Electrolyte for lithium secondary battery and lithium secondary battery including the same
Provided is a lithium secondary battery comprising: a cathode comprising a cathode active material, an anode comprising an anode active material, a separator interposed between the cathode and the anode, and an electrolyte for a secondary battery, wherein the cathode active material is Li x (Ni a Co b Mn c )O 2 , wherein 0.90≤x≤1.10, 0.5≤a≤0.99, 0.005≤b<0.5, 0.005≤c<0.5, and a+b+c=1, and the electrolyte for a secondary battery comprises a lithium salt, a nonaqueous organic solvent, and a cyclic phosphate compound represented by the following Chemical Formula 2: wherein R 1 to R 6 and R′ and R″ are independently of one another hydrogen or C 1 -C 4 alkyl; L 2 is —CR 7 R 8 —; and R 7 and R 8 are independently of each other C 1 -C 4 alkyl .
1. A lithium secondary battery comprising:
a cathode comprising a cathode active material,
an anode comprising an anode active material,
a separator interposed between the cathode and the anode, and
an electrolyte for a secondary battery,
wherein the cathode active material is Li x (Ni a Co b Mn c )O 2 , wherein 0.90≤x≤1.10, 0.5≤a≤0.99, 0.005≤b<0.5, 0.005≤c<0.5, and a+b+c=1, and
the electrolyte for a secondary battery comprises a lithium salt, a nonaqueous organic solvent, an oxalatoborate-based compound, and a cyclic phosphate compound represented by the following Chemical Formula 2:
wherein
R 1 to R 6 and R′ and R″ are independently of one another hydrogen or C1-C4 alkyl;
L 2 is -CR 7 R 8 -; and
R 7 and R 8 are independently of each other hydrogen or C1-C4 alkyl..
2. The lithium secondary battery of claim 1 , wherein the cathode active material is Li(Ni a Co b Mn c )O 2 , wherein 0.5≤a≤0.8, 0.1≤b<0.5, 0.1≤c<0.5, and a+b+c=1; and
the cyclic phosphate compound is represented by the following Chemical Formula 3:
wherein R 7 and R 8 are independently of each other hydrogen or C1-C3 alkyl.
3. The lithium secondary battery of claim 2 , wherein the cathode active material is LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.5 Co 0.2 ; Mn 0.3 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , or a mixture thereof.
4. The lithium secondary battery of claim 1 , wherein the cyclic phosphate compound is any one selected from the following structures:
5. The lithium secondary battery of claim 4 , wherein the cyclic phosphate compound is included at 0.1 to 5.0 wt %, based on a total weight of the electrolyte.
6. The lithium secondary battery of claim 1 , wherein the electrolyte further comprises: one or two or more additives selected from the group consisting of an oxalatophosphate-based additive, a fluorine-substituted carbonate-based compound, a vinylidene carbonate-based compound, and a sulfinyl group-containing.
7. The lithium secondary battery of claim 6 , wherein the electrolyte further comprises: any one or two or more additives selected from the group consisting of lithium tetrafluoro(oxalato)phosphate, lithium difluoro bis(oxalato)phosphate, fluoroethylene carbonate, difluoroethylene carbonate, fluorodimethyl carbonate, fluoroethylmethyl carbonate, vinylene carbonate, vinyl ethylene carbonate, dimethyl sulfone, diethyl sulfone, ethyl methyl sulfone, methyl vinyl sulfone, divinyl sulfone, ethylene sulfite, methyl ethylene sulfite, ethyl ethylene sulfite, 4,5-dimethyl ethylene sulfite, 4,5-diethyl ethylene sulfite, propylene sulfite, 4,5-dimethyl propylene sulfite, 4,5-diethyl propylene sulfite, 4,6-dimethyl propylene sulfite, 4,6-diethyl propylene sulfite, 1,3-butylene glycol sulfite, methyl methanesulfonate, ethyl methanesulfonate, methyl ethanesulfonate, propyl methanesulfonate, methyl propanesulfonate, ethyl propanesulfonate, vinyl methanesulfonate, allyl methanesulfonate, vinyl benzenesulfonate, allyl prop-2-enesulfonate, ethanesultone, 1,3-propanesultone, 1,4-butanesultone, ethenesultone, 1,3-propenesultone, 3-fluoro-1,3-propanesultone, 1,4-butenesultone, ethylene sulfate, propylene sulfate, 2,3-butylene sulfate, 1,3-propylene sulfate, 1,3-butylene sulfate and mixtures thereof.
8. The lithium secondary battery of claim 6 , wherein the additive is included at 0.1 to 5.0 wt %, based on the total weight of the electrolyte.
9. The lithium secondary battery of claim 1 , wherein the nonaqueous organic solvent is selected from the group consisting of a cyclic carbonate-based solvent, a linear carbonate-based solvent, and a mixed solvent thereof.
10. The lithium secondary battery of claim 9 , wherein the cyclic carbonate-based solvent is selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, vinylethylene carbonate, fluoroethylene carbonate, and a mixture thereof, and the linear carbonate is selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethylmethyl carbonate, methylpropyl carbonate, methylisopropyl carbonate, ethylpropyl carbonate, and a mixture thereof.
11. The lithium secondary battery of claim 9 , wherein the nonaqueous organic solvent has a mixed volume ratio of the linear carbonate solvent to the cyclic carbonate solvent of 1:1 to 9:1.
12. The lithium secondary battery of claim 1 , wherein the lithium salt is one or two or more selected from the group consisting of LiPF 6 , LiBF 4 , LiClO 4 , LiSbF 6 , LiAsF 6 , LiN(SO 2 C 2 F 5 ) 2 , LiN(CF 3 SO 2 ) 2 , LiN(SO 3 C 2 F 5 ) 2 , LiN(SO 2 F) 2 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiC 6 H 5 SO 3 , LiSCN, LiAlO 2 , LiAlCl 4 , LiN(C x F 2x+1 SO 2 )(C y F 2y+1 SO 2 ) (wherein x and y are independently of each other a natural number), LiCl, LiI, and LiB(C 2 O 4 ) 2 .
13. The lithium secondary battery of claim 1 , wherein the lithium salt is present at a concentration of 0.1 to 2.0 M.
14. The lithium secondary battery of claim 1 , wherein the oxalatoborate-based compound is at least one of lithium difluoro(oxalato)borate and/or lithium bis(oxalato)borate.