Surface-stabilized and prelithiated anode active materials for lithium batteries and production method

1. A prelithiated and surface-stabilized anode active material for use in a lithium battery, comprising a protected anode active material particle comprising a surface-stabilizing layer embracing a core particle, wherein said surface-stabilizing layer comprises a lithium- or sodium-containing species chemically bonded to said core particle and said lithium- or sodium-containing species is selected from Li 2 CO 3 , Li 2 C 2 O 4 , LiOH, LiCl, LiI, LiBr, ROCO 2 Li, HCOLi, ROLi, (ROCO 2 Li) 2 , (CH 2 OCO 2 Li) 2 , Li 2 S, Li x SO y , Li 4 B, Na 4 B, Na 2 CO 3 , Na 2 O, Na 2 C 2 O 4 , NaOH, NaX, ROCO 2 Na, HCONa, RONa, (ROCO 2 Na) 2 , (CH 2 OCO 2 Na) 2 , Na 2 S, Na x SO y , a combination thereof, a combination thereof with Li 2 O or LiF, or a combination of Li 2 O and LiF, wherein X=F, Cl, I, or Br, R=a hydrocarbon group, 0<x≤1, 1≤y≤4; and wherein said core particle is prelithiated to contain an amount of lithium from 1% to 100% of a maximum lithium content contained in said core particle of anode active material.

2. The prelithiated and surface-stabilized anode active material of claim 1 , wherein said core particle is selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide, ZnCo 2 O 4 ; (f) particles of graphite and carbon; and (g) combinations thereof.

3. The prelithiated and surface-stabilized anode active material of claim 1 , wherein said core particle is in a form of nano particle, nanowire, nanofiber, nanotube, nanosheet, nanobelt, nanoribbon, nanodisc, nanoplatelet, or nanohorn having a thickness or diameter from 0.5 nm to 100 nm.

4. The prelithiated and surface-stabilized anode active material of claim 1 , wherein said core particle contains a sub-micron or micron particle having a dimension (diameter or thickness) from 100 nm to 30 μm.

5. The prelithiated and surface-stabilized anode active material of claim 1 , wherein said core particle is coated with a layer of carbon, graphene, electron-conducting polymer, ion-conducting polymer, or a combination thereof that is disposed between said core particle and said surface-stabilizing layer.

6. The prelithiated and surface-stabilized anode active material of claim 1 , wherein said protected anode particle further contains a layer of carbon, graphene, electron-conducting polymer, ion-conducting polymer, or a combination thereof that is coated on said surface-stabilizing layer.

7. The prelithiated and surface-stabilized anode active material of claim 1 , wherein said anode active material comprises silicon and said prelithiated core particle is selected from Li x Si, wherein numerical x is from 0.01 to 4.4.

8. A mass of anode active material powder comprising the prelithiated and surface-stabilized anode active material of claim 1 .

9. An anode electrode comprising particles of the prelithiated and surface-stabilized anode active material of claim 1 , an optional conductive additive, and an optional binder.

10. A lithium-ion or lithium metal battery containing the anode electrode of claim 9 , a cathode electrode, and an electrolyte in ionic contact with the anode electrode and the cathode electrode.

11. The surface-stabilized anode active material of claim 1 , wherein said core particle of anode active material comprises a doped semiconductor material selected from Si or Ge doped with n-type and/or p-type dopants.

12. The prelithiated and surface-stabilized anode active material of claim 1 , further comprising a thin layer of a high-elasticity polymer encapsulating said surface stabilized and prelithiated core particles wherein said high-elasticity polymer has a fully recoverable tensile strain from 5% to 700%, a thickness from 0.5 nm to 2 μm, and a lithium ion conductivity from 10 −7 S/cm to 5×10 −2 S/cm at room temperature.

13. A method of producing the prelithiated and surface-stabilized anode active material of claim 1 , said method comprising:

(a) providing a plurality of particles of an anode active material;

(b) prelithiating said particles to form prelithiated particles that each contains an amount of lithium from 1% to 100% of a maximum lithium content contained in said anode active material; and

(c) depositing a surface-stabilizing layer to embrace at least one of said prelithiated particles, wherein said surface-stabilizing layer comprises a lithium- or sodium-containing species chemically bonded to said at least one prelithiated particle and wherein said lithium- or sodium-containing species is selected from Li 2 CO 3 , Li 2 O, Li 2 C 2 O 4 , LiOH, LiX, ROCO 2 Li, HCOLi, ROLi, (ROCO 2 Li) 2 , (CH 2 OCO 2 Li) 2 , Li 2 S, Li x SO y , Li 4 B, Na 4 B, Na 2 CO 3 , Na 2 O, Na 2 C 2 O 4 , NaOH, NaX, ROCO 2 Na, HCONa, RONa, (ROCO 2 Na) 2 , (CH 2 OCO 2 Na) 2 , Na 2 S, Na x SO y , or a combination thereof, wherein X=F, Cl, I, or Br, R=a hydrocarbon group, 0<x≤1, and 1≤y≤4.

14. The method of claim 13 , wherein said step of depositing includes conducting an electrochemical decomposition reaction of electrolyte to form said lithium- or sodium-containing species that chemically bond to a surface of at least one of said prelithiated particles.

15. The method of claim 13 , wherein said particles of anode active material are selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide, ZnCo 2 O 4 ; (f) particles of graphite and carbon; and (g) combinations thereof.

16. The method of claim 13 , wherein said step of prelithiating includes electrochemical prelithiation, chemical prelithiation, physical prelithiation, or a combination thereof.

17. The method of claim 13 , wherein said anode active material comprises silicon and said prelithiated particles comprise a prelithiated silicon Li 4 Si, Li 4.4 Si, or Li x Si, wherein numerical x is from 1 to 4.4.

18. The method of claim 13 , wherein said step of providing particles of an anode active material comprises providing a doped semiconductor material selected from Si or Ge doped with n-type and/or p-type dopants.

19. The method of claim 13 , further comprising a step of coating a surface of said prelithiated particles with a thin layer of carbon, graphene, electron-conducting polymer, or ion-conducting polymer having a thickness from 0.5 nm to 1 μm, prior to step (c).

20. The method of claim 19 , wherein said thin layer of carbon is obtained from pyrolization of a polymer, pitch, or organic precursor or obtained by chemical vapor deposition, physical vapor deposition, or sputtering.

21. The method of claim 13 , wherein said step of prelithiating includes conducting electrochemical prelithiation in a first electrochemical reactor and said step of depositing a surface-stabilizing layer includes conducting said depositing in a second electrochemical reactor, wherein said first electrochemical reactor is the same as the second electrochemical reactor.

22. A method of producing a lithium-ion battery comprising (A) preparing an anode from the prelithiated and surface-stabilized particles produced by the method of claim 13 ; and (B) combining said anode with a cathode, and an electrolyte to form said battery.

23. A surface-stabilized anode active material for use in a lithium-ion battery, comprising a protected anode active material particle comprising a surface-stabilizing layer embracing a core particle, wherein said surface-stabilizing layer comprises a lithium- or sodium-containing species chemically bonded to said core particle and said lithium- or sodium-containing species is selected from Li 2 CO 3 , Li 2 O, Li 2 C 2 O 4 , LiOH, LiX, ROCO 2 Li, HCOLi, ROLi, (ROCO 2 Li) 2 , (CH 2 OCO 2 Li) 2 , Li 2 S, Li x SO y , Li 4 B, Na 4 B, Na 2 CO 3 , Na 2 O, Na 2 C 2 O 4 , NaOH, NaX, ROCO 2 Na, HCONa, RONa, (ROCO 2 Na) 2 , (CH 2 OCO 2 Na) 2 , Na 2 S, Na x SO y , or a combination thereof, wherein X=F, Cl, I, or Br, R=a hydrocarbon group, 0<x≤1, and 1≤y≤4.

24. The surface-stabilized anode active material of claim 23 , wherein said core particle is selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide, ZnCo 2 O 4 ; (f) particles of graphite and carbon; and (g) combinations thereof.

25. The surface-stabilized anode active material of claim 23 , wherein said core particle is in a form of nano particle, nanowire, nanofiber, nanotube, nanosheet, nanobelt, nanoribbon, nanodisc, nanoplatelet, or nanohorn having a thickness or diameter from 0.5 nm to 100 nm.

26. The surface-stabilized anode active material of claim 23 , wherein said core particle contains a sub-micron or micron particle having a dimension from 100 nm to 30 μm.

27. The surface-stabilized anode active material of claim 23 , wherein said core particle is coated with a layer of carbon, graphene, electron-conducting polymer, ion-conducting polymer, or a combination thereof that is disposed between said core particle and said surface-stabilizing layer.

28. The surface-stabilized anode active material of claim 23 , wherein said protected anode particle further contains a layer of carbon, graphene, electron-conducting polymer, ion-conducting polymer, or a combination thereof that is coated on said surface-stabilizing layer.

29. A mass of anode active material powder comprising the surface-stabilized anode active material of claim 23 .

30. An anode electrode comprising particles of the surface-stabilized anode active material of claim 23 , an optional conductive additive, and an optional binder.

31. A lithium-ion or lithium metal battery containing the anode electrode of claim 30 , a cathode electrode, and an electrolyte in ionic contact with the anode electrode and the cathode electrode.

32. The surface-stabilized anode active material of claim 23 , further comprising a thin layer of a high-elasticity polymer encapsulating said surface stabilized core particles wherein said high-elasticity polymer has a fully recoverable tensile strain from 5% to 700%, a thickness from 0.5 nm to 2 μm, and a lithium ion conductivity from 10 −7 S/cm to 5×10 −2 S/cm at room temperature.

33. A method of producing the surface-stabilized anode active material of claim 23 , said method comprising:

(a) providing a plurality of particles of an anode active material; and

(b) depositing a surface-stabilizing layer to embrace at least one of said particles, wherein said surface-stabilizing layer comprises a lithium- or sodium-containing species chemically bonded to said at least one particle and wherein said lithium- or sodium-containing species is selected from Li 2 CO 3 , Li 2 O, Li 2 C 2 O 4 , LiOH, LiX, ROCO 2 Li, HCOLi, ROLi, (ROCO 2 Li) 2 , (CH 2 OCO 2 Li) 2 , Li 2 S, Li x SO y , Li 4 B, Na 4 B, Na 2 CO 3 , Na 2 O, Na 2 C 2 O 4 , NaOH, NaX, ROCO 2 Na, HCONa, RONa, (ROCO 2 Na) 2 , (CH 2 OCO 2 Na) 2 , Na 2 S, Na x SO y , or a combination thereof, wherein X=F, Cl, I, or Br, R=a hydrocarbon group, 0<x≤1, and 1≤y≤4.

34. The method of claim 33 , wherein said step of depositing includes conducting an electrochemical decomposition reaction of electrolyte to form said lithium- or sodium-containing species that chemically bond to a surface of at least one of said particles.

35. The method of claim 33 , wherein said particles of anode active material are selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide, ZnCo 2 O 4 ; (f) particles of graphite and carbon; and (g) combinations thereof.

36. The method of claim 33 , further comprising a step of coating a surface of said particles with a thin layer of carbon, graphene, electron-conducting polymer, or ion-conducting polymer having a thickness from 0.5 nm to 1 μm prior to step (c).

37. The method of claim 36 , wherein said thin layer of carbon is obtained from pyrolization of a polymer, pitch, or organic precursor or obtained by chemical vapor deposition, physical vapor deposition, or sputtering.

38. A method of producing a lithium-ion battery comprising (A) preparing an anode from the surface-stabilized particles produced by the method of claim 33 ; and (B) combining said anode with a cathode, and an electrolyte to form said battery.

39. A prelithiated and surface-stabilized anode active material for use in a lithium battery, comprising a protected anode active material particle comprising a surface-stabilizing layer embracing a core particle, wherein said surface-stabilizing layer comprises a lithium- or sodium-containing species chemically bonded to said core particle and said lithium- or sodium-containing species is selected from Li 2 CO 3 , Li 2 C 2 O 4 , LiOH, LiX, Li 2 O, ROCO 2 Li, HCOLi, ROLi, (ROCO 2 Li) 2 , (CH 2 OCO 2 Li) 2 , Li 2 S, Li x SO y , Li 4 B, Na 4 B, Na 2 CO 3 , Na 2 O, Na 2 C 2 O 4 , NaOH, NaX, ROCO 2 Na, HCONa, RONa, (ROCO 2 Na) 2 , (CH 2 OCO 2 Na) 2 , Na 2 S, Na x SO y , or a combination thereof, wherein X=F, Cl, I, or Br, R=a hydrocarbon group, 0<x≤1, 1≤y≤4; and wherein said core particle is prelithiated to contain an amount of lithium from 1% to 100% of a maximum lithium content contained in said core particle of anode active material and said core particle is selected from the group consisting of: (a) germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide, ZnCo 2 O 4 ; (f) particles of graphite and carbon; (g) combinations thereof; and (h) combinations thereof with Si.