Magnesium ion-containing non-aqueous electrolyte and a production process thereof, as well as electrochemical device
View Patent ↗A magnesium ion containing non-aqueous electrolyte in which magnesium ions and aluminum ions are dissolved in an organic etheric solvent, and which is formed by: adding metal magnesium, a halogenated hydrocarbon RX, an aluminum halide AlY 3 , and a quaternary ammonium salt R 1 R 2 R 3 R 4 N + Z − to an organic etheric solvent; and applying a heating treatment while stirring them (in the general formula RX representing the halogenated hydrocarbon, R is an alkyl group or an aryl group, X is chlorine, bromine, or iodine, in the general formula AlY 3 representing the aluminum halide, Y is chlorine, bromine, or iodine, in the general formula R 1 R 2 R 3 R 4 N + Z − representing the quaternary ammonium salt, R 1 , R 2 , R 3 , and R 4 represent each an alkyl group or an aryl group, and Z − represents chloride ion, bromide ion, iodide ion, acetate ion, perchlorate ion, tetrafluoro borate ion, hexafluoro phosphate ion, hexafluoro arsenate ion, perfluoroalkyl sulfonate ion, or perfluoroalkyl sulfonylimide ion.
1. A magnesium ion containing non-aqueous electrolyte comprising magnesium and aluminum ions dissolved in an organic etheric solvent, the stoichiometric ratio of the aluminum ions and the magnesium falling within a range of 1.0 to 2.0, the electrolyte formed by:
adding metal magnesium, a halogenated hydrocarbon RX, an aluminum halide AlY 3 , and a quaternary ammonium salt R 1 R 2 R 3 R 4 N + Z to the organic etheric solvent to form a mixture, wherein R is an alkyl group or an aryl group, X is chlorine, bromine, or iodine, Y is chlorine, bromine, or iodine, and wherein R 1 , R 2 , R 3 , and R 4 represent each an alkyl group or an aryl group, and Z − represents a chloride ion (Cl − ), a bromide ion (B − ), an iodide ion (I − ), an acetate ion (CH 3 COO − ), a perchlorate ion (ClO 4 − ), a tetrafluoro borate ion (BF 4 − ), a hexafluoro phosphate ion (PF 6 − ), a hexafluoro arsenate ion (AsF 6 − ), a perfluoroalkyl sulfonate ion (Rf1SO 3 − ) (Rf1 is perfluoroalkyl group), or a perfluoroalkyl sulfonylimide ion ((Rf2SO 2 ) 2 N − )(Rf2 is a perfluoroalkyl group); and
applying a heating treatment while stirring the mixture, wherein the electrolyte has a higher oxidation potential than a Grignard reagent formed by a reaction between the metal magnesium and the halogenated hydrocarbon RX.
2. The magnesium ion containing non-aqueous electrolyte according to claim 1 , wherein the halogenated hydrocarbon comprises at least one element selected from a group consisting of iodomethane, iodoethane, 1-iodopropane, 2-iodopropane, 1-iodobutane, 2-iodobutane, bromoethane, 1-bromopropane, 2-bromopropane, 1-bromobutane, 2-bromobutane, bromobenzene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, 1-chloropropane, 2-chloropropane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene.
3. The magnesium ion containing non-aqueous electrolyte according to claim 1 , wherein the halogenated hydrocarbon is added to the organic etheric solvent at a ratio in a range from 0.8 to 1.2 mol based on 1 mol of the metal magnesium.
4. The magnesium ion containing non-aqueous electrolyte according to claim 1 , wherein the aluminum halide is aluminum chloride.
5. The magnesium ion containing non-aqueous electrolyte according to claim 1 , wherein the aluminum halide is added to the organic etheric solvent at a ratio in a range from 1.0 to 2.0 mol based on 1 mol of the metal magnesium.
6. The magnesium ion containing non-aqueous electrolyte according to claim 1 , wherein the quaternary ammonium salt is tetrabutyl ammonium trifluoromethane sulfonate (CF 3 SO 3 N(C 4 H 9 ) 4 ).
7. The magnesium ion containing non-aqueous electrolyte according to claim 1 , wherein the quaternary ammonium salt is added to the organic etheric solvent at a ratio in a range of 1.0 to 2.0 mol based on 1 mol of the metal magnesium.
8. The magnesium ion containing non-aqueous electrolyte according to claim 1 , wherein the organic etheric solvent is 1,2-dimethoxyethane.
9. The magnesium ion containing non-aqueous electrolyte according to claim 1 , wherein the metal magnesium is added to the organic etheric solvent at a ratio in a range from 0.25 to 1.0 mol per liter of the organic etheric solvent.
10. The magnesium ion containing non-aqueous electrolyte according to claim 1 , wherein a heating temperature during the heating treatment is in a range from 50 to 80° C.
11. An electrochemical device having a first electrode, a second electrode, and a magnesium ion containing non-aqueous electrolyte according to claim 1 , wherein an active substance of the second electrode is constituted so as to be oxidized to form magnesium ions.
12. The electrochemical device according to claim 11 , wherein the active substance of the second electrode is elemental metal of magnesium or an alloy containing magnesium.
13. The electrochemical device according to claim 11 , wherein an active substance of the first electrode comprises a compound reactive with the magnesium ions or a compound occluding the magnesium ions.
14. The electrochemical device according to claim 11 , which is constituted as a battery.
15. The electrochemical device according to claim 14 , which is constituted as a secondary battery chargeable by reverse reaction.
16. The magnesium ion containing non-aqueous electrolyte according to claim 1 , further comprising a hydrocarbon, the stoichiometric ratio of the hydrocarbon and the magnesium falling within a range of 0.8 to 1.2.
17. The magnesium ion containing non-aqueous electrolyte according to claim 1 , further comprising an ammonium salt, the stoichiometric ratio of the ammonium salt and the magnesium falling within a range of 1.0 to 2.0.
18. The magnesium ion containing non-aqueous electrolyte according to claim 1 , wherein the ratio of magnesium to the organic etheric solvent falls within a range of 0.25 to 1.00 mol/L.