Composition for gel polymer electrolyte and lithium secondary battery including the same

Patent metadata

Field	Value
Publication number	US-9882239-B2
Application number	US-201414248448-A
Country	US
Kind code	B2
Filing date	Apr 9, 2014
Priority date	Jan 28, 2013
Publication date	Jan 30, 2018
Grant date	Jan 30, 2018

Abstract

Provided are a composition for a gel polymer electrolyte including i) an electrolyte solution solvent, ii) an ionizable lithium salt, iii) a polymerization initiator, and iv) a monomer having a functional group bondable to metal ions, and a lithium secondary battery including the composition for a gel polymer electrolyte.
In a case where the composition for a gel polymer electrolyte of the present invention is used in a lithium secondary battery, since the movement of metal ions dissolved from a cathode to an anode may be prevented or the precipitation of metal on the anode may be reduced, the lifetime of the battery may not only be improved but capacity characteristics of the battery may also be excellent even in the case in which the battery is charged at a high voltage as well as normal voltage.

First claim

The invention claimed is:

1. A composition for a gel polymer electrolyte for a lithium secondary battery, the composition comprising:
i) an electrolyte solution solvent;
ii) an ionizable lithium salt;
iii) a polymerization initiator; and
iv) a monomer having a functional group bondable to metal ions,

wherein the monomer is an acrylate-based monomer having the functional group selected from the group consisting of

which are substituted or unsubstituted with C 1 -C 5 alkyl or halogen, and a mixture of two or more thereof.

2. The composition for a gel polymer electrolyte of claim 1 , wherein the acrylate-based monomer having the functional group is any one selected from the group consisting of the following compounds and a mixture of two or more thereof:
(1) ethyl (E)-3-(pyridin-2-yl)-acrylate;
(2) ethyl (E)-3-(4-pyridinyl)-2-propenoate;
(3) 2-propenoic acid, 3,3′-[2,2′-bipyridine]-4,4′-diylbis-, dimethyl ester;
(4) 2-propenoic acid, 2-[2,2′-bipyridine]-6-ylethyl ester;
(5) 2-propenoic acid, 2-[2,2′-bipyridine]-5-ylethyl ester;
(6) 2-propenoic acid, 2-[2,2′-bipyridine]-4-ylethyl ester;
(7) 2-propenoic acid, 1,1′-[[2,2′-bipyridine]-4,4′-diylbis(methylene)] ester;
(8) 2-propenoic acid, 1,10-phenanthroline-2,9-diylbis(methylene) ester;
(9) 2-propenoic acid, 3-(1,10-phenanthroline-2-yl)-phenylmethyl ester; and
(10) 2-propenoic acid, 2-[[(1-oxo-2-propenyl)oxy]methyl]-2-[(1,10-phenanthroline-5-ylmethoxy)methyl]-1,3-propanediyl ester.

3. The composition for a gel polymer electrolyte of claim 1 , further comprising a monomer having 2 to 6 acrylate groups,
wherein the monomer is a branched monomer.

4. The composition for a gel polymer electrolyte of claim 3 , wherein the branched monomer is any one selected from the group consisting of ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and a mixture of two or more thereof.

5. The composition for a gel polymer electrolyte of claim 1 , wherein the monomer having the functional group is included in an amount of 0.1 wt % to 10 wt % based on a total weight of the composition.

6. The composition for a gel polymer electrolyte of claim 3 , wherein the branched monomer is included in an amount of 0.1 wt % to 10 wt % based on the total weight of the composition.

7. The composition for a gel polymer electrolyte of claim 3 , wherein a content ratio(weight ratio) of the monomer having the functional group to the branched monomer is in a range of 1:0.1 to 1:10.

8. The composition for a gel polymer electrolyte of claim 1 , wherein the lithium salt is any one selected from the group consisting of LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiN(C 2 F 5 SO 2 ) 2 , LiN(CF 3 SO 2 ) 2 , CF 3 SO 3 Li, LiC(CF 3 SO 2 ) 3 , LiC 4 BO 8 , and a mixture of two or more thereof.

9. The composition for a gel polymer electrolyte of claim 1 , wherein the electrolyte solution solvent is linear carbonate, cyclic carbonate, or a combination thereof.

10. The composition for a gel polymer electrolyte of claim 9 , wherein the linear carbonate comprises any one selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethylmethyl carbonate, methylpropyl carbonate, and ethylpropyl carbonate, and a mixture of two or more thereof, and the cyclic carbonate comprises any one selected from the group consisting of ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate, a halide thereof, and a mixture of two or more thereof.

11. A lithium secondary battery comprising:
a cathode;
an anode;
a separator; and
a gel polymer electrolyte,
wherein the gel polymer electrolyte is formed by polymerizing the composition for a gel polymer electrolyte of claim 1 .

12. The lithium secondary battery of claim 11 , wherein the composition for a gel polymer electrolyte further comprises a monomer having 2 to 6 acrylate groups,
wherein the monomer is a branched monomer.

13. The lithium secondary battery of claim 12 , wherein the branched monomer is any one selected from the group consisting of ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and a mixture of two or more thereof.

14. The lithium secondary battery of claim 11 , wherein a charge voltage of the lithium secondary battery is in a range of 3.0 V to 5.0 V.

15. The lithium secondary battery of claim 14 , wherein the charge voltage of the lithium secondary battery is in a range of 4.3 V to 5.0 V.

16. The lithium secondary battery of claim 15 , wherein a cathode active material for the cathode is any one selected from the group consisting of compounds of Chemical Formulas 1 to 3, and a mixture of two or more thereof:
Li[Li x Ni a Co b Mn c ]O 2   <Chemical Formula 1>

(where 0<x≦0.3, 0.3≦c≦0.7, 0<a+b<0.5, and x+a+b+c=1);
LiMn 2-x M x O 4 <  Chemical Formula 2>

(where M is one or more elements selected from the group consisting of nickel (Ni), cobalt (Co), iron (Fe), phosphorus (P), sulfur (S), zirconium (Zr), titanium (Ti), and aluminum (Al), and 0<x≦2);
Li 1+a Co x M 1−x AX 4 <  Chemical Formula 3>

(where M is one or more elements selected from the group consisting of Al, magnesium (Mg), Ni, Co, manganese (Mn), Ti, gallium (Ga), copper (Cu), vanadium (V), niobium (Nb), Zr, cerium (Ce), indium (In), zinc (Zn), and yttrium (Y), X is one or more elements selected from the group consisting of oxygen (O), fluorine (F), and nitrogen (N), A is P, S, or a mixed element thereof, 0≦a≦0.2, and 0.5≦x≦1).

17. The lithium secondary battery of claim 14 , wherein a cathode active material for the cathode is any one selected from the group consisting of LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , LiNi 1−y Co y O 2 (0≦y<1), LiCo 1−y Mn y O 2 (0≦y<1), LiNi 1−y Mn y O 2 (0≦y<1), Li(Ni a Co b Mn c )O 2 (0<a,b,c≦1, a+b+c=1), and a mixture of two or more thereof.

18. A composition for a gel polymer electrolyte for a lithium secondary battery, the composition consisting of:
i) an electrolyte solution solvent;
ii) an ionizable lithium salt;
iii) a polymerization initiator; and
iv) a monomer having a functional group bondable to metal ions,

wherein the monomer is an acrylate-based monomer having the functional group selected from the group consisting of

which are substituted or unsubstituted with C 1 -C 5 alkyl or halogen, and a mixture of two or more thereof.

Assignees

• Lg Chemical Ltd

Inventors

• Yu Sung Hoon
• Yang Doo Kyung
• Shin Sun Sik
• Oh Song Taek
• Kang Yoo Sun
• Lee Kyung Mi
• Park Jin Hyun
• Suk Jung Don

Classifications

• H01M2300/0085

  Immobilising or gelification of electrolyte · CPC title

• H01M10/0565 Primary

  Polymeric materials, e.g. gel-type or solid-type · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M10/052

  Li-accumulators · CPC title

• C08L33/18

  Homopolymers or copolymers of nitriles · CPC title