Random copolymer, electrolyte, protected anode and lithium battery including the same, and method of preparing the random copolymer

1. A random copolymer represented by Formula 3:

wherein CY1 and CY2 are each independently a substituted or unsubstituted C 6 -C 30 aryl ring or a substituted or unsubstituted C 2 -C 30 heteroaryl ring;

A is a single bond, a substituted or unsubstituted C 1 -C 30 alkylene group, a substituted or unsubstituted C 6 -C 30 arylene group, a substituted or unsubstituted C 3 -C 30 heteroarylene group, a substituted or unsubstituted C 4 -C 30 cycloalkylene group, or a substituted or unsubstituted C 3 -C 30 heterocycloalkylene group;

is a 3 to 31-membered ring comprising X and 2 to 30 carbon atoms;

X is S, N(R 9 ), or P(R 10 );

R 1 to R 10 are each independently hydrogen, a halogen atom, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 1 -C 30 heteroalkyl group, a substituted or unsubstituted C 1 -C 30 alkoxy group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 7 -C 30 arylalkyl group, a substituted or unsubstituted C 6 -C 30 aryloxy group, a substituted or unsubstituted C 6 -C 30 arylthio group, a substituted or unsubstituted C 3 -C 30 heteroaryl group, a substituted or unsubstituted C 4 -C 30 heteroarylalkyl group, a substituted or unsubstituted C 3 -C 30 heteroaryloxy group, a substituted or unsubstituted C 3 -C 30 heteroarylthio group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyloxy group, a substituted or unsubstituted C 3 -C 30 heterocycloalkyl group, a substituted or unsubstituted C 3 -C 30 alkenyl group, a substituted or unsubstituted C 3 -C 30 alkynyl group, or a substituted or unsubstituted C 2 -C 100 alkyleneoxide group;

Y − is an anion;

0.01≤a≤0.99, 0.01≤b≤0.99, provided that a+b=1; and

n is an integer of 10 to 5,000.

2. The random copolymer of claim 1 , wherein, in Formula 3,

is represented by Formula 4:

wherein Z is S, N, or P; and

R 11 to R 25 are each independently hydrogen, a halogen atom, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 1 -C 30 heteroalkyl group, a substituted or unsubstituted C 1 -C 30 alkoxy group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 7 -C 30 arylalkyl group, a substituted or unsubstituted C 6 -C 30 aryloxy group, a substituted or unsubstituted C 6 -C 30 arylthio group, a substituted or unsubstituted C 3 -C 30 heteroaryl group, a substituted or unsubstituted C 4 -C 30 heteroarylalkyl group, a substituted or unsubstituted C 3 -C 30 heteroaryloxy group, a substituted or unsubstituted C 3 -C 30 heteroarylthio group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyloxy group, a substituted or unsubstituted C 3 -C 30 heterocycloalkyl group, a substituted or unsubstituted C 3 -C 30 alkenyl group, a substituted or unsubstituted C 3 -C 30 alkynyl group, or a substituted or unsubstituted C 2 -C 100 alkyleneoxide group, provided that R 11 is absent when Z is S.

3. The random copolymer of claim 1 , wherein, in Formula 3,

is represented by Formula 5:

wherein R 11 is hydrogen, a halogen atom, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 1 -C 30 heteroalkyl group, a substituted or unsubstituted C 1 -C 30 alkoxy group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 7 -C 30 arylalkyl group, a substituted or unsubstituted C 6 -C 30 aryloxy group, a substituted or unsubstituted C 6 -C 30 arylthio group, a substituted or unsubstituted C 3 -C 30 heteroaryl group, a substituted or unsubstituted C 4 -C 30 heteroarylalkyl group, a substituted or unsubstituted C 3 -C 30 heteroaryloxy group, a substituted or unsubstituted C 3 -C 30 heteroarylthio group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyloxy group, a substituted or unsubstituted C 3 -C 30 heterocycloalkyl group, a substituted or unsubstituted C 3 -C 30 alkenyl group, a substituted or unsubstituted C 3 -C 30 alkynyl group, or a substituted or unsubstituted C 2 -C 100 alkyleneoxide group.

4. The random copolymer of claim 1 , wherein the random copolymer is represented by Formula 6:

wherein CY1 and CY2 are each independently a substituted or unsubstituted C 6 -C 30 aryl ring or a substituted or unsubstituted C 2 -C 30 heteroaryl ring;

A is a single bond, a substituted or unsubstituted C 1 -C 30 alkylene group, a substituted or unsubstituted C 6 -C 30 arylene group, a substituted or unsubstituted C 3 -C 30 heteroarylene group, a substituted or unsubstituted C 4 -C 30 cycloalkylene group, or a substituted or unsubstituted C 3 -C 30 heterocycloalkylene group;

R 1 , R 8 , and R 11 are each independently hydrogen, a halogen atom, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 1 -C 30 heteroalkyl group, a substituted or unsubstituted C 1 -C 30 alkoxy group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 7 -C 30 arylalkyl group, a substituted or unsubstituted C 6 -C 30 aryloxy group, a substituted or unsubstituted C 6 -C 30 arylthio group, a substituted or unsubstituted C 3 -C 30 heteroaryl group, a substituted or unsubstituted C 4 -C 30 heteroarylalkyl group, a substituted or unsubstituted C 3 -C 30 heteroaryloxy group, a substituted or unsubstituted C 3 -C 30 heteroarylthio group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyloxy group, a substituted or unsubstituted C 3 -C 30 heterocycloalkyl group, a substituted or unsubstituted C 3 -C 30 alkenyl group, a substituted or unsubstituted C 3 -C 30 alkynyl group, or a substituted or unsubstituted C 2 -C 100 alkyleneoxide group;

Y − is BF 4 − , PF 6 − , AsF 6 − , SbF 6 − , AlCl 4 − , HSO 4 − , CH 3 SO 3 − , (CF 3 SO 2 ) 2 N − , Cl − , Br − , I − , SO 4 − , PF 6 − , ClO 4 − , CF 3 SO 3 − , CF 3 CO 2 − , (C 2 F 5 SO 2 ) 2 N − , C 2 F 5 SO 2 )(CF 3 SO 2 )N − , (CF 3 SO 2 ) 2 N − , NO 3 − , Al 2 Cl 7 − , AsF 6 − , SbF 6 − , CH 3 COO − , (CF 3 SO 2 ) 3 C − , (CF 3 ) 2 PF 4 − , (CF 3 ) 3 PF 3 − , (CF 3 ) 4 PF 2 − , (CF 3 ) 5 PF − , (CF 3 ) 6 P − , SF 5 CF 2 SO 3 − , SF 5 CHFCF 2 SO 3 − , CF 3 CF 2 (CF 3 ) 2 CO − , (CF 3 SO 2 ) 2 CH − , (SF 5 ) 3 C − , (O(CF 3 ) 2 C 2 (CF 3 ) 2 O) 2 PO − , or a combination thereof;

0.01≤a≤0.99, 0.01≤b≤0.99, provided that a+b=1; and

n is an integer of 10 to 5,000.

5. The random copolymer of claim 1 , wherein the random copolymer is represented by Formula 7:

wherein R 26 , R 27 , and R 28 are each independently hydrogen, a halogen atom, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 1 -C 30 alkoxy group, or a substituted or unsubstituted C 2 -C 100 alkyleneoxide group;

Y − is BF 4 − , PF 6 − , AsF 6 − , SbF 6 − , AlCl 4 − , HSO 4 − , CH 3 SO 3 − , (CF 3 SO 2 ) 2 N − , Cl − , Br − , I − , SO 4 − , PF 6 − , ClO 4 − , CF 3 SO 3 − , CF 3 CO 2 − , (C 2 F 5 SO 2 ) 2 N − , C 2 F 5 SO 2 )(CF 3 SO 2 )N − , (CF 3 SO 2 ) 2 N − , NO 3 − , Al 2 Cl 7 − , AsF 6 − , SbF 6 − , CH 3 COO − , (CF 3 SO 2 ) 3 C − , (CF 3 ) 2 PF 4 − , (CF 3 ) 3 PF 3 − , (CF 3 ) 4 PF 2 − , (CF 3 ) 5 PF − , (CF 3 ) 6 P − , SF 5 CF 2 SO 3 − , SF 5 CHFCF 2 SO 3 − , CF 3 CF 2 (CF 3 ) 2 CO − , (CF 3 SO 2 ) 2 CH − , (SF 5 ) 3 C − , (O(CF 3 ) 2 C 2 (CF 3 ) 2 O) 2 PO − , or a combination thereof;

0.01≤a≤0.99, 0.01≤b≤0.99, provided that a+b=1; and

m is an integer of 1 to 10 and n is an integer of 10 to 5,000.

6. The random copolymer of claim 5 , wherein R 28 is a methyl group, an ethyl group, a propyl group, or a butyl group.

7. The random copolymer of claim 1 , wherein the random copolymer has a number average molecular weight of about 3,000 Daltons to about 200,000 Daltons.

8. The random copolymer of claim 1 , wherein the random copolymer has a polydispersity index of about 1 to about 3.

9. The random copolymer of claim 1 , wherein the random copolymer further comprises a third repeating unit.

10. The random copolymer of claim 1 , wherein the random copolymer is electrochemically stable to −0.4 Volts versus lithium.

11. An electrolyte comprising the random copolymer according to claim 1 .

12. A protected anode comprising:

an anode; and

a protective layer disposed on the anode,

wherein the protective layer comprises the random copolymer according to claim 1 .

13. The protected anode of claim 12 , wherein the anode comprises lithium, a lithium alloy, a metal alloyable with lithium, or a combination thereof.

14. The protected anode of claim 12 , wherein the protective layer further comprises a lithium salt.

15. The protected anode of claim 12 , wherein the protective layer has a thickness of about 0.1 micrometers to about 100 micrometers.

16. A lithium battery comprising:

a cathode;

the protected anode according to claim 12 ; and

an electrolyte disposed between the cathode and the protected anode.

17. The lithium battery of claim 16 , wherein the electrolyte is a liquid electrolyte or a solid electrolyte.