Anodeless lithium metal battery and method of manufacturing the same

Patent metadata

Field	Value
Publication number	US-11355778-B2
Application number	US-201816236689-A
Country	US
Kind code	B2
Filing date	Dec 31, 2018
Priority date	Jan 5, 2018
Publication date	Jun 7, 2022
Grant date	Jun 7, 2022

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. An anodeless lithium metal battery comprising:
a cathode comprising a cathode current collector and a cathode active material layer comprising a cathode active material on the cathode current collector;
an anode current collector;
a composite electrolyte between the cathode and the anode current collector, wherein the composite electrolyte comprises a first electrolyte and a particle comprising a metal,
wherein the metal particle comprises at least one of lithium metal or a lithium metal alloy, and
wherein the first electrolyte comprises a lithium salt and a first organic solvent, wherein the first organic solvent comprises an ether compound or a sulfone compound, wherein the ether compound comprises at least one of a glyme compound, a dioxolane compound, or a fluorinated ether compound; and
a liquid-impermeable ion-conductive composite membrane 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 a solid ionic conductor and a non-ionic conductor.

2. The anodeless lithium metal battery of claim 1 , wherein the liquid-impermeable ion-conductive composite membrane is configured to physically and chemically separate the cathode and the composite electrolyte.

3. The anodeless lithium metal battery of claim 1 , wherein the solid ionic conductor comprises at least one of Li 1+x Ti 2-x Al x (PO 4 ) 3 wherein 0≤x<4, a material comprising Li, Ge, P, and S, Li 1+x+y Al x Ti 2-x Si y P 3-y O 12 wherein 0<x<2 and 0≤y<3, 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 0≤y<1, Pb(Mg 1/3 Nb 2/3 )O 3 —PbTiO 3 , HfO 2 , SrTiO 3 , SnO 2 , CeO 2 , Na 2 O, MgO, NiO, CaO, BaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , TiO 2 , SiO 2 , SiC, 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, L 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, 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, Li 2 O, LiF, LiOH, Li 2 CO 3 , LiAlO 2 , a Li 2 O—Al 2 O 3 —SiO 2 —P 2 O 5 —TiO 2 —GeO 2 ceramic, or Li 3+x La 3 M 2 O 12 wherein 0≤x≤5 and M is Te, Nb, or Zr.

4. The anodeless lithium metal battery of claim 3 , wherein the solid ionic conductor comprises at least one 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 10 GeP 2 S 12 , Li 7 La 3 Zr 2 O 12 , lithium phosphorousoxynitride, Li 5 La 3 Ta 2 O 12 , Li 0.33 La 0.55 TiO 3 , Al 1.5 Al 0.5 Ge 1.5 P 3 O 12 , Li 3 BO 3 , Li 4 SiO 4 —Li 3 PO 4 , Li 4 SiO 4 , Li 1/3 La 1/3 TiO 3 , or Li 2 O—Al 2 O 3 —SiO 2 —P 2 O 5 —TiO 2 —GeO 2 .

5. The anodeless lithium metal battery of claim 1 , wherein the liquid-impermeable ion-conductive composite membrane has a thickness of about 10 micrometers to about 150 micrometers.

6. The anodeless lithium metal battery of claim 1 , wherein the non-ionic conductor comprises at least one 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 monomer selected from ethoxylated neopentyl glycol diacrylate, ethoxylated bisphenol A diacrylate, ethoxylated aliphatic urethane acrylate, ethoxylated C1-C5 alkylphenol acrylate, or a C1-C5 alkyl acrylate.

7. The anodeless 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 of an ether compound, a sulfone compound, or a carbonate compound, and
wherein the first electrolyte has a composition which the same or different than a composition of the second electrolyte.

8. The anodeless lithium metal battery of claim 7 , wherein the first electrolyte has a composition which different than the composition of the second liquid electrolyte.

9. The anodeless lithium metal battery of claim 7 , wherein the first electrolyte and the second electrolyte each independently further comprise at least one of an ionic liquid or a polymer ionic liquid, wherein the ionic liquid or the polymer ionic liquid of the first electrolyte or the ionic liquid or the polymer ionic liquid of the second electrolyte, if present, are the same or different.

10. The anodeless 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.

11. The anodeless 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 2 molar to about 5 molar.

12. The anodeless lithium metal battery of claim 7 , wherein the ether compound of the second organic solvent is at least one of a glyme compound, a dioxolane compound, or fluorinated ether compound.

13. The anodeless lithium metal battery of claim 1 , wherein the lithium alloy comprises lithium and at least one of Si, Sn, Al, Ge, Pb, Bi, Sb, a Si—Y′ alloy wherein Y′ is at least one of an alkaline metal, an alkaline earth metal, a Group 13 to Group 16 element, a transition metal, or a rare earth element, and is not Si, a Sn—Y′ alloy wherein Y′ is at least one of an alkaline metal, an alkaline earth metal, a Group 13 to Group 16 element, a transition metal, or a rare earth element, and is not Sn, or MnO x wherein 0<x≤2.

14. The anodeless lithium metal battery of claim 1 , wherein an amount of the metal is about 1 part by weight to about 50 parts by weight, with respect to 100 parts by weight of a total weight of the composite electrolyte.

15. The anodeless lithium metal battery of claim 1 , wherein the particle has a size of about 5 micrometers to about 50 micrometers.

16. The anodeless lithium metal battery of claim 1 , wherein the metal is lithium metal.

17. The anodeless lithium metal battery of claim 1 , further comprising a porous polyme

Assignees

• Samsung Electronics Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Chang Wonseok
• Kang Hyorang
• Kim Jirae

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M10/0525 Primary

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M50/457

  comprising three or more layers · CPC title

• H01M50/426

  Fluorocarbon polymers · CPC title

• H01M50/417

  Polyolefins · CPC title