Lithium battery

1. A lithium battery, comprising:

a cathode including a cathode active material;

an anode including an anode active material; and

an organic electrolytic solution between the cathode and the anode,

wherein:

the anode active material includes a metal-based anode active material,

the organic electrolytic solution includes a first lithium salt; an organic solvent; and a bicyclic sulfate-based compound represented by Formula 1 below:

in Formula 1, each of A 1 , A 2 , A 3 , and A 4 is independently a covalent bond, a substituted or unsubstituted C 1 -C 5 alkylene group, a carbonyl group, or a sulfinyl group, provided that A 1 and A 2 are not simultaneously a covalent bond and provided that A 3 and A 4 are not simultaneously a covalent bond,

the metal-based anode active material includes a composite of a silicon-based compound and a carbonaceous compound,

the composite of the silicon-based compound and the carbonaceous compound includes carbon-coated silicon nanoparticles, and

the composite of the silicon-based compound and the carbonaceous compound has a mean particle diameter of about 5 μm to about 20 μm.

2. The lithium battery as claimed in claim 1 , wherein at least one of A 1 , A 2 , A 3 , and A 4 is an unsubstituted or substituted C 1 -C 5 alkylene group, wherein a substituent of the substituted C 1 -C 5 alkylene group is a halogen-substituted or unsubstituted C 1 -C 20 alkyl group, a halogen-substituted or unsubstituted C 2 -C 20 alkenyl group, a halogen-substituted or unsubstituted C 2 -C 20 alkynyl group, a halogen-substituted or unsubstituted C 3 -C 20 cycloalkenyl group, a halogen-substituted or unsubstituted C 3 -C 20 heterocyclic group, a halogen-substituted or unsubstituted C 6 -C 40 aryl group, a halogen-substituted or unsubstituted C 2 -C 40 heteroaryl group, or a polar functional group having at least one heteroatom.

3. The lithium battery as claimed in claim 2 , wherein the substituted C 1 -C 5 alkylene group is substituted with a polar functional group including at least one heteroatom, wherein the polar functional group is —F, —Cl, —Br, —I, —C(═O)OR 16 , —OR 16 , —OC(═O)OR 16 , —R 15 OC(═O)OR 16 , —C(═O)R 16 , —R 15 C(═O)R 16 , —OC(═O)R 16 , —R 15 OC(═O)R 16 , —C(═O)—O—C(═O)R 16 , —R 15 C(═O)—O—C(═O)R 16 , —SR 16 , —R 15 SR 16 , —SSR 16 , —R 15 SSR 16 , —S(═O)R 16 , —R 15 S(═O)R 16 , —R 15 C(═S)R 16 , —R 15 C(═S)SR 16 , —R 15 SO 3 R 16 , —SO 3 R 16 , —NNC(═S)R 16 , —R 15 NNC(═S)R 16 , —R 15 N═C═S, —NCO, —R 15 —NCO, —NO 2 , —R 15 NO 2 , —R 15 SO 2 R 16 , —SO 2 R 16 ,

wherein, in the formulae above, each of R 11 and R 15 is independently a halogen-substituted or unsubstituted C 1 -C 20 alkylene group, a halogen-substituted or unsubstituted C 2 -C 20 alkenylene group, a halogen-substituted or unsubstituted C 2 -C 20 alkynylene group, a halogen-substituted or unsubstituted C 3 -C 12 cycloalkylene group, a halogen-substituted or unsubstituted C 6 -C 40 arylene group, a halogen-substituted or unsubstituted C 2 -C 40 heteroarylene group, a halogen-substituted or unsubstituted C 7 -C 15 alkylarylene group, or a halogen-substituted or unsubstituted C 7 -C 15 aralkylene group; and

each of R 12 , R 13 , R 14 and R 16 is independently hydrogen, a halogen, a halogen-substituted or unsubstituted C 1 -C 20 alkyl group, a halogen-substituted or unsubstituted C 2 -C 20 alkenyl group, a halogen-substituted or unsubstituted C 2 -C 20 alkynyl group, a halogen-substituted or unsubstituted C 3 -C 12 cycloalkyl group, a halogen-substituted or unsubstituted C 6 -C 40 aryl group, a halogen-substituted or unsubstituted C 2 -C 40 heteroaryl group, a halogen-substituted or unsubstituted C 7 -C 15 alkylaryl group, a halogen-substituted or unsubstituted C 7 -C 15 trialkylsilyl group, or a halogen-substituted or unsubstituted C 7 -C 15 aralkyl group.

4. The lithium battery as claimed in claim 1 , wherein at least one of A 1 , A 2 , A 3 , and A 4 is an unsubstituted or substituted C 1 -C 5 alkylene group, wherein a substituent of the substituted C 1 -C 5 alkylene group is a halogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a trifluoromethyl group, a tetrafluoroethyl group, a phenyl group, a naphthyl group, a tetrafluorophenyl group, a pyrrolyl group, or a pyridinyl group.

5. The lithium battery as claimed in claim 1 , wherein the bicyclic sulfate-based compound represented by Formula 1 is represented by Formula 2 or 3:

wherein, in Formulae 2 and 3, each of B 1 , B 2 , B 3 , B 4 , D 1 , and D 2 is independently —C(E 1 )(E 2 )-, a carbonyl group, or a sulfinyl group; and

each of E 1 and E 2 is independently hydrogen, a halogen, a halogen-substituted or unsubstituted C 1 -C 20 alkyl group, a halogen-substituted or unsubstituted C 2 -C 20 alkenyl group, a halogen-substituted or unsubstituted C 2 -C 20 alkynyl group, a halogen-substituted or unsubstituted C 3 -C 20 cycloalkenyl group, a halogen-substituted or unsubstituted C 3 -C 20 heterocyclic group, a halogen-substituted or unsubstituted C 6 -C 40 aryl group, or a halogen-substituted or unsubstituted C 2 -C 40 heteroaryl group.

6. The lithium battery as claimed in claim 5 , wherein each of E 1 and E 2 is independently hydrogen, a halogen, a halogen-substituted or unsubstituted C 1 -C 10 alkyl group, a halogen-substituted or unsubstituted C 6 -C 40 aryl group, or a halogen-substituted or unsubstituted C 2 -C 40 heteroaryl group.

7. The lithium battery as claimed in claim 5 , wherein each of E 1 and E 2 is independently hydrogen, fluorine (F), chlorine (Cl), bromine (Br), iodine (I), a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a trifluoromethyl group, a tetrafluoroethyl group, a phenyl group, a naphthyl group, a tetrafluorophenyl group, a pyrrolyl group, or a pyridinyl group.

8. The lithium battery as claimed in claim 1 , wherein the bicyclic sulfate-based compound represented by Formula 1 is represented by Formula 4 or 5:

wherein, in Formulae 4 and 5, each of R 1 , R 2 , R 3 , R 4 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 is independently hydrogen, a halogen, a halogen-substituted or unsubstituted C 1 -C 20 alkyl group, a halogen-substituted or unsubstituted C 6 -C 40 aryl group, or a halogen-substituted or unsubstituted C 2 -C 40 heteroaryl group.

9. The lithium battery as claimed in claim 8 , wherein each of R 1 , R 2 , R 3 , R 4 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 is independently hydrogen, F, Cl, Br, I, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a trifluoromethyl group, a tetrafluoroethyl group, a phenyl group, a naphthyl group, a tetrafluorophenyl group, a pyrrolyl group, or a pyridinyl group.

10. The lithium battery as claimed in claim 1 , wherein the bicyclic sulfate-based compound represented by Formula 1 is represented by one of Formulae 6 to 17 below:

11. The lithium battery as claimed in claim 1 , wherein an amount of the bicyclic sulfate-based compound is from about 0.4 wt % to about 5 wt % based on a total weight of the organic electrolytic solution.

12. The lithium battery as claimed in claim 1 , wherein an amount of the bicyclic sulfate-based compound is from about 0.4 wt % to about 3 wt % based on a total weight of the organic electrolytic solution.

13. The lithium battery as claimed in claim 1 , wherein the first lithium salt in the organic electrolytic solution includes LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiAlO 2 , LiAlCl 4 , LiN(C x F 2x+1 SO 2 )(C y F 2y+1 SO 2 ) where 2≤x≤20 and 2≤y≤20, LiCl, or LiI.

14. The lithium battery as claimed in claim 1 , wherein the organic electrolytic solution further includes a cyclic carbonate compound, wherein the cyclic carbonate compound includes-vinylene carbonate (VC); VC substituted with a halogen, a cyano (CN) group, or a nitro group (NO 2 ); vinylethylene carbonate (VEC); VEC substituted with a halogen, CN, or NO 2 ; fluoroethylene carbonate (FEC); or FEC substituted with a halogen, CN, or NO 2 .

15. The lithium battery as claimed in claim 14 , wherein an amount of the cyclic carbonate compound is from about 0.6 wt % to about 10 wt % based on a total weight of the organic electrolytic solution.

16. The lithium battery as claimed in claim 15 , wherein an amount of the second lithium salt is from about 0.1 wt % to about 5 wt % based on a total weight of the organic electrolytic solution.

17. The lithium battery as claimed in claim 1 , wherein the organic electrolytic solution further includes a second lithium salt different from the first lithium salt and represented by one of Formulae 18 to 25 below:

18. The lithium battery as claimed in claim 1 , wherein the composite of the silicon-based compound and the carbonaceous compound has a mean particle diameter of about 5 μm to about 20 μm, and the silicon nanoparticles have a mean particle diameter of about 10 nm to about 200 nm.

19. The lithium battery as claimed in claim 1 , wherein an amount of the metal-based anode active material is from about 1 wt % to about 10 wt % based on a total weight of an anode mixture.

20. The lithium battery as claimed in claim 1 , wherein:

the metal-based anode active material is included in an amount of about 1 wt % to about 10 wt % based on a total weight of an anode mixture;

the bicyclic sulfate-based compound is included in the organic electrolyte solution in an amount of about 0.4 wt % to about 5 wt % based on a total weight of the organic electrolytic solution, and

the organic electrolytic solution further includes a fluoroethylene carbonate (FEC) in an amount of from about 0.6 wt % to about 10 wt % based on a total weight of the organic electrolytic solution.

21. A lithium battery, comprising:

a cathode including a cathode active material;

an anode including an anode active material; and

an organic electrolytic solution between the cathode and the anode,

wherein:

the anode active material includes a metal-based anode active material,

the organic electrolytic solution includes a first lithium salt; an organic solvent; and a bicyclic sulfate-based compound represented by Formula 1 below:

in Formula 1, each of A 1 , A 2 , A 3 , and A 4 is independently a covalent bond, a substituted or unsubstituted C 1 -C 5 alkylene group, a carbonyl group, or a sulfinyl group, provided that A 1 and A 2 are not simultaneously a covalent bond and provided that A 3 and A 4 are not simultaneously a covalent bond, and

the metal-based anode active material is a silicon-based active material and is included in an amount of about 1 wt % to about 10 wt % based on a total weight of an anode mixture.

22. The lithium battery as claimed in claim 21 , wherein the metal-based anode active material includes a silicon oxide, SiOx, in which where 0<x<2.

23. A lithium battery, comprising:

a cathode including a cathode active material;

an anode including an anode active material; and

an organic electrolytic solution between the cathode and the anode,

wherein:

the anode active material includes a metal-based anode active material,

the organic electrolytic solution includes a first lithium salt; an organic solvent; and a bicyclic sulfate-based compound represented by Formula 1 below:

in Formula 1, each of A 1 , A 2 , A 3 , and A 4 is independently a covalent bond, a substituted or unsubstituted C 1 -C 5 alkylene group, a carbonyl group, or a sulfinyl group, provided that A 1 and A 2 are not simultaneously a covalent bond and provided that A 3 and A 4 are not simultaneously a covalent bond,

the metal-based anode active material includes a composite of a silicon-based compound and a carbonaceous compound,

the composite of the silicon-based compound and the carbonaceous compound includes carbon-coated silicon nanoparticles, and

an amount of the metal-based anode active material is from about 1 wt % to about 10 wt % based on a total weight of an anode mixture.