Lithium metal battery

Patent metadata

Field	Value
Publication number	US-9831529-B2
Application number	US-201615047187-A
Country	US
Kind code	B2
Filing date	Feb 18, 2016
Priority date	May 20, 2015
Publication date	Nov 28, 2017
Grant date	Nov 28, 2017

Abstract

A lithium metal battery including: a lithium negative electrode including lithium metal; a positive electrode; and an electrolyte interposed between the lithium negative electrode and the positive electrode, wherein the electrolyte contains non-fluorine substituted ether, which is capable of solvating lithium ions, a fluorine substituted ether represented by the following Formula 1, and a lithium salt, wherein an amount of the fluorine substituted ether represented by Formula 1 is greater than an amount of the non-fluorine substituted ether,

R—{O(CH 2 ) a } b —CH 2 —O—C n F 2n H  Formula 1
wherein R is —C m F 2m H or —C m F 2m+1 , n is an integer of 2 or greater, m is an integer of 1 or greater, a is an integer of 1 or 2, and b is 0 or 1.

First claim

What is claimed is:

1. A lithium metal battery comprising:
a negative electrode comprising lithium metal;
a positive electrode; and
an electrolyte interposed between the lithium negative electrode and the positive electrode,
wherein the electrolyte contains
a non-fluorine substituted ether, which is capable of solvating lithium ions,
a fluorine substituted ether represented by Formula 1, and
a lithium salt,
wherein an amount of the fluorine substituted ether represented by Formula 1 is greater than an amount of the non-fluorine substituted ether,
R—{O(CH 2 ) a } b —CH 2 —O—C n F 2n H  Formula 1

wherein R is —C m F 2m H or —C m F 2m+1 , n is an integer of 2 or greater, m is an integer of 1 or greater, a is an integer of 1 or 2, and b is 0 or 1, and
wherein a concentration of the lithium salt is from about 3.3 molar to about 7 molar.

2. The lithium metal battery of claim 1 , wherein the electrolyte has a viscosity of about 5 centipoise or less.

3. The lithium metal battery of claim 1 , wherein a concentration of the lithium salt is in a range of about 5 molar to about 7 molar.

4. The lithium metal battery of claim 1 , wherein an amount of the fluorine substituted ether represented by Formula 1 is in a range of about 55% by volume to about 85% by volume, based on a total volume of the non-fluorine substituted ether and the fluorine substituted ether.

5. The lithium metal battery of claim 1 , wherein an amount of the non-fluorine substituted ether is in a range of about 15% by volume to about 45% by volume, based on a total volume of the non-fluorine substituted ether and the fluorine substituted ether.

6. The lithium metal battery of claim 1 , wherein a concentration of the lithium salt is in a range of about 4 molar to about 6 molar.

7. The lithium metal battery of claim 1 , wherein n is an integer of 2 to 5, and m is an integer of 1 to 5.

8. The lithium metal battery of claim 1 , wherein R is —CF 2 CF 2 H, —CF 2 CF 2 CF 2 H, —CF 2 CF 2 CF 2 CF 2 H, or —CF 3 .

9. The lithium metal battery of claim 1 , wherein the fluorine substituted ether is of the formula
R—{O(CH 2 ) a } b —CH 2 —O—CF 2 CF 2 H,

R—{O(CH 2 ) a } b —CH 2 —O—CF 2 CF 2 CF 2 H, or

R—{O(CH 2 ) a } b —CH 2 —O—CF 2 CF 2 CF 2 CF 2 H.

10. The lithium metal battery of claim 1 , wherein the fluorine substituted ether is a compound represented by Formula 2:
R—CH 2 —O—C n F 2n H  Formula 2

wherein R is —C m+1 H m F 2m or —C m F 2m+1 , n is an integer of 2 to 5, and m is an integer of 1 to 5.

11. The lithium metal battery of claim 1 , wherein the fluorine substituted ether represented by Formula 1 is one or more selected from HCF 2 CF 2 CH 2 OCF 2 CF 2 H, HCF 2 CF 2 CH 2 OCF 2 CF 2 CF 2 CF 2 H, HCF 2 CF 2 OCH 2 CF 3 , HCF 2 CF 2 OCH 2 CH 2 OCF 2 CF 2 H, HCF 2 CF 2 OCH 2 CH 2 OCF 2 CF 2 H, HCF 2 CF 2 OCH 2 CH 2 CH 2 OCF 2 CF 2 H, HCF 2 CF 2 CH 2 OCF 2 CF 2 CF 2 H, HCF 2 CF 2 OCH 2 CH 2 OCF 2 CF 2 CF 2 H, and HCF 2 CF 2 OCH 2 CH 2 CH 2 OCF 2 CF 2 CF 2 H.

12. The lithium metal battery of claim 1 , wherein the non-fluorine substituted ether is a glyme solvent.

13. The lithium metal battery of claim 1 , wherein the non-fluorine substituted ether is one or more selected from ethyleneglycol dimethylether, ethyleneglycol diethylether, propyleneglycol dimethylether, propyleneglycol diethylether, butyleneglycol dimethylether, butyleneglycol diethylether, diethyleneglycol dimethylether, triethyleneglycol dimethylether, tetraethyleneglycol dimethyl ether, diethyleneglycol diethylether, triethyleneglycol diethylether, tetraethyleneglycol diethylether, dipropyleneglycol dimethylether, tripropyleneglycol dimethylether, tetrapropyleneglycol dimethylether, dipropyleneglycol diethylether, tripropyleneglycol diethylether, tetrapropyleneglycol diethylether, dibutyleneglycol dimethylether, tributyleneglycol dimethylether, tetrabutyleneglycol dimethylether, dibutyleneglycol diethylether, tributyleneglycol diethylether, tetrabutyleneglycol diethylether, poly(ethylene glycol) dilaurate, poly(ethylene glycol) monoacrylate, and poly(ethylene glycol) diacrylate.

14. The lithium metal battery of claim 1 , wherein the lithium salt is one or more 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, and lithium bis(oxalato)borate.

15. The lithium metal battery of claim 1 , wherein the lithium salt is a fluorine-containing sulfone and is one or more selected from LiN(FSO 2 ) 2 , LiN(CF 3 SO 2 ) 2 , LiN(CF 2 SO 2 )(CF 3 CF 2 CF 2 CF 2 SO 2 ), LiN(CF 3 CF 2 SO 2 ) 2 , LiC(CF 3 SO 2 ) 2 , and LiC(CF 3 CF 2 SO 2 ) 2 .

16. The lithium metal battery of claim 1 , wherein a concentration of the lithium salt is from about 5 molar to about 7 molar, and
wherein the electrolyte has a viscosity range of about 5 centipoise or less.

17. The lithium metal battery of claim 1 , wherein the electrolyte has an ion conductivity of about 1.0 milliSiemens per centimeter or greater at 25° C.

18. The lithium metal battery of claim 1 , wherein the non-fluorine substituted ether is contained in an amount ranging from about 20% by volume to about 40% by volume, based on the total amount of the non-fluorine substituted ether and the fluorine substituted ether.

19. The lithium metal battery of claim 1 , wherein the electrolyte comprises ethylene glycol dimethyl ether, one or more selected from HCF 2 CF 2 CH 2 OCF 2 CF 2 H and HCF 2 CF 2 CH 2 OCF 2 CF 2 CF 2 CF 2 H, and one or more selected from LiN(FSO 2 ) 2 and LiN(CF 4 SO 2 ) 2 .

20. The lithium metal battery of claim 1 , wherein the electrolyte further comprises one or more selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, butylene carbonate, ethylmethyl carbonate, fluoroethylene carbonate, methylpropyl carbonate, ethylpropyl carbonate, methylisopropyl carbonate, dipropyl carbonate, dibutyl carbonate, gamma butyrolactone, dimethylene glycol dimethyl ether, trimethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, succinonitrile, dimethyl sulfone, ethylmethyl sulfone, diethyl sulfone, adiponitrile, 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether, 2,3,3,4,4,5,5-octafluoropentyl 1,1,2,2-tetrafluoroethyl ether, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, γ-butyrolactone, dioxolane, 4-methyldioxolane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, dioxane, sulfolane, dichloroethane, chlorobenzene, and nitrobenzene.

21. An electrolyte for a lithium metal battery, the electrolyte comprising:
a non-fluorine substituted ether, which is capable of solvating lithium ions,
a fluorine substituted ether represented by Formula 1, and
a lithium salt,
wherein the amount of the fluorine substituted ether represented by Formula 1 is greater than an amount of the non-fluorine substituted ether,
R—{O(CH 2 ) a } b —CH 2 —O—C n F 2n H  Formula 1

wherein R is —C m F 2m H or —C m F 2m+1 , n is an integer of 2 or greater, m is an integer of 1 or greater, a is an integer of 1 or 2, and b is 0 or 1 and
wherein a concentration of the lithium salt is from about 3.3 molar to about 7 molar.

22. The electrolyte of claim 21 , wherein the amount of the fluorine substitute

Assignees

• Samsung Electronics Co Ltd

Inventors

• Chang Wonseok
• Mizumo Tomonobu
• Sugimoto Toshinori
• Kang Hyorang
• Park Joungwon
• Lee Yonggun
• Choi Hongsoo
• Park Hosang

Classifications

• H01M50/426

  Fluorocarbon polymers · CPC title

• H01M50/417

  Polyolefins · CPC title

• H01M50/491

  Porosity · CPC title

• H01M2004/027

  Negative electrodes · CPC title

• H01M4/134

  Electrodes based on metals, Si or alloys · CPC title