Lithium secondary battery

Patent metadata

Field	Value
Publication number	US-10439188-B2
Application number	US-201514716266-A
Country	US
Kind code	B2
Filing date	May 19, 2015
Priority date	Aug 10, 2009
Publication date	Oct 8, 2019
Grant date	Oct 8, 2019

Abstract

A lithium secondary battery includes a cathode, an anode, a separator interposed between the cathode and the anode, and a non-aqueous electrolyte solution obtained by dissolving lithium salt in a non-aqueous solvent. The separator includes a porous substrate having pores; and a porous coating layer located on at least one surface of the porous substrate and having inorganic particles and a binder polymer, the inorganic particles being connected and fixed to each other by means of the binder polymer, the porous coating layer having pores therein formed by interstitial volumes among the inorganic particles. The non-aqueous electrolyte solution has a viscosity of 1.4 cP or above at 25° C. This lithium secondary battery gives improved safety and excellent charging/discharging characteristics due to a low risk of leakage of a non-aqueous electrolyte solution and good wettability of separator with the solvent.

First claim

What is claimed is:

1. A lithium secondary battery, which includes a cathode, an anode, a separator interposed between the cathode and the anode, and a non-aqueous electrolyte solution comprising a lithium salt and a non-aqueous solvent,
wherein the separator includes:
a porous substrate having pores; and
a porous coating layer located on at least one surface of the porous substrate and having inorganic particles and a binder polymer, the inorganic particles being connected and fixed to each other by means of the binder polymer, and the porous coating layer having pores therein formed by interstitial volumes among the inorganic particles,
wherein the non-aqueous electrolyte solution has a viscosity of 3.5 cP or above and 60 cP or less at 25° C., and
wherein the non-aqueous solvent is a high-viscous non-aqueous solvent having a viscosity of 4.1 cP or above and 50 cP or less at 25° C.

2. The lithium secondary battery according to claim 1 , wherein the non-aqueous solvent is selected from group consisting of γ-butyrolactone, fluoroethylene carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, 2,3-butylene carbonate, iso-butylene carbonate, difluoroethylene carbonate, sulfolane, succinonitrile, glutaronitrile, adiponitrile, suberonitrile, sebaconitrile, and their mixtures.

3. The lithium secondary battery according to claim 1 , wherein the lithium salt is included in a concentration of 0.8 M or above and 2.0 M or less in the non-aqueous electrolyte solution.

4. The lithium secondary battery according to claim 1 , wherein the lithium salts are at least one selected from the group consisting of LiPF 6 , LiBF 4 , LiFSI (Lithium bis(fluorosulfonyl)imide, F 2 NO 4 S 2 Li), LiBETI (lithium bisperfluoroethanesulfonimide, LiN(C 2 F 5 SO 2 ) 2 ), LiTFSI (lithium (bis)trifluoromethanesulfonimide, LiN(CF 3 SO 2 ) 2 ), CF 3 SO 3 Li, LiC(CF 3 SO 2 ) 3 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiDFOB (LiC 2 BO 4 F 2 ), LiTFOP (LiC 2 PO 4 F 4 ), LiDFOP (LiC 4 PO 4 F 2 ), LiDFP (LiPO 2 F 2 ), LiN(C 2 F 5 SO 2 ) 2 and LiBOB(LiC 4 BO 8 ) and mixtures thereof.

5. The lithium secondary battery according to claim 1 ,
wherein the non-aqueous electrolyte solution has a viscosity of 3.5 cP or above and 50 cP or less at 25° C.

6. The lithium secondary battery according to claim 1 ,
wherein the porous substrate is a polyolefin-based porous film.

7. The lithium secondary battery according to claim 5 , wherein the polyolefin-based porous film is any one polymer selected from the group consisting of polyethylene, polypropylene, polybutylene and polypentene, or their mixtures.

8. The lithium secondary battery according to claim 1 , wherein the porous substrate is a non-woven fabric made of any one polymer selected from the group consisting of polyester, polyacetal, polyamide, polycarbonate, polyimide, polyetheretherketone, polyethersulfone, polyphenylene oxide, polyphenylene sulfide and polyethylene naphthalene, or their mixtures.

9. The lithium secondary battery according to claim 1 , wherein the inorganic particles have an average diameter of 0.001 to 10 μm.

10. The lithium secondary battery according to claim 1 , wherein the inorganic particles are selected from the group consisting of inorganic particles having a dielectric constant of 5 or above and inorganic particles having lithium ion transferring capability, or their mixtures.

11. The lithium secondary battery according to claim 10 , wherein the inorganic particles having a dielectric constant of 5 or above are any one kind of inorganic particles selected from the group consisting of BaTiO 3 , Pb(Zr,Ti)O 3 (PZT), Pb 1-x La x Zr 1-y Ti y O 3 (PLZT, here 0<x<1, 0<y<1), Pb(Mg 1/3 Nb 2/3 )O 3 —PbTiO 3 (PMN-PT), hafnia (HfO 2 ), SrTiO 3 , SnO 2 , CeO 2 , MgO, NiO, CaO, ZnO, ZrO 2 , SiO 2 , Y 2 O 3 , Al 2 O 3 , SiC and TiO 2 , or their mixtures.

12. The lithium secondary battery according to claim 10 , wherein the inorganic particles having lithium ion transferring capability are any one kind of inorganic particles selected from the group consisting of lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li x Ti y (PO 4 ) 3 , 0<x<2, 0<y<3), lithium aluminum titanium phosphate (Li x Al y Ti z (PO 4 ) 3 , 0<x<2, 0<y<1, 0<z<3), (LiAlTiP) x O y -based glass (0<x<4, 0<y<13), lithium lanthanum titanate (Li x La y TiO 3 , 0<x<2, 0<y<3), lithium germanium thiophosphate (Li x Ge y P z S w , 0<x<4, 0<y<1, 0<z<1, 0<w<5), lithium nitride (Li x N y , 0<x<4, 0<y<2), SiS 2 -based glass (Li x Si y S z , 0<x<3, 0<y<2, 0<z<4) and P 2 S 5 -based glass (Li x P y S z , 0<x<3, 0<y<3, 0<z<7), or their mixtures.

13. The lithium secondary battery according to claim 1 , wherein the binder polymer has a solubility parameter of 15 to 45 Mpa 1/2 .

14. The lithium secondary battery according to claim 1 , wherein the binder polymer is any one binder polymer selected from the group consisting of polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene, polymethylmethacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinylacetate, polyethylene-co-vinyl acetate, polyethylene oxide, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cyanoethylpullulan, cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose, pullulan and carboxyl methyl cellulose, or their mixtures.

15. The lithium secondary battery according to claim 1 , wherein a weight ratio of the inorganic particles and the binder polymer in the porous coating layer is 50:50 to 99:1.

16. The lithium secondary battery according to claim 1 , wherein the porous substrate has a thickness of 1 to 100 μm, and the porous coating layer has a thickness of 0.01 to 20 μm.

17. The lithium secondary battery according to claim 1 , wherein the anode is composed of at least one selected from the group consisting of lithium metal, lithium alloy, carbon, petroleum coke, activated carbon, graphite and lithium adsorption material.

18. The lithium secondary battery according to claim 1 , wherein the non-aqueous solvent is at least one selected from the group consisting of γ-butyrolactone, fluoroethylene carbonate, ethylene carbonate, dimethyl carbonate, 1-ethyl-3-methylimidazolium (EMI)-trifluoromethanesulfonylamide (CF 3 SO 2 ) 2 N), and their mixtures.

Assignees

• Lg Chemical Ltd
• Toray Battery Separator Film
• Toray Industries

Inventors

• Yu Sung-Hoon

Classifications

• H01M10/0569 Primary

  characterised by the solvents · CPC title

• H01M50/457

  comprising three or more layers · CPC title

• H01M50/451

  comprising layers of only organic material and layers containing inorganic material · CPC title

• H01M50/491

  Porosity · CPC title

• H01M2300/004

  Three solvents · CPC title