IP Library › Granted Patent US 11,316,194
Granted Patent B2
US 11,316,194 · App. 16/761,488 · Granted Apr 26, 2022

Gel polymer electrolyte composition, gel polymer electrolyte prepared thereby, and lithium secondary battery including the gel polymer electrolyte

Inventors: Won Kyung Shin (Daejeon, KR); Kyoung Ho Ahn (Daejeon, KR); Chul Haeng Lee (Daejeon, KR)
Assignee: LG Energy Solution, Ltd.
H01M10/0565H01M10/052H01M10/0525H01M2300/0045H01M2300/0082H01M2300/0085
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Quick Facts
Patent No.
US 11,316,194
App. No.
16/761,488
Granted
Apr 26, 2022
Kind
B2
Abstract

The present invention relates to a gel polymer electrolyte composition and a lithium secondary battery including the same, and particularly, to a gel polymer electrolyte composition, in which flame retardancy is improved by including an ionic liquid, instead of a non-aqueous organic solvent, as well as a lithium salt, a polymerization initiator, and an oligomer having a specific structure, and a lithium secondary battery in which high-temperature stability is improved by including the same.

Claims (55)

1. A gel polymer electrolyte composition for a lithium secondary battery, the gel polymer electrolyte composition comprising:

a lithium salt, an ionic liquid, a polymerization initiator, and

an oligomer, represented by Formula 1:

wherein, in Formula 1,

R is an aliphatic hydrocarbon group or an aromatic hydrocarbon group,

R a , R b , R c , and R d are each independently an unsubstituted or substituted alkyl group having 1 to 3 carbon atoms,

R 0 is an unsubstituted or substituted alkylene group having 1 to 5 carbon atoms or

wherein R 01 is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, an unsubstituted or substituted alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms which has a heteroatom, an unsubstituted or substituted aryl group, or an unsubstituted or substituted heteroaryl group, R 02 is hydrogen or an unsubstituted or substituted alkyl group having 1 to 3 carbon atoms,

R′ and R″ are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms,

R e is an unsubstituted or substituted alkylene group having 1 to 5 carbon atoms,

a is an integer of 1 to 3,

b is an integer of 0 to 2,

n, m, o, x, and y are numbers of repeating units,

n is an integer of 1 to 10,

m and o are each independently an integer of 1 to 5, and

x and y are each independently an integer of 1 to 15,

wherein the ionic liquid includes an anion component selected from the group consisting of ClO 4 − , bis(fluorosulfonyl)imide (N(SO 2 F) 2 − ; FSI), bisperfluoroethanesulfonimide (N(SO 2 C 2 F 5 ) 2 − ), and oxalyldifluoroborate (BF 2 (C 2 O 4 ) − ; ODFB).

2. The gel polymer electrolyte composition for a lithium secondary battery of claim 1 , wherein the lithium salt comprises Li + as a cation, and at least one anion selected from the group consisting of BF 4 − , PF 6 − , ClO 4 − , bis(fluorosulfonyl)imide (N(SO 2 F) 2 − ; FSI), (bis)trifluoromethanesulfonimide (N(SO 2 CF 3 ) 2 − , TFSI), bisperfluoroethanesulfonimide (N(SO 2 C 2 F 5 ) 2 − ), and oxalyldifluoroborate (BF 2 (C 2 O 4 ) − , ODFB).

3. The gel polymer electrolyte composition for a lithium secondary battery of claim 1 , wherein the ionic liquid comprises an anion component which is the same as an anion of the lithium salt, and a cation component comprising comprises at least one selected from the group consisting of compounds represented by Formulae 2 to 6:

wherein, in Formula 2, R 1 , R 2 , R 3 , and R 4 are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms,

wherein, in Formula 3, R 5 and R 6 are each independently an alkyl group having 1 to 5 carbon atoms,

wherein, in Formula 4, R 7 and R 8 are each independently an alkyl group having 1 to 5 carbon atoms,

wherein, in Formula 5, R 9 , R 10 , R 11 , and R 12 are each independently an alkyl group having 1 to 5 carbon atoms,

wherein, in Formula 6, R 13 , R 14 , R 15 , and R 16 are each independently an alkyl group having 1 to 5 carbon atoms.

4. The gel polymer electrolyte composition for a lithium secondary battery according to claim 3 , wherein the cation represented by Formula 2 is at least one selected from the group consisting of cations represented by Formulae 2a and 2b:

5. The gel polymer electrolyte composition for a lithium secondary battery of claim 3 , wherein the cation component represented by Formula 3 comprises at least one selected from the group consisting of compounds represented by Formulae 3a and 3b:

6. The gel polymer electrolyte composition for a lithium secondary battery of claim 3 , wherein the cation component represented by Formula 4 comprises at least one selected from the group consisting of compounds represented by Formulae 4a and 4b:

7. The gel polymer electrolyte composition for a lithium secondary battery according to claim 3 , wherein, in Formula 5, R 9 , R 10 , R 11 , and R 12 are each independently an alkyl group having 1 to 3 carbon atoms.

8. The gel polymer electrolyte composition for a lithium secondary battery according to claim 3 , wherein the cation component represented by Formula 6 comprises a cation represented by Formula 6a:

9. The gel polymer electrolyte composition for a lithium secondary battery according to claim 1 , wherein, in Formula 1, R a , R b , R c , and R d are each independently an unsubstituted or substituted alkyl group having 1 to 2 carbon atoms,

R 0 is an unsubstituted or substituted alkylene group having 1 to 5 carbon atoms,

R′ and R″ are each independently hydrogen or an alkyl group having 1 to 2 carbon atoms,

R e is an unsubstituted or substituted alkylene group having 1 to 3 carbon atoms, and

m and o are each independently an integer of 2 to 4.

10. The gel polymer electrolyte composition for a lithium secondary battery according to claim 1 , wherein, in Formula 1, the aliphatic hydrocarbon group of R comprises (a) at least one alicyclic hydrocarbon group or (b) at least one linear hydrocarbon group,

wherein the alicyclic hydrocarbon group is selected from the group consisting of an unsubstituted or substituted cycloalkylene group having 4 to 20 carbon atoms, an unsubstituted or substituted cycloalkenylene group having 4 to 20 carbon atoms, and an unsubstituted or substituted heterocycloalkylene group having 2 to 20 carbon atoms, and

wherein the linear hydrocarbon group is selected from the group consisting of an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms, an unsubstituted or substituted alkoxylene group having 1 to 20 carbon atoms, an unsubstituted or substituted alkenylene group having 2 to 20 carbon atoms, and an unsubstituted or substituted alkynylene group having 2 to 20 carbon atoms, and

the aromatic hydrocarbon group of R comprises at least one selected from the group consisting of an unsubstituted or substituted arylene group having 6 to 20 carbon atoms and an unsubstituted or substituted heteroarylene group having 2 to 20 carbon atoms.

11. The gel polymer electrolyte composition for a lithium secondary battery according to claim 1 , wherein, in Formula 1, R is an aliphatic hydrocarbon group,

wherein the aliphatic hydrocarbon group comprises (a) at least one alicyclic hydrocarbon group or (b) at least one linear hydrocarbon group,

wherein the alicyclic hydrocarbon group is selected from the group consisting of an unsubstituted or substituted cycloalkylene group having 4 to 10 carbon atoms, an unsubstituted or substituted cycloalkenylene group having 4 to 10 carbon atoms, and an unsubstituted or substituted heterocycloalkylene group having 2 to 10 carbon atoms, and

wherein the linear hydrocarbon group is selected from the group consisting of an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an unsubstituted or substituted alkoxylene group having 1 to 10 carbon atoms, an unsubstituted or substituted alkenylene group having 2 to 10 carbon atoms, and an unsubstituted or substituted alkynylene group having 2 to 10 carbon atoms.

12. The gel polymer electrolyte composition for a lithium secondary battery according to claim 1 , wherein the oligomer represented by Formula 1 is an oligomer represented by Formula 1a:

wherein, in Formula 1a,

n1, x1, and y1 are numbers of repeating units,

n1 is an integer of 1 or 10,

x1 is an integer of 1 to 15, and

y1 is an integer of 1 to 15.

13. The gel polymer electrolyte composition for a lithium secondary battery according to claim 1 , wherein the oligomer represented by Formula 1 is included in an amount of 0.2 wt % to 30 wt % based on a total weight of the gel polymer electrolyte composition for a lithium secondary battery.

14. A gel polymer electrolyte prepared by polymerizing the gel polymer electrolyte composition for a lithium secondary battery of claim 1 .

15. A lithium secondary battery comprising the gel polymer electrolyte of claim 14 .

16. A lithium secondary battery comprising the gel polymer electrolyte composition of claim 1 .

17. The gel polymer electrolyte composition for a lithium secondary battery of claim 1 , wherein a weight-average molecular weight (Mw) of the oligomer represented by Formula 1 is present in a range of about 1,000 g/mol to about 100,000 g/mol.

18. The gel polymer electrolyte composition for a lithium secondary battery of claim 1 , wherein the gel polymer electrolyte composition does not include a non-aqueous organic solvent.

19. The gel polymer electrolyte composition for a lithium secondary battery of claim 1 , wherein the ionic liquid is included in an amount of 50 wt % or more based on a total weight of the gel polymer electrolyte composition.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 4, 2021
From: LG CHEM, LTD.
To: LG ENERGY SOLUTION, LTD.
Reel/Frame 058295/0068 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 5, 2020
From: SHIN, WON KYUNG; AHN, KYOUNG HO; LEE, CHUL HAENG
To: LG CHEM, LTD.
Reel/Frame 052574/0420 →
Priority Claims (2)
KR 10-2018-0000795 · Jan 3, 2018 · national
KR 10-2019-0000622 · Jan 3, 2019 · national
Continuity (1)
Related Publication 20200295402A1 · Sep 17, 2020