Non-aqueous electrolyte for high voltage rechargeable magnesium batteries
An electrolyte for use in electrochemical cells is provided. The properties of the electrolyte include high conductivity, high Coulombic efficiency, and an electrochemical window that can exceed 3.5 V vs. Mg/Mg +2 . The use of the electrolyte promotes the electrochemical deposition and dissolution of Mg without the use of any Grignard reagents, other organometallic materials, tetraphenyl borate, or tetrachloroaluminate derived anions. Other Mg-containing electrolyte systems that are expected to be suitable for use in secondary batteries are also described.
1. A non-aqueous electrolyte solution for use in an electrochemical cell, comprising:
at least one organic solvent; and
at least one electrolytically active, soluble, inorganic Magnesium (Mg) salt complex represented by the formula Mg n+1 X (2*n) Z 2 in which n is in the range from one-quarter to four, X is a halide, and Z is an inorganic polyatomic monovalent anion.
2. The non-aqueous electrolyte solution of claim 1 , wherein Z is a polyatomic monovalent anion selected from the group of polyatomic monovalent anions described in Table I, and mixtures thereof.
3. The non-aqueous electrolyte solution of claim 1 , wherein n is in the range from 0.25 to 4, said halide is chlorine.
4. The non-aqueous electrolyte solution of claim 1 , wherein n is in the range from 0.25 to 4, said halide is chlorine, and Z is N(CF 3 SO 2 ) 2 −1 .
5. The non-aqueous electrolyte solution of claim 1 , a Mg molarity is in the range from 0.1 M to 2 M.
6. The non-aqueous electrolyte solution of claim 1 , wherein a solution conductivity is greater than 1 mS/cm at 25 degrees Celsius.
7. The non-aqueous electrolyte solution of claim 1 , a solution Coulombic efficiency is greater than 98% at 25 degrees Celsius.
8. The non-aqueous electrolyte solution of claim 1 , wherein said at least one organic solvent is a solvent selected from the group consisting of an ether, an organic carbonate, a lactone, a ketone, a glyme, a nitrile, an ionic liquid, an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent and an organic nitro solvent, and mixtures thereof.
9. The non-aqueous electrolyte solution of claim 1 , wherein said at least one organic solvent is a solvent selected from the group consisting of THF, 2-methyl THF, dimethoxyethane, diglyme, triglyme, tetraglyme, diethoxyethane, diethylether, proglyme, ethyl diglyme, butyl diglyme, dimethylsulfoxide, dimethylsulfite, sulfolane, ethyl methyl sulfone, acetonitrile, hexane, toluene, nitromethane, 1-3 dioxalane, 1-4 dioxane, trimethyl phosphate, tri-ethyl phosphate, hexa-methyl-phosphoramide (HMPA), N,N-propyl-methyl-pyrrolidinium-bis(trifluoromethylsulfonyl)imide (P13-TFSI), N,N-propyl-methyl-pyrrolidinium-diacetamide (P13-DCA), propyl-methyl-pyrrolidinium-bis(fluorosulfonyl)imide (P13-FSI), ethyl-dimethyl-propyl-ammonium-bis(trifluoromethylsulfonyl)imide (PDEA-TFSI), 1-(methoxyethyl)-1-methylpiperidinium-bis(trifluoromethylsulfonyl)imide (MOEMPP-TFSI), and mixtures thereof.
10. The non-aqueous electrolyte solution of claim 1 , wherein said at least one organic solvent comprises at least one of THF, dimethoxyethane, ethyl diglyme, and butyl diglyme.
11. A non-aqueous electrolyte solution for use in an electrochemical cell comprising:
at least one organic solvent; and
a magnesium halide complex that is a reaction product of magnesium halide and another inorganic salt containing a polyatomic monovalent anion of anodic stability limit greater than 2.5 V vs. Mg/Mg 2+ , wherein said magnesium halide to magnesium salt ratio is in the range from 4:1 and 1:4.
12. The non-aqueous electrolyte solution of claim 11 , wherein said magnesium salt containing a polyatomic monovalent anion of anodic stability limit greater than 2.5 V vs. Mg/Mg 2+ is selected from the group of polyatomic monovalent anions described in Table I, and mixtures thereof.
13. The non-aqueous electrolyte solution of claim 11 , wherein said magnesium halide is a magnesium chloride.
14. The non-aqueous electrolyte solution of claim 11 , wherein said Mg molarity is in the range from 0.1 M to 2 M.
15. The non-aqueous electrolyte solution of claim 11 , wherein a solution conductivity is greater than 1 mS/cm at 25 degrees Celsius.
16. The non-aqueous electrolyte solution of claim 11 , wherein a solution Coulombic efficiency is greater than 98% at 25 degrees Celsius.
17. The non-aqueous electrolyte solution of claim 11 , wherein said at least one organic solvent is a solvent selected from the group consisting of an ether, an organic carbonate, a lactone, a ketone, a glyme, a nitrile, an ionic liquid, an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent and an organic nitro solvent, and mixtures thereof.
18. The non-aqueous electrolyte solution of claim 11 , wherein said at least one organic solvent is a solvent selected from the group consisting of THF, 2-methyl THF, dimethoxyethane, diglyme, triglyme, tetraglyme, diethoxyethane, diethylether, proglyme, ethyl diglyme, butyl diglyme, dimethylsulfoxide, dimethylsulfite, sulfolane, ethyl methyl sulfone, acetonitrile, hexane, toluene, nitromethane, 1-3 dioxalane, 1-4 dioxane, trimethyl phosphate, tri-ethyl phosphate, hexa-methyl-phosphoramide (HMPA), N,N-propyl-methyl-pyrrolidinium-bis(trifluoromethylsulfonyl)imide (P13-TFSI), N,N-propyl-methyl-pyrrolidinium-diacetamide (P13-DCA), propyl-methyl-pyrrolidinium-bis(fluorosulfonyl)imide (P13-FSI), ethyl-dimethyl-propyl-ammonium-bis(trifluoromethylsulfonyl)imide (PDEA-TFSI), 1-(methoxyethyl)-1-methylpiperidinium-bis(trifluoromethylsulfonyl)imide (MOEMPP-TFSI), and mixtures thereof.
19. The non-aqueous electrolyte solution of claim 11 , wherein said at least one organic solvent comprises at least one of THF, dimethoxyethane, ethyl diglyme, and butyl diglyme.