High-Energy Density Lithium-Ion Battery Containing Stable Artificial Solid-Electrolyte Interface

1 . A lithium-ion battery comprising an anode, a cathode, a lithium-ion permeable and electrically insulating separator that electrically separates the anode from the cathode, wherein the anode comprises (i) multiple particles of an anode active material selected from the group consisting of silicon (Si), germanium (Ge), phosphorus (P), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), cadmium (Cd), alloys thereof, oxides thereof, alloys thereof with lithium (Li), and combinations thereof; (ii) from 0.1% to 15% by weight of an ion-conducting protective polymer that is in physical contact with multiple particles of the anode active material to protect the particles, wherein the polymer has a lithium-ion conductivity no less than 10 −6 S/cm; (iii) from 0% to 10% by weight of a conductive additive; (iv) from 0% to 10% by weight of a binder resin; and (v) from 5% to 80% by volume of pores in the anode.

2 . The lithium-ion battery of claim 1 , wherein the ion-conducting protective polymer comprises an elastic polymer having a reversible tensile strain of from 5% to 1,500%.

3 . The lithium-ion battery of claim 2 , wherein the elastic polymer is selected from natural polyisoprene, synthetic polyisoprene, polybutadiene, chloroprene rubber, polychloroprene, butyl rubber, styrene-butadiene rubber, nitrile rubber, ethylene propylene rubber, ethylene propylene diene rubber, epichlorohydrin rubber, polyacrylic rubber, polysiloxane or 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 polyurethane copolymer, or a combination thereof.

4 . The lithium-ion battery of claim 2 , wherein the elastic polymer contains a cross-linked network of polymer chains.

5 . The lithium-ion battery of claim 4 , wherein the cross-linked network of polymer chains contains an ether linkage, nitrile-derived linkage, benzo peroxide-derived linkage, ethylene oxide linkage, propylene oxide linkage, vinyl alcohol linkage, cyano-resin linkage, triacrylate monomer-derived linkage, tetraacrylate monomer-derived linkage, or a combination thereof in said cross-linked network of polymer chains.

6 . The lithium-ion battery of claim 4 , wherein the cross-linked network of polymer chains comprise nitrile-containing polyvinyl alcohol chains, cyanoresin chains, pentaerythritol tetraacrylate chains, pentaerythritol triacrylate chains, ethoxylated trimethylolpropane triacrylate (ETPTA) chains, ethylene glycol methyl ether acrylate (EGMEA) chains, or a combination thereof.

7 . The lithium-ion battery of claim 1 , wherein the protective polymer contains a conducting polymer or a conductive polymer network of cross-linked chains comprising chains of a conjugated polymer selected from polyacetylene, polythiophene, poly(3-alkylthiophenes), polypyrrole, polyaniline, poly(isothianaphthene), poly(3,4-ethylenedioxythiophene), alkoxy-substituted poly(p-phenylene vinylene), poly(2,5-bis(cholestanoxy) phenylene vinylene), poly(p-phenylene vinylene), poly(2,5-dialkoxy) paraphenylene vinylene, poly[(1,4-phenylene-1,2-diphenylvinylene)], poly(3′,7′-dimethyloctyloxy phenylene vinylene), polyparaphenylene, polyparaphenylene, polyparaphenylene sulphide, polyheptadiyne, poly(3-hexylthiophene), poly(3-octylthiophene), poly(3-cyclohexylthiophene), poly(3-methyl-4-cyclohexylthiophene), poly(2,5-dialkoxy-1,4-phenyleneethynylene), poly(2-decyloxy-1,4-phenylene), poly(9,9-dioctylfluorene), polyquinoline, a derivative thereof, a copolymer thereof, a sulfonated version thereof, or a combination thereof.

8 . The lithium-ion battery of claim 1 , wherein the protective polymer comprises a polymer selected from poly(ethylene oxide), polypropylene oxide, polyoxymethylene, polyvinylene carbonate, polypropylene carbonate, poly(ethylene glycol), poly(acrylonitrile), poly(methyl methacrylate), poly(vinylidene fluoride), poly bis-methoxy ethoxyethoxide-phosphazenex, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene, cyanoethyl poly(vinyl alcohol), a pentaerythritol tetraacrylate-based polymer, an aliphatic polycarbonate, a single Li-ion conducting solid polymer with a carboxylate anion, a sulfonylimide anion, or sulfonate anion, poly(ethylene glycol) diacrylate, poly(ethylene glycol) methyl ether acrylate, polyurethane, polyurethan-urea, polyacrylamide, a polyionic liquid, polymerized 1,3-dioxolane, polyepoxide ether, polysiloxane, poly(acrylonitrile-butadiene), polynorbornene, poly(hydroxyl styrene), poly(ether ether ketone), polypeptoid, poly(ethylene-maleic anhydride), polycaprolactone, poly(trimethylene carbonate), a copolymer thereof, a sulfonated derivative thereof, or a combination thereof.

9 . The lithium-ion battery of claim 1 , further comprising an artificial solid-electrolyte interface (SEI) layer disposed between the anode and the separator wherein the artificial SEI layer has a lithium-ion conductivity greater than 10 −6 S/cm.

10 . The lithium-ion battery of claim 9 , wherein said artificial SEI layer has a lithium-ion conductivity from 10 −5 S/cm to 10 −2 S/cm.

11 . The lithium-ion battery of claim 9 , wherein said artificial SEI layer comprises a lithium- or sodium-containing species 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 , Na 2 CO 3 , Na 2 O, Na 2 C 2 O 4 , NaOH, NaiX, 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, x=0-1, y=1-4.

12 . The lithium-ion battery of claim 9 , wherein said artificial SEI layer comprises a matrix of amorphous carbon, polymeric carbon, or a polymer, and from 0% to 50% by weight of a reinforcement phase dispersed in said matrix, and a lithium- or sodium-containing species that are chemically bonded to or dispersed in said matrix and/or said reinforcement phase to form an integral layer, 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 , Na 2 CO 3 , Na 2 O, Na 2 C 2 O 4 , NaOH, NaiX, 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, x=0-1, y=1-4; and wherein said lithium- or sodium-containing species is derived from an electrochemical decomposition reaction, wherein the matrix is from 5% to 95% by volume of the integral layer, and wherein a weight ratio of the matrix to the lithium- or sodium-containing species is from 1/100 to 100/1.

13 . The lithium-ion battery of claim 9 , wherein said artificial SEI layer comprises a product of electrochemical reductive or oxidative degradation of an electrolyte.

14 . The lithium-ion battery of claim 9 , wherein the conductive additive contains a material selected from carbon particles, expanded graphite flakes, carbon black particles, carbon nanotubes, carbon nano-fibers, carbon fibers, graphite fibers, conductive polymer fibers, coke particles, meso-phase carbon particles, meso-porous carbon particles, electro-spun nano fibers, carbon-coated metal nanowires, conductive polymer-coated nanowires or nano-fibers, graphene sheets or platelets, or a combination thereof.

15 . The lithium-ion battery of claim 12 , wherein the reinforcement phase contains a material selected from ceramic particles or fibers, glass particles or fibers, carbon particles, expanded graphite flakes, carbon black particles, carbon nanotubes, carbon nano-fibers, carbon fibers, graphite fibers, polymer fibers, coke particles, meso-phase carbon particles, meso-porous carbon particles, electro-spun nano fibers, carbon-coated metal nanowires, conductive polymer-coated nanowires or nano-fibers, graphene sheets or platelets, or a combination thereof.

16 . The lithium-ion battery of claim 15 , wherein said graphene sheets or platelets include single-layer sheets or multi-layer platelets of a graphene material selected from pristine graphene, graphene oxide having 2% to 46% by weight of oxygen, reduced graphene oxide having 0.01% to 2% by weight of oxygen, chemically functionalized graphene, nitrogen-doped graphene, boron-doped graphene, fluorinated graphene, or a combination thereof.

17 . The lithium-ion battery of claim 1 , wherein the separator comprises a porous polymer or polymer membrane, a fabric, a solid polymer electrolyte, an inorganic solid electrolyte, or a combination thereof.

18 . The lithium-ion battery of claim 17 , wherein the inorganic solid electrolyte is selected from an oxide type, Perovskite, sulfide type, Argyrodite, hydride type, halide type, borate type, phosphate type, lithium phosphorus oxynitride (LiPON), garnet-type, lithium superionic conductor (LISICON) type, sodium superionic conductor (NASICON) type, or a combination thereof.

19 . The lithium-ion battery of claim 17 , wherein the solid polymer electrolyte is selected from poly(ethylene oxide), polypropylene oxide, polyoxymethylene, polyvinylene carbonate, polypropylene carbonate, poly(ethylene glycol), poly(acrylonitrile), poly(methyl methacrylate), poly(vinylidene fluoride), poly bis-methoxy ethoxyethoxide-phosphazenex, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene, cyanoethyl poly(vinyl alcohol), a pentaerythritol tetraacrylate-based polymer, an aliphatic polycarbonate, a single Li-ion conducting solid polymer with a carboxylate anion, a sulfonylimide anion, or sulfonate anion, poly(ethylene glycol) diacrylate, poly(ethylene glycol) methyl ether acrylate, polyurethane, polyurethan-urea, polyacrylamide, a polyionic liquid, polymerized 1,3-dioxolane, polyepoxide ether, polysiloxane, poly(acrylonitrile-butadiene), polynorbornene, poly(hydroxyl styrene), poly(ether ether ketone), polypeptoid, poly(ethylene-maleic anhydride), polycaprolactone, poly(trimethylene carbonate), a copolymer thereof, a sulfonated derivative thereof, or a combination thereof.

20 . The lithium-ion battery of claim 17 , wherein the porous polymer or polymer membrane, the fabric, or the solid polymer electrolyte is further soaked or impregnated with a liquid electrolyte comprising a lithium salt dissolved in a liquid solvent.

21 . The lithium-ion battery of claim 1 , wherein the protective polymer is further mixed with a liquid solvent or a liquid electrolyte wherein the liquid-to-protective polymer ratio is from 1/100 to 1/1.

22 . The lithium-ion battery of claim 1 , wherein said artificial SEI layer has a thickness from 10 nm to 20 μm.

23 . A process for producing the lithium-ion battery of claim 1 , said process comprising the steps of:

A) preparing an anode by mixing (i) multiple particles of an anode active material, (ii) a solution comprising a first ion-conducting protective polymer or a precursor to said first polymer dispersed or dissolved in a liquid medium, (iii) from 0% to 10% by weight of a conductive additive; and (iv) from 0% to 10% by weight of a binder resin to form a wet anode electrode, followed by removing the liquid medium or converting the liquid medium to a solid to form the anode containing from 5% to 80% by volume of pores dispersed therein, wherein the first protective polymer occupies from 0.1% to 15% by weight of the anode and is in physical contact with multiple particles of the anode active material to protect the particles, and the first polymer has a lithium-ion conductivity no less than 10 −6 S/cm;

B) preparing a cathode;

C) preparing a lithium-ion permeable and electrically insulating separator; and

D) combining the anode, the separator, and the cathode to form the lithium-ion battery.

24 . The process of claim 23 , wherein the procedure of removing the liquid medium or converting the liquid medium to a solid is conducted before or after step (D) of forming the battery.

25 . The process of claim 23 , wherein the procedure of converting the liquid medium to a solid comprises polymerizing a monomer or crosslinking a precursor polymer or oligomer.

26 . The process of claim 23 , wherein step (B) comprising mixing (i) multiple particles of a cathode active material, (ii) a solution comprising a second ion-conducting protective polymer or a precursor to said second polymer dispersed or dissolved in a liquid medium, (iii) from 0.1% to 15% by weight of a conductive additive; and (iv) from 0.1% to 15% by weight of a binder resin to form a wet cathode electrode, followed by removing the liquid medium or converting the liquid medium to a solid to form the cathode, wherein the second protective polymer occupies from 0.1% to 15% by weight of the cathode and is in physical contact with multiple particles of the cathode active material to protect the particles, and the second polymer has a lithium-ion conductivity no less than 10 −6 S/cm.

27 . A process for producing the lithium-ion battery of claim 1 , said process comprising the steps of:

e) preparing an anode by (a1) dispersing multiple particles of an anode active material, 0%-15% by weight of a conductive additive, and 0.1%-15% by weight of a binder resin in a first liquid medium to form a slurry; (a2) coating a layer of the slurry onto one or two primary surfaces of an anode current collector and removing the first liquid medium to form a dry, porous anode electrode having pores therein; (a3) impregnating a liquid polymer or monomer solution into the pores of the anode electrode wherein the solution comprises a first ion-conducting protective polymer or a polymer precursor dispersed or dissolved in a second liquid medium to form a wet anode electrode; and (a4) removing the second liquid medium and/or converting the polymer precursor to a polymer solid to form the anode containing from 5% to 80% by volume of pores dispersed therein, wherein the first protective polymer occupies from 0.1% to 15% by weight of the anode and is in physical contact with multiple particles of the anode active material to protect the particles, and the first polymer has a lithium-ion conductivity no less than 10 −6 S/cm;

f) preparing a cathode;

g) preparing a lithium-ion permeable and electrically insulating separator; and

h) combining the anode, the separator, and the cathode to form the lithium-ion battery.

28 . The process of claim 27 , wherein the procedure of converting the polymer precursor to a polymer solid comprises polymerizing a monomer or crosslinking a precursor polymer or oligomer.

29 . The process of claim 27 , wherein the procedure of removing the second liquid medium or converting the polymer precursor to a polymer solid is conducted before or after step (D) of forming the battery.

30 . The process of claim 23 , further comprising implementing an artificial SEI layer between the anode and the separator.