Negative electrode for lithium metal battery and lithium metal battery comprising the same

Patent metadata

Field	Value
Publication number	US-2017324097-A1
Application number	US-201715584430-A
Country	US
Kind code	A1
Filing date	May 2, 2017
Priority date	May 9, 2016
Publication date	Nov 9, 2017
Grant date	—

Abstract

A negative electrode for a lithium metal battery, the negative electrode including: a lithium metal electrode comprising lithium metal or a lithium metal alloy; and a protective layer on at least a portion of the lithium metal electrode, wherein the protective layer has a Young's modulus of about 10 6 Pascals or greater, wherein the protective layer includes at least one first particle, wherein the first particle includes an organic particle, an inorganic particle, an organic-inorganic particle, or a combination thereof, and wherein the first particle has a particle size of greater than 1 micrometer to about 100 micrometers, and a crosslinked material comprising a polymerizable oligomer, which is disposed between first particles of the at least one first particle.

First claim

What is claimed is:

1 . A negative electrode for a lithium metal battery, the negative electrode comprising:
a lithium metal electrode comprising lithium metal or a lithium metal alloy; and a protective layer on at least a portion of the lithium metal electrode, wherein the protective layer has a Young's modulus of about 10 6 Pascals or greater, wherein the protective layer comprises
at least one first particle, wherein the first particle comprises an organic particle, an inorganic particle, an organic-inorganic particle, or a combination thereof, and wherein the first particle has a particle size of greater than 1 micrometer to about 100 micrometers, and
a crosslinked material of a polymerizable oligomer, which is disposed between first particles of the at least one first particle.

2 . The negative electrode of claim 1 , wherein the polymerizable oligomer has a weight average molecular weight of about 5,000 Daltons or less.

3 . The negative electrode of claim 1 , wherein the polymerizable oligomer comprises diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylated trimethylolpropane triacrylate, acrylate-functionalized ethylene oxide, 1,6-hexanediol diacrylate, ethoxylated neopentyl glycol diacrylate; propoxylated neopentyl glycol diacrylate, allyl methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, ethoxylated propoxylated trimethylolpropane triacrylate propoxylated glyceryl triacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol tetraacrylate, di pentaerythritol pentaacrylate, or a combination thereof.

4 . The negative electrode of claim 1 , wherein an amount of the cross-linked material of the polymerizable oligomer is from about 10 parts by weight to about 50 parts by weight, based on 100 parts by weight of the at least one first particle in the protective layer.

5 . The negative electrode of claim 1 , wherein the at least one first particle in the protective layer comprises a compound having a chemically or physically cross-linked structure.

6 . The negative electrode of claim 1 , wherein the at least one first particle comprises a microsphere having an average particle diameter of about 1.1 micrometer to about 50 micrometers.

7 . The negative electrode of claim 1 , wherein the at least one first particle in the protective layer comprises a polymer comprising a polystyrene homopolymer, a copolymer comprising a styrene repeating unit, a copolymer comprising a repeating unit having a cross-linkable functional group, a cross-linked polymer, or a combination thereof.

8 . The negative electrode of claim 7 , wherein the polymer comprises homopolystyrene, a poly(styrene-divinylbenzene) copolymer, a poly(methyl methacrylate-divinylbenzene) copolymer, a poly(ethyl methacrylate-divinylbenzene) copolymer, a poly(pentyl methacrylate-divinylbenzene) copolymer, a poly(butyl methacrylate-divinylbenzene) copolymer, a poly(propyl methacrylate-divinylbenzene) copolymer, a poly(styrene-ethylene-butylene-styrene) copolymer, a poly(styrene-methyl methacrylate) copolymer, a poly(styrene-acrylonitrile) copolymer, a poly(styrene-vinylpyridine) copolymer, a poly(acrylonitrile-butadiene-styrene) copolymer, a poly(acrylonitrile-ethylene-propylene-styrene) copolymer, a poly(methyl methacrylate-acrylonitrile-butadiene-styrene) copolymer, a poly((C1-C9 alkyl) methacrylate-butadiene-styrene) copolymer, a poly(styrene-(C1-C9 alkyl) acrylate) copolymer, a poly(acrylonitrile-styrene-(C1-C9alkyl) acrylate) copolymer,
a cross-linked polymer, or a combination thereof.

9 . The negative electrode of claim 1 , wherein the at least one first particle in the protective layer comprises a cage-structured silsesquioxane, a metal-organic framework compound, 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, Li 1+x+y (Al 1-q Ga q ) x (Ti 1-r Ge r ) 2-x Si y P 3-y O 12 wherein 0≦x≦1, 0≦y≦1, 0≦q≦1, and 0≦r≦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, 0<y<2, a glass of the formula Li x Si y S z wherein 0≦x<3, 0<y<2, and 0<z<4, a glass of the formula 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, a garnet ceramic of the formula Li 3+x La 3 M 2 O 12 wherein 0≦x≦5, and M is Te, Nb, or Zr, or a combination thereof,
a cross-linked structure thereof, or a combination thereof.

10 . The negative electrode of claim 1 , wherein the at least one first particle in the protective layer comprises a polymer comprising a poly(styrene-divinylbenzene) copolymer, a poly(methyl methacrylate-divinylbenzene) copolymer, a poly(ethyl methacrylate-divinylbenzene) copolymer, a poly(pentyl methacrylate-divinylbenzene) copolymer, a poly(butyl methacrylate-divinylbenzene) copolymer, a poly(propyl methacrylate-divinylbenzene) copolymer, a poly(styrene-ethylene-butylene-styrene) copolymer, a poly(styrene-methyl methacrylate) copolymer, a poly(styrene-acrylonitrile) copolymer, a poly(styrene-vinylpyridine) copolymer, a poly(acrylonitrile-butadiene-styrene) copolymer, a poly(acrylonitrile-ethylene-propylene-styrene) copolymer, a poly(methyl methacrylate-acrylonitrile-butadiene-styrene) copolymer, a poly((C1-C9 alkyl) methacrylate-butadiene-styrene) copolymer, a poly(styrene-(C1-C9 alkyl) acrylate) copolymer, a poly(acrylonitrile-styrene-(C1-C9 alkyl) acrylate) copolymer, or a combination thereof.

11 . The negative electrode of claim 1 , wherein the protective layer further comprises a lithium salt or a liquid electrolyte.

12 . The negative electrode of claim 11 , wherein the liquid electrolyte occupies about 30 volume percent to about 60 volume percent of the total volume of the protective layer.

13 . The negative electrode of claim 11 , wherein the liquid electrolyte comprises a lithium salt and an organic solvent.

14 . The negative electrode of claim 13 , wherein the lithium salt comprises LiSCN, LiN(CN) 2 , LiClO 4 , LiBF 4 , LiAsF 6 , LiPF 6 , LiCF 3 SO 3 , LiC(CF 3 SO 2 ) 3 , LiN(SO 2 C 2 F 5 ) 2 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 F) 2 , LiSbF 6 , LiPF 3 (CF 2 CF 3 ) 3 , LiPF 3 (CF 3 ) 3 , LiB(C 2 O 4 ) 2 , or a combination thereof.

15 . The negative electrode of claim 13 , wherein the organic solvent comprises ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, fluoroethylene carbonate, γ-butyrolactone, 1,2-dimethoxy ethane, 1,2-diethoxy ethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, succinonitrile, sulfolane, dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone, adiponitrile, tetraethyleneglycol dimethyl ether, 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether, or a combination thereof.

16 . The negative electrode of claim 1 , wherein the protective layer further comprises an ion conductive polymer.

17 . The negative electrode of claim 16 , wherein the ion conductive polymer is a homopolym

Assignees

• Samsung Electronics Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Lee Yonggun
• Ryu Saebom
• Sugimoto Toshinori
• Chang Wonseok

Classifications

• H01M2220/20

  Batteries in motive systems, e.g. vehicle, ship, plane · CPC title

• C08K3/30

  Sulfur-, selenium- or tellurium-containing compounds · CPC title

• H01M2004/021

  Physical characteristics, e.g. porosity, surface area · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M10/4235

  Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence) · CPC title