Anodeless lithium metal battery and method of manufacturing the same

Patent metadata

Field	Value
Publication number	US-12438150-B2
Application number	US-202217749355-A
Country	US
Kind code	B2
Filing date	May 20, 2022
Priority date	Jan 5, 2018
Publication date	Oct 7, 2025
Grant date	Oct 7, 2025

Abstract

An anodeless lithium metal battery includes: a cathode including a cathode current collector and a cathode active material layer on the cathode current collector; an anode current collector on the cathode; a composite electrolyte between the cathode and the anode current collector, wherein the composite electrolyte, wherein the composite electrolyte includes a first liquid electrolyte and a metal comprising at least one of a lithium metal and a lithium metal alloy; and a liquid-impermeable ion-conductive composite membrane between the cathode and the composite electrolyte.

First claim

What is claimed is:

1. A charged lithium metal battery comprising:
a cathode comprising a cathode current collector and a cathode active material layer on the cathode current collector;
an anode current collector, wherein the anode current collector is a mesh current collector;
a composite electrolyte between the cathode and the anode current collector, wherein the composite electrolyte comprises
a first electrolyte comprising a lithium salt and a first organic solvent, and
an interconnected network structure disposed on a surface of the anode current collector, the interconnected network structure comprising a plurality of connected metal particles, each metal particle comprising a core of at least one of lithium or lithium metal alloy, and lithium from the lithium salt is electrodeposited on a surface of the core of the metal particles,
wherein the electrodeposited lithium connects the metal particles to form a layer, and

a liquid-impermeable ion-conductive composite membrane disposed between the cathode and the composite electrolyte, wherein the liquid-impermeable ion-conductive composite membrane comprises at least one of a solid ionic conductor or a composite comprising the solid ionic conductor and a non-ionic conductor.

2. The charged lithium metal battery of claim 1 ,
The charged lithium metal battery of claim 1 , wherein the first organic solvent comprises at least one selected from the group consisting of an ether compound and a sulfone compound.

3. The charged lithium metal battery of claim 2 , wherein the first organic solvent comprises the ether compound, wherein the ether compound is at least one selected from the group consisting of a glyme compound, a dioxolane compound, and a fluorinated ether compound.

4. The charged lithium metal battery of claim 3 , wherein the glyme compound is at least one selected from the group consisting of ethylene glycol dimethylether, ethylene glycol diethylether, propylene glycol dimethylether, propylene glycol diethylether, butylene glycol dimethylether, butylene glycol diethylether, diethylene glycol dimethylether, triethylene glycol dimethylether, tetraethylene glycol dimethylether, diethylene glycol diethylether, triethylene glycol diethylether, tetraethylene glycol diethylether, dipropylene glycol dimethylether, tripropylene glycol dimethylether, tetrapropylene glycol dimethylether, dipropylene glycol diethylether, tripropylene glycol diethylether, tetrapropylene glycol diethylether, dibutylene glycol dimethylether, tributylene glycol dimethylether, tetrabutylene glycol dimethylether, dibutylene glycol diethylether, tributylene glycol diethylether, and tetrabutylene glycol diethylether, the dioxolane compound is at least one selected from the group consisting of 1,3-dioxolane, 4,5-dimethyl-1,3-dioxolane, 4,5-diethyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, 4-ethyl-1,3-dioxolane, 2-methyl-1,3-dioxolane, 2-vinyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, and 2-ethyl-2-methyl-1,3-dioxolane, and
the fluorinated ether compound is at least one selected from the group consisting of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether, and 2,2,3,3,4,4,5,5-octafluoropentyl 1,1,2,2-tetrafluoroethyl ether.

5. The charged lithium metal battery of claim 4 , wherein the first organic solvent comprises the fluorinated ether compound.

6. The charged lithium metal battery of claim 2 ,
wherein the first organic solvent is selected from the group consisting of dimethyl sulfone, diethyl sulfone, and ethylmethyl sulfone.

7. The charged lithium metal battery of claim 1 , wherein the cathode active material layer further comprises a second electrolyte comprising a lithium salt and a second organic solvent, and
the second organic solvent comprises at least one selected from the group consisting of an ether compound, a sulfone compound, and a carbonate compound,
wherein the first electrolyte has a composition which is the same or different than a composition of the second electrolyte.

8. The charged lithium metal battery of claim 7 , wherein a concentration of the lithium salt in the first electrolyte and a concentration of the lithium salt in the second electrolyte are each independently about 1 molar to about 8 molar.

9. The charged lithium metal battery of claim 8 , wherein a concentration of the lithium salt in the first electrolyte and a concentration of the lithium salt in the second electrolyte are each independently about 2 molar to about 5 molar.

10. The charged lithium metal battery of claim 1 , wherein the composite electrolyte has a viscosity at 25° C. of about 0.05 centipoise to about 60 centipoise.

11. The charged lithium metal battery of claim 1 , wherein the solid ionic conductor comprises at least one selected from the group consisting of Li 1+x Ti 2−x Al x (PO 4 ) 3 wherein 0≤x<4, Li 1+x+y Al x Ti 2−x Si y P 3−y O 12 wherein BaTiO 3 , Pb(Zr 1−x Ti x )O 3 wherein 0≤x≤1, Pb 1−x La x Zr 1−y Ti y O 3 wherein 0≤x<1 and O≤y<1, Pb(Mg 1/3 Nb 2/3 )O 3 —PbTiO 3 , Li 3 PO 4 , Li x Ti y (PO 4 ) 3 wherein 0<x<2, and 0<y<3, Li x Al y Ti z (PO 4 ) 3 wherein 0<x<2, 0<y<1, and 0<z<3, Li 1+x+y (Al 1−a Ga a ) x (Ti 1−b Ge b ) 2−x Si y P 3−y O 12 wherein 0≤x≤1, 0≤y≤1, 0≤a≤1, and 0≤b≤1, Li x La y TiO 3 wherein 0<x<2 and 0<y<3, Li x Ge y P z S w wherein 0<x<4, 0<y<1, 0<z<1, and 0<w<5, Li x N y , wherein 0<x<4 and 0<y<2, Li x Si y S z wherein 0<x<3, 0<y<2, and 0<z<4, Li x P y S z wherein 0<x<3, 0<y<3, and 0<z<7, LiAlO 2 , a Li 2 O—Al 2 O 3 —SiO 2 —P 2 O 5 —TiO 2 —GeO 2 and Li 3+x La 3 M 2 O 12 wherein 0≤x≤5 and M is Te, Nb, or Zr.

12. The charged lithium metal battery of claim 11 , wherein the solid ionic conductor comprises at least one selected from the group consisting of Li 1.4 Ti 1.6 Al 0.4 P 3 O 12 , Li 1.3 Ti 1.7 Al 0.3 P 3 O 12 ,Li 7 La 3 Zr 2 O 12 , Li 5 La 3 Ta 2 O 12 , Li 0.33 La 0.55 TiO 3 , Li 1/3 La 1/3 TiO 3 , and Li 2 O—Al 2 O 3 —SiO 2 —P 2 O 5 —TiO 2 —GeO 2 .

13. The charged lithium metal battery of claim 11 , wherein the liquid-impermeable ion-conductive composite membrane is the composite comprising the solid ionic conductor and the non-ionic conductor, wherein the non-ionic conductor comprises a polymer selected from the group consisting of polyvinyl alcohol, polyacrylonitrile, polyimide, epoxy resin, an acrylic resin, polyethylene, polyethylene oxide, polyvinylidene fluoride, polyvinylpyrrolidone, poly 2-vinylpyridine, polytetrafluoroethylene, a tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, a perfluoroalkoxy copolymer, fluorinated cyclic ether, polyethylene oxide diacrylate, polyethylene oxide dimethacrylate, polypropylene oxide diacrylate, polypropylene oxide dimethacrylate, polymethyleneoxide diacrylate, polymethyleneoxide dimethacrylate, poly (C1-C5 alkyldiol) diacrylate, poly (C1-C5 alkyldiol) dimethacrylate, polydivinylbenzene, polyether, polycarbonate, polyamide, polyester, polyvinyl chloride, polycarboxylic acid, polysulfonic acid, polysulfone, polystyrene, polypropylene, poly (p-phenylene), polyacetylene, poly (p-phenylene vinylene), polyaniline, polypyrrole, polythiophene, polyacene, poly (naphthalene-2,6-diyl), polypropylene oxide, a vinylidene fluoride-hexafluoropropylene copolymer, poly (vinyl acetate), poly (vinyl butyral-co-vinyl alcohol-co-vinyl acetate), poly (methyl methacrylate-co-ethyl acrylate), polyvinyl chloride-co-vinyl acetate, poly (l-vinyl pyrrolidone-co-vinyl acetate), polyacrylate, polymethacrylate, polyurethane, polyvinyl ether, an acrylonitrile-butadiene rubber, a styrene-butadiene rubber, an acrylonitrile-butadiene-styrene rubber, a sulfonated styrene/ethylene-butylene triblock copolymer, a polymer obtained from at least one acrylate mon

Assignees

• Samsung Electronics Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Chang Wonseok
• Kang Hyorang
• Kim Jirae

Classifications

• H01M2300/0094

  in the form of layered products, e.g. coatings · CPC title

• H01M2300/0091

  in the form of mixtures · CPC title

• H01M2300/0068

  inorganic · CPC title

• H01M10/0569

  characterised by the solvents · CPC title

• H01M10/0562

  Solid materials · CPC title