Composite electrolyte structure and lithium metal battery including the same

Patent metadata

Field	Value
Publication number	US-2018166743-A1
Application number	US-201715840168-A
Country	US
Kind code	A1
Filing date	Dec 13, 2017
Priority date	Dec 13, 2016
Publication date	Jun 14, 2018
Grant date	—

Abstract

A composite electrolyte structure includes: a protective layer having a Young's modulus of about 10 6 pascals or greater and including a first particle, the first particle including an organic particle, an inorganic particle, an organic-inorganic particle, or a combination thereof, wherein the particle in the protective layer has a particle size of greater than 1 micrometer to about 100 micrometers, and a solid electrolyte layer including a second particle including an organic particle, an inorganic particle, an organic-inorganic particle, or a combination thereof, wherein the second particle has a particle size of greater than 1 micrometer to about 100 micrometers, wherein the first particle and the second particle are the same or different, and wherein the protective layer is on the solid electrolyte layer.

First claim

What is claimed is:

1 . A composite electrolyte structure comprising:
a protective layer having a Young's modulus of about 10 6 pascals or greater and comprising
a first particle, the first comprising an organic particle, an inorganic particle, an organic-inorganic particle, or a combination thereof, wherein the first particle has a particle size of greater than 1 micrometer to about 100 micrometers, and
a solid electrolyte layer comprising
a second particle, the second particle comprising an organic particle, an inorganic particle, an organic-inorganic particle, or a combination thereof, wherein the second particle has an average particle size of greater than 1 micrometer to about 100 micrometers, and
wherein the first particle and the second particle are the same or different, and wherein the protective layer is on the solid electrolyte layer.

2 . The composite electrolyte structure of claim 1 , wherein the first particle and the second particle are each independently a porous hollow particle or a non-porous particle.

3 . The composite electrolyte structure of claim 1 , wherein the solid electrolyte layer comprises
a first electrolyte comprising the second particle, a polymer, and a lithium salt, and a second electrolyte comprising a ceramic conductor.

4 . The composite electrolyte structure of claim 1 , wherein the solid electrolyte layer comprises a first lithium salt, and the solid electrolyte layer further comprises,
a third electrolyte comprising the second particle, a polymer, and a second lithium salt, wherein the first lithium salt and the second lithium salt are the same or different.

5 . The composite electrolyte structure of claim 4 , wherein the first particle or the second particle comprises a porous particle having an average pore diameter of about 10 nanometers to about 50 nanometers.

6 . The composite electrolyte structure of claim 1 , wherein the first particle or the second particle each independently comprises a microsphere having an average diameter of about 1.1 micrometer to about 50 micrometers.

7 . The composite electrolyte structure of claim 1 , wherein the protective layer further comprises a liquid electrolyte.

8 . The composite electrolyte structure of claim 1 , wherein the protective layer further comprises a crosslinked polymer, and the crosslinked polymer is a crosslinked material of polymerizable compound.

9 . The composite electrolyte structure of claim 8 , wherein the polymerizable compound 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, glyceryl/propoxylated triacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, or a combination thereof.

10 . The composite electrolyte structure of claim 8 , wherein an amount of the crosslinked polymerizable compound is in a range of about 10 parts by weight to about 50 parts by weight, based on 100 parts by weight of the particle in the protective layer.

11 . The composite electrolyte structure of claim 1 , wherein the particle in the protective layer comprises a homopolystyrene, 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.

12 . The composite electrolyte structure of claim 1 , wherein the first particle comprises silica, titania, alumina, BaTiO 3 , 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, 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 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 a Ga 1−a ) x (Ti b Ge 1−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, 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 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.

13 . The composite electrolyte structure of claim 1 , wherein the protective layer further comprises an ionic liquid, a metal salt containing a Group 1 element or a Group 2 element, a nitrogen-containing compound, boron nitride, an ion conductive polymer, or a combination thereof.

14 . The composite electrolyte structure of claim 1 , wherein the protective layer is directly on the solid electrolyte layer.

15 . A composite electrolyte structure comprising:
a first electrolyte comprising
a first particle comprising an organic particle, an inorganic particle, an organic-inorganic particle, or a combination thereof, wherein the first particle has a particle size of greater than 1 micrometer to about 100 micrometers,
a polymer, and
a lithium salt; and
a second electrolyte comprising a ceramic conductor on the first electrolyte.

16 . The composite electrolyte structure of claim 15 , wherein the ceramic conductor comprises Li 2 S—P 2 S 5 , Li 2 S—P 2 S 5 —Li 4 SiO 4 , Li 2 S—Ga 2 S 3 —GeS 2 , Li 2 S—Sb 2 S 3 —GeS 2 , Li 3.25 —Ge 0.25 —P 0.75 S 4 , (La a Li 1−a )TiO 3 wherein 0≤a≤1, Li 6 La 2 CaTa 2 O 12 , Li 6 La 2 ANb 2 O 12 wherein A is Ca or Sr, Li 2 Nd 3 TeSbO 12 , Li 3 BO 2.5 N 0.5 , Li 9 SiAlO 8 , Li 1+x Al x Ge 2−x (PO 4 ) 3 wherein 0.1≤x≤0.7, Li 1+x Al x Ti 2−x (PO 4 ) 3 wherein 0.1≤x≤0.7, Li 1+x Ti 2−x Al x Si y (PO 4 ) 3−y wherein 0.1≤x≤0.7 and 0.1≤y<1, LiAl x Zr 2−x (PO 4 ) 3 wherein 0.1≤x≤0.7, LiTi x Zr 2−x (PO 4 ) 3 wherein 0.1≤x≤0.7, or a combination thereof.

17 . The composite electrolyte structure of claim 15 , 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.

18 . The composite electrolyte structure of claim 15 , wherein the second electrolyte further comprises a binder.

19 . The composite electrolyte structure of claim 15 , wherein the first particle comprises a microsphere having an average diameter of about 1.1 micrometer to about 50 micrometers.

20 . A lithium metal battery comprising:
a lithium metal electrode comprising lithium metal or a lithium metal alloy; the composite electrolyte structure of claim 1 on at least a portion of the lithium metal electrode; and a cathode.

21 . The lithium metal battery of claim

Assignees

• Samsung Electronics Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Lee Yonggun
• Ryu Saebom
• Yu Taehwan
• Chang Wonseok

Classifications

• H01M50/457

  comprising three or more layers · CPC title

• H01M50/491

  Porosity · CPC title

• H01M50/417

  Polyolefins · CPC title

• H01M50/434

  Ceramics · CPC title

• H01M50/426

  Fluorocarbon polymers · CPC title