Composite, method of preparing the composite, electrolyte comprising the composite, and lithium secondary battery comprising the electrolyte

Patent metadata

Field	Value
Publication number	US-10290898-B2
Application number	US-201514838472-A
Country	US
Kind code	B2
Filing date	Aug 28, 2015
Priority date	Aug 29, 2014
Publication date	May 14, 2019
Grant date	May 14, 2019

Abstract

A composite including a metal-organic framework; and an ionic liquid disposed in a pore defined by the metal-organic framework. Also a method of preparing the composite, an electrolyte including the composite, and a lithium secondary battery including the electrolyte.

First claim

What is claimed is:

1. A composite comprising:
a metal-organic framework; and
an ionic liquid disposed in a pore defined by the metal-organic framework, wherein an amount of the ionic liquid is in a range of about 0.1 parts to about 20 parts by weight, based on 100 parts by weight of a total weight of the composite,
wherein the metal-organic framework is a compound represented by Formula 1:
M m O k X l L p   Formula 1

wherein, in Formula 1,
M is at least one selected from Ti 4+ , Zr 4+ , Mn 4+ , Si 4+ , Al 3+ , Cr 3+ , V 3+ , Ga 3+ , Mn 3+ , Zn +3 , Mn 2+ , Mg 2+ , Fe 2+ , Fe 3+ , and Cu +2 ,
m is an integer of 1 to 10,
k is 0 or an integer of 1 to 10,
l is 0 or an integer of 1 to 10,
p is an integer of 1 to 10,
X is H, OH − , Cl − , F − , I − , Br − , SO 4 2− , NO 3 − , ClO 4 − , PF 6 − , BF 3 − , R 1 —(COO) n − , R 1 —(SO 3 ) n − , or R 1 —(PO 3 ) n − , where R 1 is at least one selected from a hydrogen and a C1-C30 alkyl group,
n is an integer of 1 to 4, and
L is a ligand of the formula R—(*COO—#) q , wherein q is an integer of 1 to 6, * indicates a binding site of the carboxylate group to R, # indicates a binding site of the carboxylate group to metal ion M, and R is selected from a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted monocyclic C6-C30 aryl group, a substituted or unsubstituted polycyclic C10-C30 aryl group, a substituted or unsubstituted monocyclic C3-C30 heteroaryl group, and a substituted or unsubstituted polycyclic C10-C30 heteroaryl group, and
wherein,
when M is Zr 4+ , Cr 3+ , Zn +3 , Mn 2+ , Mg 2+ , or Cu +2 , at least one of k and 1 is an integer of 1 to 10,
when M is Cr 3+ , X is Cl—, I—, Br—, SO 4 2 —, NO 3 —, ClO 4 —, PF 6 —, BF 3 − , R 1 —(COO) n − , R 1 —(SO 3 ) n − , or R 1 —(PO 3 ) n − , and
when M is Al 3+ , Fe 2+ , or Fe 3+ , X is Cl—, F—, I—, Br—, SO 4 2− , NO 3 − , ClO 4 − , PF 6 − , BF 3 —, R 1 —(COO)n-, R 1 —(SO 3 )n-, or R 1 —(PO 3 )n-.

2. The composite of claim 1 , wherein the metal-organic framework is a compound represented by Formula 2:
M′ m O k X′ l L′ p   Formula 2

wherein, in Formula 2,
M′ is at least one selected from Ti 4+ , Zr 4+ , V″, Zn +3 , Fe 2+ , Fe 3+ , and Cu +2 ,
L′ is at least one selected from C 6 H 4 (CO 2 − ) 2 , C 2 H 2 (CO 2 − ) 2 , C 4 H 4 (CO 2 − ) 2 , C 5 H 3 S(CO 2 − ) 2 , C 6 H 2 N 2 (CO 2 ) 2 , C 2 H 4 (CO 2 − ) 2 , C 3 H 6 (CO 2 − ) 2 , C 4 H 8 (CO 2 − ) 2 , C 10 H 6 (CO 2 − ) 2 , C 12 H 8 (CO 2 − ) 2 , C 12 H 8 N 2 (CO 2 − ) 2 , C 6 H 3 (CO 2 − ) 3 , C 6 H 3 (CO 2 − ) 3 , C 24 H 15 (CO 2 − ) 3 , C 6 H 2 (CO 2 − ) 4 , C 10 H 4 (CO 2 − ) 4 , C 10 H 4 (CO 2 − ) 4 , and C 12 H 6 (CO 2 − ) 4 ,
X′ is at least one selected from OH − , Cl − , F − , CH 3 COO − , PF 6 − , and ClO 4 − ,
m is an integer of 1 to 8,
k is 0 or an integer of 1 to 8,
l is 0 or an integer of 1 to 8, and
p is an integer of 1 to
wherein,
when M is Zr 4+ , Cr 3+ , Zn +3 , Mn 2+ , Mg 2+ , or Cu +2 , at least one of k and 1 is an integer of 1 to 8,
when M is Cr 3+ , X is Cl—, I—, Br—, SO 4 2 —, NO 3 —, ClO 4 —, PF 6 —, BF 3 − , R 1 —(COO) n − , R 1 —(SO 3 ) n − , or R 1 —(PO 3 ) n − , and
when M is Al 3+ , Fe 2+ , or Fe 3+ , X is Cl—, F—, I—, Br—, SO 4 2− , NO 3 − , ClO 4 − , PF 6 − , BF 3 —, R 1 —(COO)n-, R 1 —(SO 3 )n-, or R 1 —(PO 3 )n-.

3. The composite of claim 1 , wherein the metal-organic framework is at least one selected from Cu(bpy)(H 2 O) 2 (BF 4 ) 2 (bpy) wherein bpy is 4,4′-bipyridine, Ti 8 O 8 (OH) 4 [O 2 C—C 6 H 4 —CO 2 ] 6 , Ti 8 O 8 (OH) 4 [O 2 C—C 6 H 3 (NH 2 )—CO 2 ] 6 , VO[C 6 H 4 (CO 2 ) 2 ], Al(OH)[C 6 H 4 (CO 2 ) 2 ], Cr 3 OX l [C 6 H 4 (CO 2 ) 2 ] 3 wherein X is at least one selected from Cl − , CH 3 COO − , PF 6 − , and ClO 4 − , and l is 0 or an integer of 1 to 8, Cr 3 OX l [C 12 H 8 (CO 2 ) 2 ] 3 wherein X is at least one selected from Cl − , CH 3 COO − , PF 6 − , and ClO 4 − , and l is 0 or an integer of 1 to 8, Cr 3 OX l [C 6 H 3 (CO 2 ) 3 ] 3 wherein X is at least one selected from Cl − , CH 3 COO − , PF 6 − , and ClO 4 − , and l is 0 or an integer of 1 to 8, Al 8 (OH) 15 (H 2 O) 3 [C 6 H 3 (CO 2 ) 3 ] 3 , V 3 OX l [C 6 H 3 (CO 2 ) 3 ] 3 wherein X is at least one selected from —H, OH − , Cl − , F − , CH 3 COO − , PF 6 − , and ClO 4 − , and l is 0 or an integer of 1 to 8, ZrO[C 6 H 4 (CO 2 ) 2 ], and Ti 8 O 8 (OH) 4 [O 2 C—C 6 H 3 (NH 2 )—CO 2 ] 6 .

4. The composite of claim 1 , wherein the ionic liquid comprises at least one compound selected from compounds each comprising
a cation of at least one selected from an ammonium, a pyrrolidinium, a pyridinium, a pyrimidinium, an imidazolium, a piperidinium, a pyrazolium, an oxazolium, a pyridazinium, a phosphonium, a sulfonium, and a triazolium, and
at least one anion selected from BF 4 − , PF 6 − , AsF 6 − , SbF 6 − , AlCl 4 − , HSO 4 − , ClO 4 − , Cl—, Br—, I—, CF 3 SO 3 − , CF 3 CO 2 − , NO 3 − , Al 2 Cl 7 − , CH 3 COO − , CH 3 SO 3 − , (CF 3 SO 2 ) 3 C − , (CF 3 CF 2 S SO 2 ) 2 N − , (CF 3 SO 2 ) 2 N—, (FSO 2 ) 2 N—, (CF 3 ) 2 PF 4 − , (CF 3 ) 3 PF 3 − , (CF 3 ) 4 PF 2 − , (CF 3 ) 5 PF − , (CF 3 ) 6 P − , SF 5 CF 2 SO 3 − , SF 5 CHFCF 2 SO 3 − , CF 3 CF 2 (CF 3 ) 2 CO − , (CF 3 SO 2 ) 2 CH − , (SF 5 ) 3 C − , (C 2 F 5 SO 2 )(CF 3 SO 2 )N − and (O(CF 3 ) 2 C 2 (CF 3 ) 2 O) 2 PO − .

5. The composite of claim 1 , wherein the ionic liquid is at least one selected from N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, N-butyl-N-methylpyrrolidinium bis(3-trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

6. The composite of claim 1 , wherein the metal-organic framework has a size of about 1 nanometer to about 1 micrometer, a specific surface area of about 100 square meters per gram or greater, and the pore defined by the metal-organic framework has an average diameter of about 0.1 nanometer to about 10 nanometers.

7. The composite of claim 1 , further comprising at least one selected from an alkali metal salt and an alkaline earth metal salt.

8. The composite of claim 1 , further comprising at least one selected from an alkali metal salt and an alkaline earth metal salt disposed in a pore defined by the metal-organic framework.

9. The composite of claim 1 , further comprising an additional metal-organic framework.

10. An electrolyte comprising an ion-conductive polymer and a composite according to claim 1 .

11. The electrolyte of claim 10 , wherein an amount of the composite is in a range of about 0.1 parts to about 60 parts by weight, based on 100 parts by weight of a total weight of the electrolyte.

12. The electrolyte of claim 10 , further comprising at least one selected from an alkali metal salt and an alkaline earth metal salt.

13. The electrolyte of claim 12 , wherein the alkali metal salt and the alkaline earth metal 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, LiSbF 6 , Li(CF 3 SO 2 ) 3 C, LiN(SO 2 C 2 F 5 ) 2 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 CF 2 CF 3 ) 2 , LiN(CF 3 SO 2 ) 2 , LiPF 3 (CF 2 CF 3 ) 3 , LiPF 3 (C 2 F 5 ) 3 , LiPF 3 (CF 3 ) 3 , LiB(C 2 O 4 ) 2 , NaSCN, NaSO 3 CF 3 , KTFSI, NaTFSI, Ba(TFSI) 2 , Pb(TFSI) 2 , Ca(TFSI) 2 , and LiPF 3 (CF 2 CF 3 ) 3 .

14. The electrolyte of claim 12 , wherein the at least one selected from the alkali metal salt and the alkaline earth metal salt ha

Assignees

• Samsung Electronics Co Ltd

Inventors

• Choi Hongsoo
• Lee Yonggun
• Lee Jenam

Classifications

• H01M10/0525 Primary

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

• H01M10/0563

  Liquid materials, e.g. for Li-SOCl2 cells · CPC title

• Y02T10/7011

  Cross-Sectional Technologies · mapped topic

• H01M2220/20

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

• H01M10/056

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