Negative electrode for lithium metal battery, method of preparing negative electrode, and lithium metal battery including the same

Patent metadata

Field	Value
Publication number	US-10971753-B2
Application number	US-201815964157-A
Country	US
Kind code	B2
Filing date	Apr 27, 2018
Priority date	Apr 28, 2017
Publication date	Apr 6, 2021
Grant date	Apr 6, 2021

Abstract

A negative electrode for a lithium metal battery, the negative electrode including: a lithium metal layer including lithium metal or a lithium metal alloy; and a protective layer on at least a portion of the lithium metal layer, wherein the protective layer includes a plurality of composite particles having a particle size of greater than about 1 micrometer to about 100 micrometers or less, wherein a composite particle of the plurality of composite particles comprises a particle comprising an organic particle, an inorganic particle, an organic-inorganic particle, or combination thereof; and a coating layer disposed on at least a portion of a surface of the particle, the coating layer including an ion conductive material including an ion conductive oligomer including an ion conductive unit, an ion conductive polymer including an ion conductive unit, or a combination thereof.

First claim

What is claimed is:

1. A negative electrode for a lithium metal battery, the negative electrode comprising:
a lithium metal layer comprising lithium metal or a lithium metal alloy; and
a protective layer on at least a portion of the lithium metal layer,
wherein the protective layer comprises a plurality of composite particles having a particle size of greater than about 1 micrometer to about 100 micrometers,
wherein the plurality of composite particles comprises
an organic particle comprising a polymer comprising polystyrene, a copolymer comprising a styrene repeating unit, a copolymer comprising a divinylbenzene repeating unit, or a combination thereof; and
a coating layer disposed on a surface of the organic particle, the coating layer comprising an ion conductive material,
wherein the ion conductive material comprises polyethylene glycol, polypropylene glycol, poly(ethylene glycol-co-propylene glycol-co-ethylene glycol), poly(propylene glycol-co-ethylene glycol-co-propylene glycol), polysiloxane, poly(oxyethylene)methacrylate, poly(ethylene glycol)diacrylate, poly(propylene glycol)diacrylate, poly(ethylene glycol)dimethacrylate, poly(propylene glycol)dimethacrylate, poly(ethylene glycol)urethane diacrylate, poly(ethylene glycol)urethane dimethacrylate, polyester diacrylate, polyester dimethacrylate, poly(ethylene glycol) urethane triacrylate, poly(ethylene glycol) urethane trimethacrylate, a polymer derived from trimethylolpropane triacrylate and trimethylolpropane trimethacrylate, poly(ethylene oxide) grafted poly(methyl methacrylate), poly(propylene oxide) grafted poly(methyl methacrylate), poly(butylene oxide) grafted poly(methyl methacrylate), polysiloxane grafted poly(methyl methacrylate), poly(ethylene glycol) grafted poly(methyl methacrylate), poly(propylene glycol) grafted poly(methyl methacrylate), or a combination thereof.

2. The negative electrode of claim 1 , wherein the protective layer has a Young's modulus of about 10 6 Pascals to about 10 11 Pascals.

3. The negative electrode of claim 1 , wherein the ion conductive material comprises polyethylene glycol.

4. The negative electrode of claim 1 , wherein a weight average molecular weight of the ion conductive material is in a range of about 200 to about 100,000 Daltons.

5. The negative electrode of claim 1 , wherein a thickness of the coating layer is about 0.2 micrometer to about 1 micrometer.

6. The negative electrode of claim 1 , wherein an amount of the ion conductive material in the coating layer is in a range of about 10 parts to about 50 parts by weight, based on 100 parts by weight of the particle.

7. The negative electrode of claim 1 , wherein the protective layer further comprises a crosslinked material of a polymerizable oligomer present between the composite particles.

8. The negative electrode of claim 7 , wherein the polymerizable oligomer is 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, trimethylol propane triacrylate, trimethylol propane trimethacrylate, pentaerythritol triacrylate, ethoxylated/propoxylated trimethylolpropane tri acrylate, propoxylated glyceryl triacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol pentaacrylate,
wherein an amount of the crosslinked material of the polymerizable oligomer is in a range of about 10 parts to about 50 parts by weight, based on 100 parts by weight of the particle.

9. The negative electrode of claim 1 , wherein the protective layer further comprises a lithium salt, or a liquid electrolyte comprising a lithium salt and an organic solvent.

10. The negative electrode of claim 9 , wherein
the lithium salt is 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, and
the organic solvent comprises ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, fluoroethylene carbonate, gamma-butyrolactone, 1,2-dimethoxyethane, 1,2-diethoxyethane, 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, 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether, or a combination thereof.

11. The negative electrode of claim 1 ,
wherein the polymer is polystyrene, 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) acrylate-acrylonitrile-butadiene-styrene) copolymer, a poly((C1-C9 alkyl) methacrylate-butadiene-styrene) copolymer, a poly((C1-C9) alkyl acrylate-butadiene-styrene) copolymer, a poly(styrene-(C1-C9 alkyl) acrylate) copolymer, a poly(acrylonitrile-styrene-(C1-C9 alkyl) acrylate) copolymer, or a combination thereof.

12. The negative electrode of claim 1 , wherein the copolymer comprising the divinylbenzene repeating unit comprises a block copolymer 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, or a combination thereof; and
the copolymer comprising the styrene repeating unit comprises 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) acrylate-acrylonitrile-butadiene-styrene) copolymer, a poly((C1-C9 alkyl) methacrylate-butadiene-styrene) copolymer, a poly((C1-C9) alkyl acrylate-butadiene-styrene) copolymer, a poly(styrene-(C1-C9 alkyl) acrylate) copolymer, a poly(acrylonitrile-styrene-(C1-C9 alkyl) acrylate) copolymer, or a combination of one of the foregoing units.

13. The negative electrode of claim 1 , wherein the protective layer is a single layer or multiple layers comprising a particle, and wherein the protective layer comprises particles having different particle sizes.

14. The negative electrode of claim 1 , wherein the organic particle is a microsphere having an average particle diameter in a range of about 1.1 micrometer to about 50 micrometers.

15. The negative electrode of claim 1 , wherein the organic particle comprises a poly(styrene-co

Assignees

• Samsung Electronics Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Lee Yonggun
• Ryu Saebom
• Yang Yooseong
• Sugimoto Toshinori
• Yu Taehwan

Classifications

• H01M50/417

  Polyolefins · CPC title

• H01M50/426

  Fluorocarbon polymers · CPC title

• H01M50/491

  Porosity · CPC title

• Y02P70/50

  Manufacturing or production processes characterised by the final manufactured product · CPC title

• H01M2004/028

  Positive electrodes · CPC title