Phosphorus electrolytic solution containing magnesium ions

Patent metadata

Field	Value
Publication number	US-10862169-B2
Application number	US-201716304488-A
Country	US
Kind code	B2
Filing date	May 26, 2017
Priority date	May 27, 2016
Publication date	Dec 8, 2020
Grant date	Dec 8, 2020

Abstract

The present invention relates to an electrolytic solution for a magnesium battery, formed by mixing a compound represented by the following general formula (I), a Lewis acid or a compound represented by the following general formula (A), and a solvent; and the like.

{In the formula, m represents 0 or 2, n represents 2 in a case of m=0 and represents 0 or 1 in a case of m=2, X 1 represents a chlorine atom or a bromine atom, and two R 1 's each independently represent a magnesium chloride oxy group; a magnesium bromide oxy group; an alkyl group which may have a halogeno group or the like as a substituent; an alkoxy group; an aryl group which may have an alkoxy group or the like as a substituent; an aryloxy group which may have an alkoxy group or the like as a substituent; or a group represented by the following general formula (1), and two R 1 's may also form the following general formula (2).}

(In the formula, four R 10 's each independently represent an alkyl group, a perfluoroalkyl group, a phenyl group, or a perfluorophenyl group.)

First claim

The invention claimed is:

1. An electrolytic solution for a magnesium battery, formed by mixing a compound represented by the following general formula (I), a Lewis acid or a compound represented by the following general formula (A), and a solvent:

where, in the formula (I), m represents 0 or 2, n represents 2 in a case of m=0 and represents 0 or 1 in a case of m=2, X 1 represents a chlorine atom or a bromine atom, each R 1 independently represents a magnesium chloride oxy group (—OMgCl); a magnesium bromide oxy group (—OMgBr); an alkyl group having 1 to 6 carbon atoms, which may have a halogeno group or an alkoxy group as a substituent; an alkoxy group having 1 to 6 carbon atoms; an aryl group having 6 to 10 carbon atoms, which may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent; an aryloxy group having 6 to 10 carbon atoms, which may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent; or a group represented by the following general formula (1), or two R 1 's may form the following general formula (2):

where, in the formula (1), a represents an integer of 1 to 3, X 2 represents a chlorine atom or a bromine atom, and each R 2 independently represents a magnesium chloride oxy group (—OMgCl); a magnesium bromide oxy group (—OMgBr); an alkyl group having 1 to 6 carbon atoms, which may have a halogeno group or an alkoxy group as a substituent; an alkoxy group having 1 to 6 carbon atoms; an aryl group having 6 to 10 carbon atoms, which may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent; or an aryloxy group having 6 to 10 carbon atoms, which may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent; and

where, in the formula (2), b represents an integer of 1 to 3, and R 2 is the same as described above; and
Mg[N(SO 2 R 10 ) 2 ] 2   (A),

where, in the formula (A), each R 10 independently represents an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms, a phenyl group, or a perfluorophenyl group.

2. The electrolytic solution for a magnesium battery according to claim 1 ,
wherein the Lewis acid contains beryllium, boron, aluminum, silicon, tin, titanium, chromium, iron, or cobalt as an element.

3. The electrolytic solution for a magnesium battery according to claim 1 ,
wherein the Lewis acid contains aluminum as an element.

4. The electrolytic solution for a magnesium battery according to claim 1 ,
wherein the Lewis acid is aluminum chloride.

5. The electrolytic solution for a magnesium battery according to claim 1 ,
wherein each R 1 in the general formula (I) independently represents a magnesium chloride oxy group (—OMgCl); an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a phenyl group which may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent; a phenoxy group which may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent; or a group represented by the following general formula (3), or two R 1 's form the following general formula (4):

where in the formula (3), each R 3 independently represents a magnesium chloride oxy group (—OMgCl); an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a phenyl group which may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent; or a phenoxy group which may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent, and a is the same as described above; and

where, in the formula (4), represents an integer of 1 to 3, and R 3 is the same as described above.

6. The electrolytic solution for a magnesium battery according to claim 1 ,
wherein each R 1 in the general formula (I) independently represents a magnesium chloride oxy group (—OMgCl); an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a phenyl group which may have an alkoxy group as a substituent; a phenoxy group; or a group represented by the following formula (5), or two R 1 's form the following formula (6),

7. The electrolytic solution for a magnesium battery according to claim 1 ,
wherein X 1 in the general formula (I) is a chlorine atom.

8. The electrolytic solution for a magnesium battery according to claim 1 ,
wherein the compound represented by the general formula (A) is magnesium bis(trifluoromethanesulfonyl)imide.

9. The electrolytic solution for a magnesium battery according to claim 1 ,
wherein the solvent comprises at least one selected from the group consisting of ether solvents, halogenated hydrocarbon solvents, carbonate solvents, nitrile solvents, and sulfone solvents.

10. An electrochemical device comprising:
the electrolytic solution according to claim 1 ;
a positive electrode; and
a negative electrode.

11. A compound represented by the following general formula (I′):

where, in the formula (I′), m represents 0 or 2,
n represents 2 when m=0 and represents 0 or 1 when m=2,
X 1 represents a chlorine atom,
each R 1 independently represents a magnesium chloride oxy group (—OMgCl); a magnesium bromide oxy group (—OMgBr); an alkyl group having 1 to 6 carbon atoms, which may have a halogeno group or an alkoxy group as a substituent; an alkoxy group having 1 to 6 carbon atoms; an aryl group having 6 to 10 carbon atoms, which may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent; an aryloxy group having 6 to 10 carbon atoms, which may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent; or a group represented by the following general formula (1), or two R 1 's may form the following general formula (2):

where, in the formula (1), a represents an integer of 1 to 3, X 2 represents a chlorine atom or a bromine atom, and each R 2 independently represents magnesium chloride oxy group (—OMgCl); magnesium bromide oxy group (—OMgBr); an alkyl group having 1 to 6 carbon atoms, which may have a halogeno group or an alkoxy group as a substituent; an alkoxy group having 1 to 6 carbon atoms; an aryl group having 6 to 10 carbon atoms, which may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent; or an aryloxy group having 6 to 10 carbon atoms, which may have a halogeno group, an alkyl group, a halogenoalkyl group, or an alkoxy group as a substituent; and

Assignees

• Fujifilm Wako Pure Chemical Corp

Inventors

• Sato Kazuhiko
• Mori Goro
• WATAHIKI Hiromi
• Okamoto Kuniaki
• Shimamura Nobutaka

Classifications

• H01M10/054 Primary

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

• C07F9/46

  Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids {including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof} · CPC title

• C07F9/38

  Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids {; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]} · CPC title

• C07F9/30

  Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids {; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]} · CPC title

• C07F3/02

  Magnesium compounds · CPC title