ELECTROCHEMICALLY STABLE ANODE PARTICULATES FOR LITHIUM SECONDARY BATTERIES AND METHOD OF PRODUCTION
Provided is a lithium battery anode electrode comprising multiple particulates of an anode active material, wherein at least a particulate comprises one or a plurality of particles of said anode active material having a volume Va, an electron-conducting material as a matrix, binder or filler material, and pores having a volume Vp which are encapsulated by a thin encapsulating layer of an electrically conducting material, wherein the thin encapsulating layer has a thickness from 1 nm to 10 μm, an electric conductivity from 10 −6 S/cm to 20,000 S/cm and a lithium ion conductivity from 10 −8 S/cm to 5×10 −2 S/cm and the volume ratio Vp/Va in the particulate is from 0.3/1.0 to 5.0/1.0. If a single primary particle is encapsulated, the single primary particle is itself porous having a free space to expand into without straining the thin encapsulating layer when the lithium battery is charged.
1 . An anode electrode for a lithium battery, said electrode comprising multiple particulates of an anode active material, wherein at least a particulate comprises a core and a thin encapsulating layer encapsulating said core, wherein said core comprises a single or a plurality of primary particles of said anode active material having a volume Va, an electron-conducting material as a matrix, binder or filler material occupying from 0% to 50% by weight of said particulate weight, and pores having a volume Vp, and said thin encapsulating layer comprises an electrically conducting material and has a thickness from 1 nm to 10 μm, an electric conductivity from 10 −6 S/cm to 20,000 S/cm and a lithium ion conductivity from 10 −8 S/cm to 5×10 −2 S/cm and wherein the volume ratio Vp/Va is from 0.5/1.0 to 5.0/1.0 and wherein, if a single primary particle is encapsulated, the single primary particle is itself porous having a free space to expand into without straining said thin encapsulating layer when said battery is charged.
2 . The anode electrode of claim 1 , wherein said thin encapsulating layer of electrically conducting material comprises a carbonaceous or graphitic material.
3 . The anode electrode of claim 1 , wherein said electron-conducting material or said carbonaceous or graphitic material is selected from a carbon nanotube, carbon nanofiber, nanocarbon particle, metal nanoparticle, metal nanowire, electron-conducting polymer, graphene, or a combination thereof, wherein said graphene is selected from pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, nitrogenated graphene, hydrogenated graphene, doped graphene, functionalized graphene, or a combination thereof and said graphene comprise single-layer graphene or few-layer graphene, wherein said few-layer graphene is defined as a graphene platelet formed of less than 10 graphene planes.
4 . The anode electrode of claim 3 , wherein said electron-conducting polymer is selected from polyaniline, polypyrrole, polythiophene, polyfuran, a bi-cyclic polymer, a sulfonated derivative thereof, or a combination thereof.
5 . The anode electrode of claim 2 , wherein said electron-conducting material or said carbonaceous or graphitic material comprises a material selected from polymeric carbon, amorphous carbon, chemical vapor deposition carbon, coal tar pitch, petroleum pitch, mesophase pitch, carbon black, coke, acetylene black, activated carbon, fine expanded graphite particle with a dimension smaller than 100 nm, artificial graphite particle, natural graphite particle, or a combination thereof.
6 . The anode electrode of claim 1 , wherein said thin encapsulating layer further comprises a polymer wherein said first carbonaceous or graphitic material is dispersed in or bonded by said polymer.
7 . The anode electrode of claim 5 , wherein said polymer contains an adhesive resin, a thermoplastic resin, an elastomer or rubber, a copolymer thereof, an interpenetrating network thereof, or a blend thereof.
8 . The anode electrode of claim 1 , wherein said 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), 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; (f) prelithiated versions thereof; (g) particles of Li, Li alloy, or surface-stabilized Li having at least 60% by weight of lithium element therein; and (h) combinations thereof.
9 . The anode electrode of claim 7 , wherein said Li alloy contains from 0.1% to 10% by weight of a metal element selected from Zn, Ag, Au, Mg, Ni, Ti, Fe, Co, V, or a combination.
10 . The anode electrode of claim 1 , wherein said anode active material contains a prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnO x , prelithiated SiO x , prelithiated iron oxide, prelithiated VO 2 , prelithiated Co 3 O 4 , prelithiated Ni 3 O 4 , lithium titanate, or a combination thereof, wherein x=1 to 2.
11 . The anode electrode of claim 1 , wherein said anode active material is in a form of nanoparticle, nanowire, nanofiber, nanotube, nanosheet, nanobelt, nanoribbon, nanodisc, nanoplatelet, or nanohorn having a thickness or diameter from 0.5 nm to 100 nm.
12 . The anode electrode of claim 1 , wherein at least one of said anode active material particles is coated with a layer of carbon or graphene prior to being encapsulated.
13 . The anode electrode of claim 1 , wherein at least one of said particulates further comprises from 0.1% to 40% by weight of a lithium ion-conducting additive dispersed in said thin encapsulating layer or in ionic contact with said anode active material particles encapsulated therein.
14 . The anode electrode of claim 13 , wherein said lithium ion-conducting additive 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 , or a combination thereof, wherein X=F, Cl, I, or Br, R=a hydrocarbon group, 0<x≤1 and 1≤y≤4.
15 . The anode electrode of claim 13 , wherein said lithium ion-conducting additive contains a lithium salt selected from lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro-methanesulfonate (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 nitrate (LiNO 3 ), Li-fluoroalkyl-phosphate (LiPF 3 (CF 2 CF 3 ) 3 ), lithium bisperfluoro-ethylsulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lithium salt, or a combination thereof.
16 . The anode electrode of claim 13 , wherein said lithium ion-conducting additive contains a lithium ion-conducting polymer selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), a sulfonated derivative thereof, or a combination thereof.
17 . The anode electrode of claim 6 , wherein said polymer contains an elastomer or rubber selected from natural polyisoprene, synthetic polyisoprene, polybutadiene, chloroprene rubber, polychloroprene, butyl rubber, styrene-butadiene rubber, nitrile rubber, ethylene propylene rubber, ethylene propylene diene rubber, metallocene-based poly(ethylene-co-octene) elastomer, poly(ethylene-co-butene) elastomer, styrene-ethylene-butadiene-styrene elastomer, epichlorohydrin rubber, polyacrylic rubber, silicone rubber, fluorosilicone rubber, perfluoroelastomers, polyether block amides, chlorosulfonated polyethylene, ethylene-vinyl acetate, thermoplastic elastomer, protein resilin, protein elastin, ethylene oxide-epichlorohydrin copolymer, polyurethane, urethane-urea copolymer, a sulfonated version thereof, or a combination thereof.
18 . A powder mass of an anode active material for a lithium battery anode electrode, said powder mass comprising multiple particulates of an anode active material, wherein at least a particulate comprises one or a plurality of particles of said anode active material having a volume Va, an electron-conducting material as a matrix, binder or filler material, and pores having a volume Vp which are encapsulated by a thin encapsulating layer of a first carbonaceous or graphitic material, wherein said thin encapsulating layer has a thickness from 1 nm to 10 μm and a lithium ion conductivity from 10 −8 S/cm to 5×10 −2 S/cm and a volume ratio Vp/Va is from 0.5/1.0 to 5.0/1.0.
19 . The powder mass of claim 18 , wherein said electron-conducting material (matrix, binder, or filler) is selected from a carbon nanotube, carbon nanofiber, nanocarbon particle, metal nanoparticle, metal nanowire, electron-conducting polymer, graphene, or a combination thereof, wherein said graphene is selected from pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, nitrogenated graphene, hydrogenated graphene, doped graphene, functionalized graphene, or a combination thereof and said graphene comprise single-layer graphene or few-layer graphene, wherein said few-layer graphene is defined as a graphene platelet formed of less than 10 graphene planes.
20 . The powder mass of claim 18 , wherein said electron-conducting polymer is selected from polyaniline, polypyrrole, polythiophene, polyfuran, a bi-cyclic polymer, a sulfonated derivative thereof, or a combination thereof.
21 . The powder mass of claim 18 , wherein said electron-conducting material or said first carbonaceous or graphitic material comprises a material selected from polymeric carbon, amorphous carbon, chemical vapor deposition carbon, coal tar pitch, petroleum pitch, mesophase pitch, carbon black, coke, acetylene black, activated carbon, fine expanded graphite particle with a dimension smaller than 100 nm, artificial graphite particle, natural graphite particle, or a combination thereof.
22 . The powder mass of claim 18 , wherein said thin encapsulating layer further comprises a polymer wherein said first carbonaceous or graphitic material is dispersed in or bonded by said polymer.
23 . The powder mass of claim 22 , wherein said polymer contains an adhesive resin, a thermoplastic resin, an elastomer or rubber, a copolymer thereof, an interpenetrating network thereof, or a blend thereof.
24 . The powder mass of claim 18 , wherein said 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), 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; (f) prelithiated versions thereof; (g) particles of Li, Li alloy, or surface-stabilized Li having at least 60% by weight of lithium element therein; and (h) combinations thereof.
25 . The powder mass of claim 24 , wherein said Li alloy contains from 0.1% to 10% by weight of a metal element selected from Zn, Ag, Au, Mg, Ni, Ti, Fe, Co, V, or a combination.
26 . The powder mass of claim 18 , wherein said anode active material contains a prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnO x , prelithiated SiO x , prelithiated iron oxide, prelithiated VO 2 , prelithiated Co 3 O 4 , prelithiated Ni 3 O 4 , lithium titanate, or a combination thereof, wherein x=1 to 2.
27 . The powder mass of claim 18 , wherein said anode active material is in a form of nanoparticle, nanowire, nanofiber, nanotube, nanosheet, nanobelt, nanoribbon, nanodisc, nanoplatelet, or nanohorn having a thickness or diameter from 0.5 nm to 100 nm.
28 . The powder mass of claim 18 , wherein at least one of said anode active material particles is coated with a layer of carbon prior to being encapsulated.
29 . The powder mass of claim 18 , wherein at least one of said particulates further comprises from 0.1% to 40% by weight of a lithium ion-conducting additive dispersed in said thin encapsulating layer or in ionic contact with said anode active material particles encapsulated therein.
30 . The powder mass of claim 29 , wherein said lithium ion-conducting additive 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 , or a combination thereof, wherein X=F, Cl, I, or Br, R=a hydrocarbon group, 0<x≤1 and 1≤y≤4.
31 . The powder mass of claim 29 , wherein said lithium ion-conducting additive contains a lithium salt selected from lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro-methanesulfonate (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 nitrate (LiNO 3 ), Li-fluoroalkyl-phosphate (LiPF 3 (CF 2 CF 3 ) 3 ), lithium bisperfluoro-ethylsulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lithium salt, or a combination thereof.
32 . The powder mass of claim 17 , wherein said anode active material is prelithiated to contain from 0.1% to 54.7% by weight of lithium.
33 . A lithium battery containing an optional anode current collector, the anode electrode as defined in claim 1 , a cathode active material layer, an optional cathode current collector, an electrolyte in ionic contact with said anode active material layer and said cathode active material layer, and an optional porous separator disposed between said anode active material layer and said cathode active material layer.
34 . The lithium battery of claim 32 , which is a lithium-ion battery, lithium metal battery, lithium-sulfur battery, lithium-selenium battery, or lithium-air battery.