 S 5 , Na 2 S 6 , Na 2 S 7 , Na 2 S 8 , Na 2 S 9 , Na 2 S 10 , K 2 S 1 , K 2 S 2 , K 2 S 3 , K 2 S 4 , K 2 S 5 , K 2 S 6 , K 2 S 7 , K 2 S 8 , K 2 S 9 , or K 2 S 10 .

11. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said carbon or graphite material in said cathode active material layer is selected from meso-phase pitch, meso-phase carbon, meso carbon micro-bead (MCMB), coke particle, expanded graphite flake, artificial graphite particle, natural graphite particle, highly oriented pyrolytic graphite, soft carbon particle, hard carbon particle, carbon nanotube, carbon nanofiber, carbon fiber, graphite nanofiber, graphite fiber, carbonized polymer fiber, activated carbon, carbon black, or a combination thereof.

12. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said graphene is selected from pristine graphene, graphene oxide, reduced graphene oxide (RGO), graphene fluoride, nitrogenated graphene, hydrogenated graphene, doped graphene, functionalized graphene, or a combination thereof.

13. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said conducting polymer-sulfur hybrid contains an intrinsically conductive polymer selected from polyaniline, polypyrrole, polythiophene, polyfuran, a bi-cyclic polymer, a sulfonated derivative thereof, or a combination thereof.

14. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said anode active material layer contains a binder that is porous having a porosity level from 1% to 90%.

15. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said anode active material layer is porous having a porosity level from 1% to 50%.

16. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said cathode active material layer contains a binder that is an elastomer having a recoverable tensile elastic deformation from 2% to 700%.

17. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said anode further comprises an amorphous carbon or polymeric carbon that forms a coating on a surface of said fine particles or forms a matrix in which said fine particles are dispersed.

18. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said anode further comprises a protective material that forms a coating on a surface of said fine particles or forms a matrix in which said fine particles are dispersed.

19. The rechargeable alkali metal-sulfur cell of claim 18 , wherein said protective material is selected from graphene, an electron-conducting polymer, an ion-conducting polymer, a carbon coating, or a combination thereof.

20. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said anode further comprises a second anode active material selected from particles of graphite, hard carbon, soft carbon, meso-carbon micro-bead, surface-modified graphite, carbon-coated graphite, or a combination thereof.

21. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said electrolyte is selected from polymer electrolyte, polymer gel electrolyte, composite electrolyte, ionic liquid electrolyte, non-aqueous liquid electrolyte, soft matter phase electrolyte, solid-state electrolyte, or a combination thereof.

22. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said electrolyte contains a salt 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(CF 3 SO 2 ) 2 , Lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 O 4 ), lithium oxalyldifluoroborate (LiBF 2 C 2 O 4 ), Lithium nitrate (LiNO 3 ), Li-Fluoroalkyl-Phosphates (LiPF3(CF 2 CF 3 ) 3 ), lithium bisperfluoroethysulfonylimide (LiBETI), an ionic liquid salt, sodium perchlorate (NaClO 4 ), potassium perchlorate (KClO 4 ), sodium hexafluorophosphate (NaPF 6 ), potassium hexafluorophosphate (KPF 6 ), sodium borofluoride (NaBF 4 ), potassium borofluoride (KBF 4 ), sodium hexafluoroarsenide, potassium hexafluoroarsenide, sodium trifluoro-metasulfonate (NaCF 3 SO 3 ), potassium trifluoro-metasulfonate (KCF 3 SO 3 ), bis-trifluoromethyl sulfonylimide sodium (NaN(CF 3 SO 2 ) 2 ), sodium trifluoromethanesulfonimide (NaTFSI), bis-trifluoromethyl sulfonylimide potassium (KN(CF 3 SO 2 ) 2 ), or a combination thereof.

23. The rechargeable alkali metal-sulfur cell of claim 1 , wherein said electrolyte contains a solvent 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.

24. A rechargeable alkali metal-sulfur cell selected from lithium-sulfur cell, sodium-sulfur cell, or potassium-sulfur cell, said alkali metal-sulfur cell comprising:

(A) an anode comprising (i) an anode active material layer composed of fine particles of a first anode active material having an average particle size from 1 nm to 10 μm, an optional conductive additive, and an optional binder that bonds said fine particles and said conductive additive together to form said anode active material layer of structural integrity and, prior to assembly of said cell, (ii) a layer of an alkali metal or alkali metal alloy having greater than 50% by weight of lithium, sodium, or potassium therein, wherein said layer of alkali metal or alkali metal alloy is in physical contact with said anode active material layer and provides from 1% to 120% of a required alkali metal storage capacity of said anode;

(B) a cathode comprising a cathode active material layer and an optional cathode current collector supporting said cathode active material layer, wherein said cathode active material layer contains a sulfur-containing material selected from a sulfur-carbon hybrid, sulfur-graphite hybrid, sulfur-graphene hybrid, conducting polymer-sulfur hybrid, metal sulfide, a sulfur compound, elemental sulfur, or a combination thereof; and

(C) an electrolyte in ionic contact with said anode active material layer and said cathode active material layer and an optional porous separator layer electronically isolating the anode from the cathode;

wherein said metal sulfide contains M x S y , wherein x is an integer from 1 to 3 and y is an integer from 1 to 10, and M is a metal element selected from an alkali metal, an alkaline metal selected from Mg or Ca, a transition metal, a metal from groups 13 to 17 of the periodic table, or a combination thereof.

25. The rechargeable alkali metal-sulfur cell of claim 24 , wherein said anode active material layer contains a binder that is porous having a porosity level from 1% to 90%.

26. The rechargeable alkali metal-sulfur cell of claim 24 , wherein said anode active material layer is porous having a porosity level from 1% to 50%.

27. The rechargeable alkali metal-sulfur cell of claim 24 , wherein said cathode active material layer contains a binder that is an elastomer having a recoverable tensile elastic deformation from 2% to 700%.

28. The rechargeable alkali metal-sulfur cell of claim 24 , wherein said anode further comprises an amorphous carbon or polymeric carbon that forms a coating on a surface of said fine particles or forms a matrix in which said fine particles are dispersed.

29. The rechargeable alkali metal-sulfur cell of claim 24 , wherein said anode further comprises a protective material that forms a coating on a surface of said fine particles or forms a matrix in which said fine particles are dispersed.

30. The rechargeable alkali metal-sulfur cell of claim 24 , wherein said anode further comprises a second anode active material selected from particles of graphite, hard carbon, soft carbon, meso-carbon micro-bead, surface-modified graphite, carbon-coated graphite, or a combination thereof.

31. The rechargeable alkali metal-sulfur cell of claim 24 , wherein said anode active material layer contains an anode active material selected from lithium metal, sodium metal, potassium metal, a lithium metal alloy, sodium metal alloy, potassium metal alloy, a lithium intercalation compound, a sodium intercalation compound, a potassium intercalation compound, a lithiated compound, a sodiated compound, a potassium-doped compound, lithiated titanium dioxide, lithium titanate, lithium manganate, a lithium transition metal oxide, Li 4 Ti 5 O 12 , or a combination thereof.

32. A rechargeable alkali metal-sulfur cell selected from lithium-sulfur cell, sodium-sulfur cell, or potassium-sulfur cell, said alkali metal-sulfur cell comprising:

(D) an anode comprising (i) an anode active material layer composed of fine particles of a first anode active material having an average particle size from 1 nm to 10 μm, an optional conductive additive, and an optional binder that bonds said fine particles and said conductive additive together to form said anode active material layer of structural integrity and, prior to assembly of said cell, (ii) a layer of an alkali metal or alkali metal alloy having greater than 50% by weight of lithium, sodium, or potassium therein, wherein said layer of alkali metal or alkali metal alloy is in physical contact with said anode active material layer and provides from 1% to 120% of a required alkali metal storage capacity of said anode;

(E) a cathode comprising a cathode active material layer and an optional cathode current collector supporting said cathode active material layer, wherein said cathode active material layer contains a sulfur-containing material selected from a sulfur-carbon hybrid, sulfur-graphite hybrid, sulfur-graphene hybrid, conducting polymer-sulfur hybrid, metal sulfide, a sulfur compound, elemental sulfur, or a combination thereof; and

(F) an electrolyte in ionic contact with said anode active material layer and said cathode active material layer and an optional porous separator layer electronically isolating the anode from the cathode;

wherein said cathode active material layer contains a binder that is an elastomer having a recoverable tensile elastic deformation from 2% to 700%.

33. The rechargeable alkali metal-sulfur cell of claim 32 , wherein lithium, sodium, or potassium ions or atoms from said alkali metal alkali metal alloy diffuse into said first anode active material particles to form lithiated, sodiated, or potassiated anode particles after said battery is assembled and said anode is brought into contact with said electrolyte.

34. The rechargeable alkali metal-sulfur cell of claim 32 , wherein said anode active material layer contains a binder that is porous having a porosity level from 1% to 90%.

35. The rechargeable alkali metal-sulfur cell of claim 32 , wherein said anode active material layer is porous having a porosity level from 1% to 50%.

36. The rechargeable alkali metal-sulfur cell of claim 32 , wherein said anode further comprises an amorphous carbon or polymeric carbon that forms a coating on a surface of said fine particles or forms a matrix in which said fine particles are dispersed.

37. The rechargeable alkali metal-sulfur cell of claim 32 , wherein said anode further comprises a protective material that forms a coating on a surface of said fine particles or forms a matrix in which said fine particles are dispersed.

38. The rechargeable alkali metal-sulfur cell of claim 32 , wherein said anode further comprises a second anode active material selected from particles of graphite, hard carbon, soft carbon, meso-carbon micro-bead, surface-modified graphite, carbon-coated graphite, or a combination thereof.

39. The rechargeable alkali metal-sulfur cell of claim 32 , wherein said anode active material layer contains an anode active material selected from lithium metal, sodium metal, potassium metal, a lithium metal alloy, sodium metal alloy, potassium metal alloy, a lithium intercalation compound, a sodium intercalation compound, a potassium intercalation compound, a lithiated compound, a sodiated compound, a potassium-doped compound, lithiated titanium dioxide, lithium titanate, lithium manganate, a lithium transition metal oxide, Li 4 Ti 5 O 12 , or a combination thereof.