Electrolyte for lithium ion rechargeable battery and lithium ion rechargeable battery including the same
The present invention is an electrolyte for a lithium ion rechargeable battery and a lithium ion rechargeable battery that includes the same. More particularly, the present invention discloses an electrolyte for a lithium ion rechargeable battery that provides excellent cycle life characteristics and high-temperatures storage stability and prevents a drop in discharge capacity of a battery at low temperature, and a lithium ion rechargeable battery including the same. The lithium ion rechargeable battery including the electrolyte provides improved cycle life characteristics and prevents the problems of a drop in discharge capacity at low temperature and high-temperature swelling through the formation of a stable SEI film at the initial charge cycle.
1. An electrolyte for a lithium rechargeable battery, comprising:
a lithium salt;
a non-aqueous organic solvent;
a first additive having a Lowest Unoccupied Molecular Orbital (LUMO) level between 0.3 eV and 0.5 eV when calculated by the AM1 (Austin Model 1) method; and
a second additive having a LUMO level between−0.2 eV and 0.3 eV or between 0.5 eV and 1.0 eV when calculated by the AM1 method.
2. The electrolyte of claim 1 , wherein the first additive is at least one compound selected from the group consisting of trimethylsilyl phosphate and lithium tetrafluoroborate.
3. The electrolyte of claim 1 , wherein the first additive has a concentration of between 0.01 wt % and 3.0 wt % based on a total weight of the electrolyte.
4. The electrolyte of claim 3 , wherein the concentration of the first additive is between 0.2 wt % and 0.5 wt %.
5. The electrolyte of claim 1 , wherein the second additive is at least one compound selected from the group consisting of vinylene carbonate and fluoroethyl carbonate.
6. The electrolyte of claim 5 , wherein the second additive has a concentration of between 0.01 wt % and 10.0 wt % based on a total weight of the electrolyte.
7. The electrolyte of claim 6 , wherein the concentration of the second additive is between 0.1 wt % and 5.0 wt %.
8. The electrolyte of claim 1 , wherein a weight ratio of the first additive to the second additive is between 0.1:1 and 1:1.
9. The electrolyte of claim 8 , wherein the weight ratio of the first additive to the second additive is between 0.2:1 and 0.5:1.
10. The electrolyte of claim 1 , wherein the non-aqueous organic solvent is selected from the group consisting of cyclic carbonate, non-cyclic carbonate, aliphatic carboxylic acid ester, non-cyclic ether, cyclic ether, alkyl phosphate ester and fluorides thereof, or a mixture containing two or more of them.
11. The electrolyte of claim 10 , wherein the cyclic carbonate is at least one compound selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate and vinylene carbonate.
12. The electrolyte of claim 10 , wherein the non-cyclic carbonate is at least one compound selected from the group consisting of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, dipropyl carbonate and methyl ethyl carbonate.
13. The electrolyte of claim 10 , wherein the aliphatic carboxylic acid ester is at least one compound selected from the group consisting of methyl formate, methyl acetate, methyl propionate and ethyl propionate.
14. The electrolyte of claim 10 , wherein the non-cyclic ether is at least one compound selected from the group consisting of gamma-lactones, 1,2-dimethoxyethane, 1,2-diethoxyethane and ethoxymethoxyethane.
15. The electrolyte of claim 10 , wherein the cyclic ether is at least one compound selected from the group consisting of tetrahydrofuran and 2-methyltetrahydrofuran.
16. The electrolyte of claim 10 , wherein the alkyl phosphate ester is at least one compound selected from the group consisting of dimethyl sulfoxide, 1,2-dioxolan, trimethyl phosphate, triethyl phosphate and trioctyl phosphate.
17. The electrolyte of claim 1 , wherein the lithium salt is at least one selected from the group consisting of LiPF 6 , LiBF 4 , LiAsF 6 , LiCIO 4 , LiCF 3 SO 3 , LiSbF 6 , LiN(SO 2 CF 3 ) 2 LiC 4 F 9 SO 3 , LiAIF 4 , LiAICI 4 LiN(SO 2 C 2 F 5 ) 2 , LiN(C x F 2x+1 So 2 )(C y F 2y+1 SO 2 ) (wherein, each of x and y is an integer), LiCI and Lil.
18. An electrolyte for a lithium rechargeable battery, comprising:
a lithium salt;
a non-aqueous organic solvent;
a first additive having a Lowest Unoccupied Molecular Orbital (LUMO) level between 0.3 eV and 0.5 eV, when calculated by the AM1 (Austin Model 1) method;
a second additive having an LUMO level between 0.5 eV and 1.0 eV, when calculated by the AM1 method; and
a third additive having an LUMO level between−0.2 eV and 0.3 eV, when calculated by the AM1 method.
19. A lithium ion rechargeable battery, comprising:
the electrolyte of claim 1 ;
a cathode including a cathode active material;
an anode including an anode active material; and
a separator disposed between the cathode and the anode.
20. The lithium ion rechargeable battery of claim 19 , wherein the cathode active material is a lithiated intercalation oxide.
21. The lithium ion rechargeable battery of claim 19 , wherein the anode active material is selected from the group consisting of crystalline carbon, amorphous carbon, carbon composites and lithium metal.
22. The lithium ion rechargeable battery of claim 21 , wherein the anode active material is crystalline carbon that has a crystalline size in the lamination direction (Lc) of 150 Å or more, d(002) of between 3.35 Å and 3.38 Å, real density of 2.2 g/cm 3 or more, BET specific surface area of between 0.5 m 2 /g and 50 m 2 /g, and average particle diameter (D50) of between 1 μm and 30 μm.
23. The lithium ion rechargeable battery of claim 21 , wherein the anode active material has an intensity ratio of I(1360) surface to I(1590) surface in the Raman spectrum [I( 1 360 cm −1 )/I(1590 cm −1 )] of 0.05 or more.
24. A lithium ion rechargeable battery of claim 21 , wherein the anode active material has a peak intensity ratio of I(110) surface to I(002) surface in the X-ray diffraction pattern [X(I(110)/I(002))] of less than 0.2.