Electrolyte for magnesium rechargeable battery and preparation method thereof

Patent metadata

Field	Value
Publication number	US-9543616-B2
Application number	US-201514633807-A
Country	US
Kind code	B2
Filing date	Feb 27, 2015
Priority date	Jul 25, 2014
Publication date	Jan 10, 2017
Grant date	Jan 10, 2017

Abstract

Disclosed is an electrolyte solution for a magnesium rechargeable battery with a high ionic conductivity and a wide electrochemical window compared to the conventional electrolyte solution. The electrolyte solution is prepared by dissolving magnesium metal into the ethereal solution using combinations of metal chloride catalysts. The electrolyte solution can be applied to fabricate magnesium rechargeable batteries and magnesium hybrid batteries with a markedly increased reversible capacity, rate capability, and cycle life compared to those batteries employing the conventional electrolyte solution. Also disclosed is a method for preparing the electrolyte.

First claim

What is claimed is:

1. An electrolyte solution for a magnesium rechargeable battery made from the combination of
metal chlorides,
magnesium metal,
an organic solvent, and
an ionic liquid comprising a compound of Formula 1:

wherein R is selected from unsubstituted C 1 -C 10 linear or branched alkyl groups, C 1 -C 10 linear or branched alkyl groups substituted with a C 1 -C 10 linear or branched alkoxy group, unsubstituted C 5 -C 12 cycloalkyl groups, C 5 -C 12 cycloalkyl groups substituted with a C 1 -C 10 linear or branched alkoxy group, unsubstituted C 5 -C 12 aryl groups, C 5 -C 12 aryl groups substituted with a C 1 -C 10 linear or branched alkoxy group, unsubstituted allyl groups, and allyl groups substituted with a C 1 -C 10 linear or branched alkoxy group, and X is selected from halogen groups, unsubstituted sulfonimide groups, sulfonimide groups substituted with a halogenated alkyl group, unsubstituted sulfonamide groups, and sulfonamide groups substituted with a halogenated alkyl group.

2. The electrolyte solution according to claim 1 , wherein the electrolyte solution is obtained by removing a solid fraction from a solution in which metal chlorides, the magnesium metal, and the magnesium ions are in equilibrium, and collecting the remaining liquid fraction.

3. The electrolyte solution according to claim 1 , wherein the metal chlorides are selected from AlCl 3-n R′ n (where n is an integer from 0 to 3 and R′ is selected from alkyl, aryl, heteroaryl, and alkenyl groups), BCl 3-n R′ n (where n and R′ are as defined above), CrCl 3 , FeCl 3 , MnCl 2 , FeCl 2 , CoCl 2 , NiCl 2 , CuCl 2 , ZnCl 2 , TiCl 4 , ZrCl 4 , VCl 4 , NbCl 5 , RhCl 3 , and mixtures thereof.

4. The electrolyte solution according to claim 1 , wherein the organic solvent is selected from tetrahydrofuran (THF), glyme, diglyme, triglyme, tetraglyme, dioxane, anisole, crown ethers, polyethylene glycol, acetonitrile, propylene carbonate, and mixtures thereof.

5. The electrolyte solution according to claim 1 , wherein the metal chloride is present at a concentration of 0.001 to 1.0 M.

6. The electrolyte solution according to claim 1 , wherein the metal chloride salt is a mixture of (i) a first metal chloride salt selected from AlCl 3-n R′ n , BCl 3-n R′ n , and mixtures thereof and (ii) a second metal chloride salt selected from CrCl 3 , FeCl 3 , MnCl 2 , FeCl 2 , CoCl 2 , NiCl 2 , CuCl 2 , ZnCl 2 , TiCl 4 , ZrCl 4 , VCl 4 , NbCl 5 , RhCl 3 , and mixtures thereof.

7. The electrolyte solution according to claim 6 , wherein each of the first and second metal chloride salts is present at a concentration of 0.01 to 1 M.

8. The electrolyte solution according to claim 1 , wherein 1-oxa-2-magnesiacyclohexane is a precursor for the formation of the electrolyte solution.

9. The electrolyte solution according to claim 1 , wherein R in Formula 1 is selected from allyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-[2-(2-methoxyethoxy)ethoxy]ethyl, cyclopentyl, cyclohexyl, and phenyl groups.

10. The electrolyte solution according to claim 9 , wherein the compound of Formula 1 is present in an amount of 0.01 to 1% by weight.

11. The electrolyte according to claim 1 , wherein the compound of Formula 1 is selected from N-allyl-N-methylpyrrolidinium chloride, N-allyl-N-methylpyrrolidinium bromide, N-allyl-N-methylpyrrolidinium bis(trifluoromethane)sulfonimide, N-butyl-N-methylpyrrolidinium bromide, N-butyl-N-methylpyrrolidinium chloride, 1-{2-[2-(2-methoxyethoxy)ethoxy]ethyl}-1-methyl-pyrrolidinium bromide, and 1-{2-[2-(2-methoxyethoxy)ethoxy]ethyl}-1-methylpyrrolidinium chloride.

12. The electrolyte solution according to claim 1 , wherein a complex of the compound of Formula 1 with magnesium ions is present in the electrolyte.

13. The electrolyte according to claim 1 , further comprising a lithium salt.

14. The electrolyte according to claim 13 , wherein the lithium salt is selected from LiCl, lithium bis(trifluoromethanesulfonyl)imide, LiClO 4 , LiBF 4 , LiPF 6 , and mixtures thereof.

15. The electrolyte according to claim 13 , wherein the lithium salt is present at a concentration of 0.1 to 0.5 M.

16. A magnesium battery comprising the electrolyte according to claim 1 , wherein the magnesium battery is a magnesium secondary battery or a magnesium hybrid battery.

17. A magnesium battery comprising the electrolyte according to claim 1 , wherein the magnesium battery is a magnesium rechargeable battery or a rechargeable magnesium hybrid battery.

18. The electrolyte solution according to claim 1 , wherein a complex of the compound of Formula 1 comprises 1-butyl-1-methylpyrrolidinium bromide (BMPBr).

19. The electrolyte solution according to claim 1 , wherein a complex of the compound of Formula 1 comprises N-allyl-N-methylpyrrolidinium chloride (AMPCl).

20. An electrolyte solution for a magnesium rechargeable battery comprising
an organic solvent selected from tetrahydrofuran (THF), glyme, diglyme, triglyme, tetraglyme, dioxane, anisole, crown ethers, polyethylene glycol, acetonitrile, propylene carbonate, and mixtures thereof;
a metal chloride selected from AlCl 3-n R′ n (where n is an integer from 0 to 3 and R′ is selected from alkyl, aryl, heteroaryl, and alkenyl groups), BCl 3-n R′ n (where n and R′ are as defined above), CrCl 3 , FeCl 3 , MnCl 2 , FeCl 2 , CoCl 2 , NiCl 2 , CuCl 2 , ZnCl 2 , TiCl 4 , ZrCl 4 , VCl 4 , NbCl 5 , RhCl 3 , and mixtures thereof;
an ionic liquid comprising a compound of Formula 1:

wherein R is selected from unsubstituted C 1 -C 10 linear or branched alkyl groups, C 1 -C 10 linear or branched alkyl groups substituted with a C 1 -C 10 linear or branched alkoxy group, unsubstituted C 5 -C 12 cycloalkyl groups, C 5 -C 12 cycloalkyl groups substituted with a C 1 -C 10 linear or branched alkoxy group, unsubstituted C 5 -C 12 aryl groups, C 5 -C 12 aryl groups substituted with a C 1 -C 10 linear or branched alkoxy group, unsubstituted allyl groups, and allyl groups substituted with a C 1 -C 10 linear or branched alkoxy group, and X is selected from halogen groups, unsubstituted sulfonimide groups, sulfonimide groups substituted with a halogenated alkyl group, unsubstituted sulfonamide groups, and sulfonamide groups substituted with a halogenated alkyl group; and
an alkylalkoxyaluminate comprising at least one of [Al(C 4 H 8 O) 2 ] − which corresponds to Formula (3):

and [AlCl 2 (C 4 H 8 O)] − which corresponds to Formula (4)

Assignees

• Korea Inst Sci & Tech

Inventors

• Oh Si Hyoung
• Cho Byung Won
• Chung Kyung Yoon
• Lee Joong Kee
• Chang Won Young
• Cho Jae Hyun
• Ha Junghoon

Classifications

• H01M10/0567 Primary

  characterised by the additives · CPC title

• H01M10/0568 Primary

  characterised by the solutes · CPC title

• H01M10/054 Primary

  Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium · CPC title

• H01M2300/0025

  Organic electrolyte · CPC title

• H01M10/0569

  characterised by the solvents · CPC title