Electrolyte for lithium metal battery and lithium metal battery including the same

Patent metadata

Field	Value
Publication number	US-11302959-B2
Application number	US-201716327050-A
Country	US
Kind code	B2
Filing date	Aug 3, 2017
Priority date	Aug 22, 2016
Publication date	Apr 12, 2022
Grant date	Apr 12, 2022

Abstract

Provided are an electrolyte for a lithium metal battery and a lithium metal battery including the electrolyte, wherein the electrolyte includes a composite including a lithium ion-conductive compound which is a non-carbonate-based substance having resistance to reduction of lithium metal, a polymerization product of a crosslinkable polymer, and a lithium salt, wherein the lithium ion-conductive compound is glycol ether.

First claim

The invention claimed is:

1. A solid electrolyte for a lithium metal battery, the solid electrolyte comprising a composite that includes:
a glycol ether,
a polymerization product of a crosslinkable polymer, and
a lithium salt, wherein:
the composite is formed by polymerizing the crosslinkable polymer after combining the crosslinkable polymer with the glycol ether and the lithium salt, and the polymerization product of the crosslinkable polymer forms a net-like matrix in which the glycol ether and the lithium salt are present.

2. The solid electrolyte of claim 1 , wherein the glycol ether is at least one selected from triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, ethylene glycol monomethyl ether (MG), diethylene glycol monomethyl ether (MDG), triethylene glycol monomethyl ether (MTG), polyethylene glycol monomethyl ether (MPG), ethylene glycol monoethyl ether (EG), diethylene glycol monoethyl ether (EDG), ethylene glycol monobutyl ether (BG), diethylene glycol monobutyl ether (BDG), triethylene glycol monobutyl ether (BTG), propylene glycol monomethyl ether (MFG), and dipropylene glycol monomethyl ether (MFDG).

3. The solid electrolyte of claim 1 , wherein the crosslinkable polymer is at least one selected from polyoxyethylene glycol diacrylate and polyoxyethylene glycol dimethacrylate.

4. The solid electrolyte of claim 1 , wherein an amount of the glycol ether is about 10 parts to about 80 parts by weight with respect to 100 parts by weight of the crosslinkable polymer.

5. The solid electrolyte of claim 1 , further comprising ion-conductive inorganic particles.

6. The solid electrolyte of claim 5 , wherein the ion-conductive inorganic particles comprise at least one selected from 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,Ti)O 3 (PZT), Pb 1−x La x Zr 1−y Ti y O 3 (PLZT) (wherein 0≤x<1 and 0≤y<1), Pb(Mg 3 Nb 2/3 )O 3 —PbTiO 3 (PMN-PT), 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, lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li x Ti y (PO 4 ) 3 , wherein 0<x<2 and 0<y<3), lithium aluminum titanium phosphate (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, Ga) x (ti, Ge) 2−x Si y P 3 O 12 (wherein 0≤x≤1 and 0≤y≤1), lithium lanthanum titanate (Li x La y TiO 3 , wherein 0<x<2 and 0<y<3), lithium germanium thiophosphate (Li x Ge y P z S w , wherein 0<x<4, 0<y<1, 0<z<1, and 0<w<5), a lithium nitride glass (Li x N y , wherein 0<x<4 and 0<y<2), SiS 2 (Li x Si y S z , wherein 0<x<3,0<y<2, and 0<z<4), a P 2 S 5 glass (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 (Li 3+x La 3 M 2 O 12 , wherein M is Te, Nb, or Zr, and x is an integer from 1 to 10), or a combination thereof.

7. The solid electrolyte of claim 1 , wherein the lithium salt is at least one selected from LiSCN, LiN(CN) 2 , LiClO 4 , LiBF 4 , LiAsF 6 , LiPF 6 , LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, Li(CF 3 SO 2 ) 3 C, LiSbF 6 , LiN(SO 2 CF 3 ) 2 , Li(FSO 2 ) 2 N, LiC 4 F 9 SO 3 , LiN(SO 2 CF 2 CF 3 ) 2 , LiSbF 6 , LiPF 3 (CF 2 CF 3 ) 3 , LiPF 3 (C 2 F 5 ) 3 , LiPF 3 (CF 3 ) 3 , LiCl, LiF, LiBr, LiI, LiB(C 2 O 4 ) 2 , lithium difluoro(oxalato)borate (LiFOB), lithium bis(oxalato)borate (LiBOB), and a mixture thereof.

8. The solid electrolyte of claim 1 , wherein an amount of the lithium salt is about 5 mol % to about 80 mol % based on a total amount of the solid electrolyte.

9. The solid electrolyte of claim 1 , wherein the solid electrolyte has a porosity of about 10% or less.

10. The solid electrolyte of claim 1 , wherein the solid electrolyte comprises triethylene glycol dimethyl ether, a polymerization product of polyoxyalkylene glycol acrylate, and a lithium salt.

11. The solid electrolyte of claim 1 , wherein the solid electrolyte comprises triethylene glycol dimethyl ether, a polymerization product of polyoxyalkylene glycol acrylate, a lithium salt, and at least one selected from alumina, titania, and silica.

12. A lithium metal battery comprising:
a lithium negative electrode comprising a lithium metal or a lithium metal alloy;
a positive electrode; and
the solid electrolyte of claim 1 between the lithium negative electrode and the positive electrode.

13. The lithium metal battery of claim 12 , wherein a separator is not present between the lithium negative electrode and the positive electrode.

14. A lithium metal battery comprising:
a lithium negative electrode comprising a lithium metal or a lithium metal alloy;
a positive electrode; and
a solid electrolyte between the lithium negative electrode and the positive electrode, the solid electrolyte comprising a composite that includes:
a glycol ether,
a polymerization product of a crosslinkable polymer, and
a lithium salt.

15. The lithium metal battery of claim 14 , wherein the glycol ether is at least one selected from triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, ethylene glycol monomethyl ether (MG), diethylene glycol monomethyl ether (MDG), triethylene glycol monomethyl ether (MTG), polyethylene glycol monomethyl ether (MPG), ethylene glycol monoethyl ether (EG), diethylene glycol monoethyl ether (EDG), ethylene glycol monobutyl ether (BG), diethylene glycol monobutyl ether (BDG), triethylene glycol monobutyl ether (BTG), propylene glycol monomethyl ether (MFG), and dipropylene glycol monomethyl ether (MFDG).

16. The lithium metal battery of claim 14 , wherein the crosslinkable polymer is at least one selected from polyoxyethylene glycol diacrylate and polyoxyethylene glycol dimethacrylate.

17. The lithium metal battery of claim 14 , wherein an amount of the glycol ether is about 10 parts to about 80 parts by weight with respect to 100 parts by weight of the crosslinkable polymer.

18. The lithium metal battery of claim 14 , wherein the solid electrolyte further comprises ion-conductive inorganic particles.

19. The lithium metal battery of claim 18 , wherein the ion-conductive inorganic particles are uniformly dispersed in the solid electrolyte.

20. The lithium metal battery of claim 14 , wherein the ion-conductive inorganic particles comprise at least one selected from 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,Ti)O 3 (PZT), Pb 1−x La x Zr 1−y Ti y O 3 (PLZT) (wherein 0≤x<1 and 0≤y<1), Pb(Mg 3 Nb 2/3 )O 3 —PbTiO 3 (PMN-PT), 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, lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li x Ti y (PO 4 ) 3 , wherein 0<x<2 and 0<y<3), lithium aluminum titanium phosphate (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, Ga) x (Ti, Ge) 2−x Si y P 3−y O 12 (wherein 0≤x<1 and 0≤y<l), lithium lanthanum titanate (Li x La y TiO 3 , wherein 0<x<2 and 0<y<3), lithium germanium thiophosphate (Li x Ge y P z S w , wherein 0<x<4, 0<y<1, 0<z<1, and 0<w<5), a lithium nitride glass (Li x N y , wherein 0<x<4 and 0<y<2), SiS 2 (Li x Si y S z , wherein 0<x<3,0<y<2, and 0<z<4), a P 2 S 5 glass (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 (Li 3+x La 3 M 2 O 12 , wherein M is Te, Nb, or Zr, and x is an integer from 1 to 10), or a combination thereof.

Assignees

• Samsung Sdi Co Ltd

Inventors

• Yoo Heeeun
• Kim Duckhyun
• Kwon Taeri
• Bae Taehyun
• Shin Woocheol
• Lee Minju
• Cha Siyoung

Classifications

• H01M10/0525

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

• H01M10/056 Primary

  characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes · CPC title

• H01M2300/0082

  Organic polymers · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M2300/0068

  inorganic · CPC title