Granted Patent B2

US 12,725,802 · App. 17/934,561 · Granted Sep 1, 2026

Inventors: Kisuk Kang (Seoul, KR); Myeong Hwan Lee (Sokcho-si, KR); Giyun Kwon (Seoul, KR)

Assignee: SEOUL NATIONAL UNIVERSITY R&DB FOUNDATION

H01M4/60H01M10/36H01M50/46H01M2004/028H01M2300/0005

Abstract

Claims (51)

1 . An aqueous rechargeable ion battery, comprising:

a positive electrode including an organic positive active material including a compound represented by Chemical Formula 1;

a negative electrode;

a separator between the positive electrode and negative electrode; and

an aqueous electrolyte including a water solvent and a metal salt with a molality of greater than or equal to about 15 m,

wherein an amount of organic positive active material dissolved in the aqueous electrolyte, as measured by the area of the absorption spectrum in a UV-visible spectroscopic analysis of the aqueous electrolyte, is less than or equal to 7.6 wt % based on a total of 100 wt % of the aqueous electrolyte and the organic positive electrode active material:

wherein, in Chemical Formula 1,

Z 1 and Z 2 are the same as or different from each other, Z 1 is NR 1 , PR 1 , O, S, S═O, or S(═O) 2 , and Z 2 is NR 2 , PR 2 , O, S, S═O, or S(═O) 2 ,

R 1 and R 2 are the same as or different from each other and are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 heteroaryl group, a substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted C2 to C20 ether group, a halogen (F, Cl, Br, or I), a hydroxy group, a nitro group, a cyano group, an amine group, an imino group, an azido group, a carbonyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, or a phosphoric acid group or a salt thereof, and

R 3 to R 10 are the same as or different from each other and are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 heteroaryl group, a substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted C2 to C20 ether group, a halogen (F, Cl, Br, or I), a hydroxy group, a nitro group, a cyano group, an amine group, an imino group, an azido group, a carbonyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, or a phosphoric acid group or a salt thereof.

2 . The aqueous rechargeable ion battery of claim 1 , wherein

in Chemical Formula 1,

Z 1 is NR 1 , and

Z 2 is NR 2 , PR 2 , O, S, S═O, or S(═O) 2 .

3 . The aqueous rechargeable ion battery of claim 1 , wherein

in Chemical Formula 1,

Z 1 is S, and

Z 2 is NR 2 , PR 2 , O, S, S═O, or S(═O) 2 .

4 . The aqueous rechargeable ion battery of claim 1 , wherein the compound represented by Chemical Formula 1 includes a phenazine-based compound, a phenoxazine-based compound, a phenothiazine-based compound, a thianthrene-based compound, a thianthrene 5-oxide-based compound, or a thianthrene 5,5-dioxide-based compound.

5 . The aqueous rechargeable ion battery of claim 1 , wherein

in Chemical Formula 1,

R 1 and R 2 are each independently a halogen-substituted C1 to C10 alkyl group, an unsubstituted C1 to C10 alkyl group, a halogen-substituted C6 to C20 aryl group, an unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C2 to C10 ether group, or a sulfonyl group, and

R 3 to R 10 are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C1 to C10 alkoxy group, a halogen, a hydroxy group, a nitro group, a cyano group, an amine group, or a thiol group.

6 . The aqueous rechargeable ion battery of claim 1 , wherein the compound represented by Chemical Formula 1 is a phenazine-based compound represented by Chemical Formula 2:

wherein, in Chemical Formula 2,

R 1 and R 2 are the same as or different from each other and are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 heteroaryl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 ether group, a halogen (F, Cl, Br, or I), a hydroxy group, a nitro group, a cyano group, an amine group, an imino group, an azido group, a carbonyl group, a thiol group, a sulfonyl group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, or a phosphoric acid group or a salt thereof, and

R 3 to R 10 are the same as or different from each other and are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 heteroaryl group, a substituted or unsubstituted C1 to C10 alkoxy group, a halogen (F, Cl, Br, or I), a hydroxy group, a nitro group, a cyano group, an amine group, an imino group, an azido group, a carbonyl group, a thiol group, a sulfonyl group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, or a phosphoric acid group or a salt thereof.

7 . The aqueous rechargeable ion battery of claim 6 , wherein

in Chemical Formula 2,

R 1 and R 2 are each independently a halogen-substituted C1 to C10 alkyl group, an unsubstituted C1 to C10 alkyl group, a halogen-substituted C6 to C20 aryl group, an unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C2 to C10 ether group, or a sulfonyl group, and

R 3 to R 10 are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C1 to C10 alkoxy group, a halogen, a hydroxy group, a nitro group, a cyano group, an amine group, or a thiol group.

8 . The aqueous rechargeable ion battery of claim 6 , wherein the phenazine-based compound represented by Chemical Formula 2 includes 5,10-dihydro-5, 10-dimethylphenazine; 1-fluoro-5,10-dihydro-5, 10-dimethylphenazine; 2,7-difluoro-5, 10-dihydro-5, 10-dimethylphenazine; 1-methyl-5, 10-dihydro-5,10-dimethylphenazine; 5,10-dihydro-5-methyl-10-(2,2,2-trifluoromethyl) phenazine; or 5,10-bis-(2-methoxyethyl)-5, 10-dihydrophenazine.

9 . The aqueous rechargeable ion battery of claim 1 , wherein the negative electrode includes a negative active material, and the negative active material includes a zinc metal-based, an aluminum metal-based, a copper metal-based, a carbon-based, or a sulfur-based material, or a combination thereof.

10 . The aqueous rechargeable ion battery of claim 1 , wherein molality of the aqueous electrolyte is about 15 m to about 40 m.

11 . The aqueous rechargeable ion battery of claim 1 , wherein molality of the aqueous electrolyte is about 15 m to about 35 m.

12 . The aqueous rechargeable ion battery of claim 1 , wherein the metal salt of the aqueous electrolyte includes a compound represented by Chemical Formula 11:

wherein, in Chemical Formula 11,

A is at least one metal ion of a lithium ion, a sodium ion, a potassium ion, a rubidium ion, a magnesium ion, a calcium ion, a strontium ion, a barium ion, a copper ion, a zinc ion, or an aluminum ion as a cation,

D is at least one atomic group ion of Cl − , SO 4 2− , NO 3 − , ClO 4 − , SCN − , CF 3 SO 3 − , C 4 F 9 SO 3 − , (CF 3 SO 2 ) 2 N − , AlO 2 − , AlCl 4 − , AsF 6 − , SbF 6 − , BF 4 − , or PO 2 F 2 − as an anion,

0<x≤2, and

0<y≤2.

13 . The aqueous rechargeable ion battery of claim 12 , in Chemical Formula 11, D is Cl − , NO 3 − , ClO 4 − , CF 3 SO 3 − , C 4 F 9 SO 3 − , (CF 3 SO 2 ) 2 N − , or combination thereof.

14 . The aqueous rechargeable ion battery of claim 1 , wherein in the aqueous electrolyte, the metal salt includes a compound represented by Chemical Formula 12 and a compound represented by Chemical Formula 13:

wherein, in Chemical Formula 12, A 12 is at least one metal ion of a lithium ion, a sodium ion, a potassium ion, a rubidium ion, a magnesium ion, a calcium ion, a strontium ion, or a barium ion, D 12 is at least one atomic group ion of Cl − , SO 4 2− , NO 3 − , ClO 4 − , SCN − , CF 3 SO 3 − , C 4 F 9 SO 3 − , (CF 3 SO 2 ) 2 N − , AlO 2 − , AlCl 4 − , AsF 6 − , SbF 6 − , BF 4 − , or PO 2 F 2 − , 0<x≤2, and 0<y≤2, and

wherein, in Chemical Formula 13, A 13 is at least one metal ion of a copper ion, a zinc ion, and an aluminum ion, D 13 is at least one atomic group ion of Cl−, SO 4 2− , NO 3 − , ClO 4 − , SCN − , CF 3 SO 3 − , C 4 F 9 SO 3 − , (CF 3 SO 2 ) 2 N − , AlO 2 − , AlCl 4 − , AsF 6 − , SbF 6 − , BF 4 − , or PO 2 F 2 − , 0<x≤2, and 0<y≤2.

15 . The aqueous rechargeable ion battery of claim 14 , wherein

molality of the compound represented by Chemical Formula 12 is about 10 m to about 40 m, and

molality of the compound represented by Chemical Formula 13 is about 0.1 m to about 5 m.

16 . The aqueous rechargeable ion battery of claim 14 , wherein the negative electrode includes a negative active material including the metal of A 13 of Chemical Formula 13.

17 . The aqueous rechargeable ion battery of claim 1 , wherein the separator is an ion exchange membrane.

18 . The aqueous rechargeable ion battery of claim 1 , wherein molality of the aqueous electrolyte is about 15 m to about 25 m.

Assignments (1)

Priority Claims (1)

Continuity (1)

References Cited (20)