One step synthesis of non-chlorinated magnesium electrolytes

Patent metadata

Field	Value
Publication number	US-10199688-B2
Application number	US-201514979254-A
Country	US
Kind code	B2
Filing date	Dec 22, 2015
Priority date	Dec 22, 2015
Publication date	Feb 5, 2019
Grant date	Feb 5, 2019

Abstract

A one-step method to prepare a magnesium electrolyte salt is provided. According to the method, the magnesium electrolyte is obtained by reacting a Grignard reagent and a fluorinated aryl borane. In addition, formation of monomeric or dimeric magnesium ion is determined by the choice of the Grignard reagent. The magnesium electrolyte may be non-chlorinated and non-corrosive. A magnesium battery containing the magnesium electrolyte is also provided.

First claim

The invention claimed is:

1. A method to prepare a magnesium salt of formula (I)
Mg(ROR) y [B(Ar F ) 3 Ph] 2   (I)

wherein
ROR is a nonaqueous solvent comprising an ether oxygen and y is an integer of 2 to 6,
Ar F is an optionally substituted phenyl group comprising at least one fluorine substituent,
Ph is a —C 6 H 5 — group,
the method comprising:
reacting PhMgI with a boron compound of formula (II),
B(Ar F ) 3   (II)

in the solvent ROR.

2. The method of claim 1 , wherein Ar F is a phenyl group which comprises at least one fluorine atom.

3. The method of claim 1 , wherein Ar F is a phenyl group which comprises at least one substituent selected from the group consisting of a CF 3 — group, a CF 2 H group and a CFH 2 — group.

4. The method of claim 1 , wherein Ar F is a —C 6 F 5 — group.

5. The method of claim 1 , wherein the nonaqueous solvent comprising an ether oxygen is at least one solvent selected from the group consisting of tetrahydrofuran (THF), dimethoxyethane (DME) and di ethylene glycol dimethyl ether (diglyme) (DGM).

6. The method of claim 1 , wherein the magnesium salt of formula (I) is Mg(THF) 6 [(C 6 F 5 ) 3 B(C 6 H 5 )] 2 .

7. A method to prepare a magnesium salt of formula (IV):
Mg(THF) 6 [(C 6 F 5 ) 3 B(C 6 H 5 )] 2   (IV)

wherein
THF is a tetrahydrofuran molecule,
the method comprising:
reacting PhMgI with B(C 6 F 5 ) 3 in THF.

8. A magnesium battery, comprising:
a negative electrode comprising magnesium as an active ingredient;
a positive electrode;
a solvent; and
a magnesium electrolyte of formula (I):
Mg(ROR) y [B(Ar F ) 3 Ph] 2   (I),

wherein
ROR is a nonaqueous solvent comprising an ether oxygen and y is an integer of 2 to 6,
Ar F is an optionally substituted phenyl group comprising at least one fluorine substituent, and
Ph is a C 6 H 5 — group.

9. The magnesium battery of claim 8 , wherein the negative electrode is magnesium.

10. The magnesium battery of claim 8 , wherein the positive electrode active material comprises at least one component selected from the group consisting of sulfur, graphitic carbon, carbon fiber, glassy carbon, pyrolitic carbon, amorphous carbon, Mo 6 S 8 , MnO 2 , CuS, Cu 2 S, Ag 2 S, CrS 2 , VOPO 4 , TiS 2 , V 2 O 5 , MgVO 3 , MoS 2 , MgV 2 O 5 , MoO 3 , CuCr 2 S 4 , MgCr 2 S 4 , MgMn 2 O 4 , Mg 2 MnO 4 , MgFe 2 (PO4) 3 , MgV 2 (PO 4 ) 3 , MgMnSiO 4 , MgFe 2 (PO 4 ) 2 , Mg 0.5 VPO 4 F, TiP 2 O 7 , VP 2 O 7 and FeF 3 .

11. The magnesium battery of claim 8 , further comprising a non-noble metal component.

12. The magnesium battery of claim 8 , wherein the solvent is selected from the group consisting of tetrahydrofuran, 2-methyl tetrahydrofuran, dimethoxyethane, glyme, monoglyme, dimethyl glycol, ethylene glycol dimethyl ether, diethyl ether, ethyl glyme, diglyme, proglyme, ethyl diglyme, triglyme, butyl diglyme, tetraglyme, polyglyme, higlyme, and a mixture thereof.

13. The magnesium battery of claim 8 , wherein Ar F is a phenyl group which comprises at least one fluorine atom.

14. The magnesium battery of claim 8 , wherein Ar F is a phenyl group which comprises at least one substituent selected from the group consisting of a CF 3 — group, a CF 2 H group and a CFH 2 — group.

15. The magnesium battery of claim 8 , wherein the magnesium electrolyte of formula (I) is Mg(THF) 6 [(C 6 F 5 ) 3 B(C 6 H 5 )] 2 .

Assignees

• Toyota Eng & Mfg North America

Inventors

• Bucur Claudiu B
• Muldoon John

Classifications

• H01M10/054

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

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title

• H01M4/133

  Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title

• H01M4/58

  of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates · CPC title

• H01M4/583

  Carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title