CN111370759B - Magnesium battery electrolyte, preparation method thereof and magnesium battery - Google Patents

Magnesium battery electrolyte, preparation method thereof and magnesium battery Download PDF

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CN111370759B
CN111370759B CN202010186246.8A CN202010186246A CN111370759B CN 111370759 B CN111370759 B CN 111370759B CN 202010186246 A CN202010186246 A CN 202010186246A CN 111370759 B CN111370759 B CN 111370759B
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magnesium
electrolyte
magnesium battery
salt
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CN111370759A (en
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张跃钢
范海燕
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Tsinghua University
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Tsinghua University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a magnesium battery electrolyte, which comprises gel-state electrolyte salt, wherein the chemical formula of the electrolyte salt is [ MgXM ] p ][B(ORO) 4 ] n Wherein, X is selected from one or more of-1-valent halogen ions and halogen-like ions, M is a complexing agent, p is selected from any integer from 1 to 5, n is selected from any positive integer, and R is selected from the general formula- (C) n1 H n2 Y n3 O n4 ) -wherein said Y is selected from one or more of-1 valent said halide and said halide-like ion, said n 1 Is selected from any integer between 2 and 10, and n is 2 、n 3 、n 4 Are all integers greater than or equal to 0, n 2 +n 3 ≤2n 1 . The invention also relates to a preparation method of the magnesium battery electrolyte, which comprises the following steps: mixing anhydrous magnesium salt, anhydrous polyhydric alcohol and non-aqueous solvent to obtain a mixture; and reacting the mixture at 25-200 ℃; wherein the anhydrous magnesium salt is MgXBH 4 And the anhydrous polyalcohol is OH-R-OH. The invention further relates to a magnesium battery comprising the magnesium battery electrolyte.

Description

Magnesium battery electrolyte, preparation method thereof and magnesium battery
Technical Field
The invention relates to the technical field of energy, in particular to a magnesium battery electrolyte, a preparation method thereof and a magnesium battery.
Background
Magnesium batteries are receiving much attention because their volumetric energy density is higher than that of lithium batteries, especially magnesium-sulfur batteries, whose theoretical energy density is more than 4000WH/L. The development of magnesium batteries is still very slow, however, one of the main reasons is the lack of suitable electrolytes.
At present, the developed HMDS system, MACC system, B-based system and Mg (TFSI) 2 The electrolyte of magnesium-sulfur batteries such as a system and the like generally has the problems of easy occurrence of internal short circuit, easy leakage and the like of the battery. The newly developed electrolyte based on magnesium borohydride-polytetrahydrofuran is in a gel state, so that the possibility of short circuit inside the battery can be well reduced, the problems of electrolyte leakage and the like are avoided, but unfortunately, the electrolyte cannot be matched with a sulfur positive electrode.
Disclosure of Invention
Based on this, there is a need to provide a gel-state magnesium battery electrolyte capable of reversibly depositing and dissolving magnesium and matching with a sulfur positive electrode, a method of preparing the same, and a magnesium battery.
The invention provides a magnesium battery electrolyte, which comprises gel-state electrolyte salt, wherein the chemical formula of the electrolyte salt is [ MgXM ] p ][B(ORO) 4 ] n Wherein, X is selected from one or more of-1-valent halogen ions and halogen-like ions, M is a complexing agent, p is selected from any integer from 1 to 5, n is selected from any positive integer, R is selected from the general formula- (C) n1 H n2 Y n3 O n4 ) -wherein said Y is selected from one or more of-1 valent said halide and said halide-like ion, said n 1 Is selected from any integer between 2 and 10, and n is 2 、n 3 、n 4 Are all integers greater than or equal to 0, n 2 +n 3 ≤2n 1 . The cation in the electrolyte salt is [ MgX ] coordinated with the complexing agent M] + The anion being [ B (ORO) having a boron-containing polymer skeleton 4 ] n － 。
In one embodiment, X is selected from F － 、Cl － 、Br － 、I － 、CN － And SCN － One or more of, Y is selected from F － 、Cl － 、Br － 、I － 、CN － And SCN － One or more of (a).
In one embodiment, X is selected from Cl - Y is selected from F - 。
In one embodiment, R is- (R) 1 OR 2 OR 3 OR 4 ) -, said R 1 、R 2 、R 3 、R 4 Each independently selected from the group consisting of m1 H m2 Y m3 ) -wherein said Y is selected from one or more of-1 valent said halide and said halide-like ion, said m 1 Is selected from any integer between 1 and 3, and m is 2 、m 3 Are all integers of 0 or more, m 2 +m 3 ≤2m 1 。
In one of which is implementedIn the examples, the R is 1 And R 4 Selected from the same group, said R 2 And R 3 Selected from the same group.
In one embodiment, the water-soluble complexing agent further comprises a non-aqueous solvent, and the complexing agent M and the non-aqueous solvent are the same kind of molecule.
In one embodiment, the non-aqueous solvent and the complexing agent are selected from one or more of an ionic liquid and an organic solvent, respectively.
In one embodiment, the ionic liquid comprises one or more of imidazole ionic liquid, piperidine ionic liquid and pyrrole ionic liquid, and the imidazole ionic liquid is selected from one or more of 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonic acid) imide; the pyrrole ionic liquid is selected from N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt, and the piperidine ionic liquid is selected from N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt.
In one embodiment, the organic solvent comprises one or more of ether compounds, lipid compounds and aromatic compounds, wherein the ether compounds are selected from one or more of tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dioxane and polyethylene glycol dimethyl ether; the ester compound is selected from ethyl acetate; the aromatic compound is selected from one or more of pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2, 6-dichloropyridine, 2-aminopyridine and azomethimazole; also comprises one or more of toluene, dimethyl sulfoxide, dimethyl formamide and acetonitrile.
In one embodiment, the electrolyte salt has the formula [ MgClM p ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n 、[MgBrM p ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n 、[MgIM p ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n 、[MgFM p ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n 、[MgCNM p ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n 、[MgSCNM p ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n 、[MgClM p ][B(OC 2 H 2 Cl 2 OC 2 Cl 4 OC 2 Cl 4 OC 2 H 2 Cl 2 ) 4 ] n 、[MgBrM p ][B(OC 2 H 2 Cl 2 OC 2 Cl 4 OC 2 Cl 4 OC 2 H 2 Cl 2 ) 4 ] n 、[MgIM p ][B(OC 2 H 2 Cl 2 OC 2 Cl 4 OC 2 Cl 4 OC 2 H 2 Cl 2 ) 4 ] n 、[MgFM p ][B(OC 2 H 2 Cl 2 OC 2 Cl 4 OC 2 Cl 4 OC 2 H 2 Cl 2 ) 4 ] n 、[MgCNM p ][B(OC 2 H 2 Cl 2 OC 2 Cl 4 OC 2 Cl 4 OC 2 H 2 Cl 2 ) 4 ] n 、[MgSCNM p ][B(OC 2 H 2 Cl 2 OC 2 Cl 4 OC 2 Cl 4 OC 2 H 2 Cl 2 ) 4 ] n 、[MgClMp][B(OC 2 H 2 Br 2 OC 2 Br 4 OC 2 Br 4 OC 2 H 2 Br 2 ) 4 ] n 、[MgBrM p ][B(OC 2 H 2 Br 2 OC 2 Br 4 OC 2 Br 4 OC 2 H 2 Br 2 ) 4 ] n 、[MgIM p ][B(OC 2 H 2 Br 2 OC 2 Br 4 OC 2 Br 4 OC 2 H 2 Br 2 ) 4 ] n 、[MgFM p ][B(OC 2 H 2 Br 2 OC 2 Br 4 OC 2 Br 4 OC 2 H 2 Br 2 ) 4 ] n 、[MgCNM p ][B(OC 2 H 2 Br 2 OC 2 Br 4 OC 2 Br 4 OC 2 H 2 Br 2 ) 4 ] n 、[MgSCNM p ][B(OC 2 H 2 Br 2 OC 2 Br 4 OC 2 Br 4 OC 2 H 2 Br 2 ) 4 ] n 、[MgClM p ][B(OC 2 H 2 I 2 OC 2 I 4 OC 2 I 4 OC 2 H 2 I 2 ) 4 ] n 、[MgBrM p ][B(OC 2 H 2 I 2 OC 2 I 4 OC 2 I 4 OC 2 H 2 I 2 ) 4 ] n 、[MgIM p ][B(OC 2 H 2 I 2 OC 2 I 4 OC 2 I 4 OC 2 H 2 I 2 ) 4 ] n 、[MgFM p ][B(OC 2 H 2 I 2 OC 2 I 4 OC 2 I 4 OC 2 H 2 I 2 ) 4 ] n 、[MgCNM p ][B(OC 2 H 2 I 2 OC 2 I 4 OC 2 I 4 OC 2 H 2 I 2 ) 4 ] n 、[MgSCNM p ][B(OC 2 H 2 I 2 OC 2 I 4 OC 2 I 4 OC 2 H 2 I 2 ) 4 ] n 、[MgClM p ][B(OC 2 H 2 (CN) 2 OC 2 (CN) 4 OC 2 (CN) 4 OC 2 H 2 (CN) 2 ) 4 ] n 、[MgBrM p ][B(OC 2 H 2 (CN) 2 OC 2 (CN) 4 OC 2 (CN) 4 OC 2 H 2 (CN) 2 ) 4 ] n 、[MgIM p ][B(OC 2 H 2 (CN) 2 OC 2 (CN) 4 OC 2 (CN) 4 OC 2 H 2 (CN) 2 ) 4 ] n 、[MgFM p ][B(OC 2 H 2 (CN) 2 OC 2 (CN) 4 OC 2 (CN) 4 OC 2 H 2 (CN) 2 ) 4 ] n 、[MgCNM p ][B(OC 2 H 2 (CN) 2 OC 2 (CN) 4 OC 2 (CN) 4 OC 2 H 2 (CN) 2 ) 4 ] n 、[MgSCNM p ][B(OC 2 H 2 (CN) 2 OC 2 (CN) 4 OC 2 (CN) 4 OC 2 H 2 (CN) 2 ) 4 ] n 、[MgClM p ][B(OC 2 H 2 (SCN) 2 OC 2 (SCN) 4 OC 2 (SCN) 4 OC 2 H 2 (SCN) 2 ) 4 ] n 、[MgBrM p ][B(OC 2 H 2 (SCN) 2 OC 2 (SCN) 4 OC 2 (SCN) 4 OC 2 H 2 (SCN) 2 ) 4 ] n 、[MgIM p ][B(OC 2 H 2 (SCN) 2 OC 2 (SCN) 4 OC 2 (SCN) 4 OC 2 H 2 (SCN) 2 ) 4 ] n 、[MgFM p ][B(OC 2 H 2 (SCN) 2 OC 2 (SCN) 4 OC 2 (SCN) 4 OC 2 H 2 (SCN) 2 ) 4 ] n 、[MgCNM p ][B(OC 2 H 2 (SCN) 2 OC 2 (SCN) 4 OC 2 (SCN) 4 OC 2 H 2 (SCN) 2 ) 4 ] n 、[MgSCNM p ][B(OC 2 H 2 (SCN) 2 OC 2 (SCN) 4 OC 2 (SCN) 4 OC 2 H 2 (SCN) 2 ) 4 ] n One or more of (a).
The invention also provides a preparation method of the magnesium battery electrolyte, which comprises the following steps: mixing anhydrous magnesium salt, anhydrous polyhydric alcohol and the non-aqueous solvent according to claims 7 to 10 to obtain a mixture; and reacting the mixture at 25-200 ℃; wherein the anhydrous magnesium salt is MgXBH 4 The anhydrous polyalcohol is OH-R-OH, and R is selected from the general formula of- (C) n1 H n2 Y n3 O n4 ) -wherein said Y is selected from one or more of said halide ions and said halide-like ions having a valence of-1, and said n 1 Is selected from any integer between 2 and 10, and n is 2 、n 3 、n 4 Are all integers greater than or equal to 0, n 2 +n 3 ≤2n 1 。
In one embodiment, the molar ratio of the anhydrous magnesium salt to the anhydrous polyol is 1: (4-6).
In one embodiment, the concentration of the anhydrous magnesium salt in the mixture is 0.1mol/L to 3mol/L.
The invention further provides a magnesium battery, which comprises the magnesium battery electrolyte.
In one embodiment, the magnesium battery is a magnesium-sulfur battery.
The magnesium battery electrolyte [ MgXM ] provided by the invention p ][B(ORO) 4 ] n Is magnesium-based gel-state electrolyte, anion [ B (ORO) 4 ] n － Having a polymer skeleton forming a spatial network structure, and a cation [ MgX ]] + Coordinately bound to a complexing agent bound by said steric network and said cation [ MgX ]] + Locking in electrolyte salt to electrify the magnesiumThe battery electrolyte is in a gel state, so that the problems of short circuit and electrolyte leakage in the battery can be effectively avoided, and the flexibility of the battery is improved. Moreover, the electrolyte salt does not contain nucleophilic bonds, is a non-nucleophilic electrolyte, can be well matched with a sulfur anode, and can be used as an electrolyte of a magnesium-sulfur battery. [ MgX ]] + The resistance is small, the mass transfer is fast, and the battery manufactured by using the magnesium battery electrolyte has excellent performance.
Drawings
Fig. 1 is a flowchart illustrating a method for preparing an electrolyte for a magnesium battery according to an embodiment of the present invention;
FIG. 2 is a photograph of an electrolyte for a magnesium battery according to an embodiment of the present invention;
FIG. 3 is an infrared spectrum of a magnesium battery electrolyte according to an embodiment of the present invention, in which MCT-B-PFTEG is MgCl (THF) 3 ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n PFTEG is fluorinated tetraethanol;
FIG. 4 is a Raman spectrum of a magnesium battery electrolyte according to an embodiment of the present invention, in which MCT-B-PFTEG is MgCl (THF) 3 ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n PFTEG is fluorinated tetraethanol;
FIG. 5 is a diagram illustrating the reaction formula of the raw materials in the method for preparing the electrolyte of the magnesium battery according to the embodiment of the present invention;
FIG. 6 is a schematic diagram of the structure of an electrolyte salt in the electrolyte of a magnesium battery according to an embodiment of the present invention;
FIG. 7 is a graph showing the cyclic voltammetry characteristics of an electrolyte for a magnesium battery on a platinum electrode according to an embodiment of the present invention;
FIG. 8 is a graph of a linear scan of a magnesium battery electrolyte on a platinum electrode in accordance with an embodiment of the present invention;
fig. 9 is a charge-discharge cycle-specific capacity curve diagram of a magnesium-sulfur battery in accordance with an embodiment of the present invention;
fig. 10 is a charging and discharging specific capacity-voltage curve diagram of a magnesium-sulfur battery according to an embodiment of the invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The embodiment of the invention provides a magnesium battery electrolyte, which comprises gel state electrolyte salt, wherein the chemical formula of the electrolyte salt is [ MgXM ] p ][B(ORO) 4 ] n Wherein, X is selected from one or more of-1-valent halogen ions and halogen-like ions, M is a complexing agent, p is selected from any integer from 1 to 5, n is selected from any positive integer, R is selected from the general formula- (C) n1 H n2 Y n3 O n4 ) -wherein said Y is selected from one or more of said halide ions and said halide-like ions having a valence of-1, and said n 1 Is selected from any integer between 2 and 10, and n is 2 、n 3 、n 4 Are all integers greater than or equal to 0, n 2 +n 3 ≤2n 1 . The cation in the electrolyte salt is [ MgX ] coordinated with the complexing agent M] + The anion being [ B (ORO) having a boron-containing polymer skeleton 4 ] n － 。
The magnesium battery electrolyte [ MgXM ] of the embodiment of the invention p ][B(ORO) 4 ] n Is a magnesium-based gel electrolyte, an anion [ B (ORO) 4 ] n － Has a polymer skeleton and a polymer matrix, wherein,form a spatial network structure, and the cation [ MgX ]] + Coordinately bound to a complexing agent bound by said steric network and said cation [ MgX ]] + The locking in the electrolyte salt makes magnesium battery electrolyte is the gel state, can effectively avoid the inside problem that takes place the short circuit and electrolyte reveals of battery, makes the flexibility of battery promote. Moreover, the electrolyte salt does not contain nucleophilic bonds, is a non-nucleophilic electrolyte, can be well matched with a sulfur anode, and can be used as an electrolyte of a magnesium-sulfur battery. [ MgX ]] + The resistance is small, the mass transfer is fast, and the battery manufactured by the magnesium battery electrolyte has excellent performance.
X and Y can be respectively selected from one or more of the halogen ions and the halogen-like ions, and the halogen ions can be selected from F － 、Cl － 、Br － And I － One or more of (a). The halogen-like ion may be selected from CN － And SCN － One or more of (a).
Preferably, X is selected from Cl - . X is Cl - Of the cation [ MgX ] formed] + Is more stable.
Preferably, Y is selected from F - . Y is F - The anion formed [ B (ORO) 4 ] n － Is more stable.
In one embodiment, R is- (R) 1 OR 2 OR 3 OR 4 ) -, said R 1 、R 2 、R 3 、R 4 Each independently selected from the group consisting of m1 H m2 Y m3 ) -wherein said Y is selected from one or more of said halide ions and said halide-like ions having a valence of-1, and m is 1 Is selected from any integer between 1 and 3, and m is 2 、m 3 Are all integers of 0 or more, m 2 +m 3 ≤2m 1 . Has a radical of formula (R) 1 OR 2 OR 3 OR 4 ) -a group of structures R, the anion formed [ B (ORO) 4 ] n － Is more stable.
Preferably, said R is 1 And R 4 Selected from the same group, said R 2 And R 3 Selected from the same group. The R is 1 And R 4 Are the same group, the R 2 And R 3 Being a homologous group, the anion formed [ B (ORO) 4 ] n － Is more stable.
The electrolyte salt may have a chemical formula of [ MgClM p ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n 、[MgBrM p ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n 、[MgIM p ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n 、[MgFM p ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n 、[MgCNM p ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n 、[MgSCNM p ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n 、[MgClM p ][B(OC 2 H 2 Cl 2 OC 2 Cl 4 OC 2 Cl 4 OC 2 H 2 Cl 2 ) 4 ] n 、[MgBrM p ][B(OC 2 H 2 Cl 2 OC 2 Cl 4 OC 2 Cl 4 OC 2 H 2 Cl 2 ) 4 ] n 、[MgIM p ][B(OC 2 H 2 Cl 2 OC 2 Cl 4 OC 2 Cl 4 OC 2 H 2 Cl 2 ) 4 ] n 、[MgFM p ][B(OC 2 H 2 Cl 2 OC 2 Cl 4 OC 2 Cl 4 OC 2 H 2 Cl 2 ) 4 ] n 、[MgCNM p ][B(OC 2 H 2 Cl 2 OC 2 Cl 4 OC 2 Cl 4 OC 2 H 2 Cl 2 ) 4 ] n 、[MgSCNM p ][B(OC 2 H 2 Cl 2 OC 2 Cl 4 OC 2 Cl 4 OC 2 H 2 Cl 2 ) 4 ] n 、[MgClMp][B(OC 2 H 2 Br 2 OC 2 Br 4 OC 2 Br 4 OC 2 H 2 Br 2 ) 4 ] n 、[MgBrM p ][B(OC 2 H 2 Br 2 OC 2 Br 4 OC 2 Br 4 OC 2 H 2 Br 2 ) 4 ] n 、[MgIM p ][B(OC 2 H 2 Br 2 OC 2 Br 4 OC 2 Br 4 OC 2 H 2 Br 2 ) 4 ] n 、[MgFM p ][B(OC 2 H 2 Br 2 OC 2 Br 4 OC 2 Br 4 OC 2 H 2 Br 2 ) 4 ] n 、[MgCNM p ][B(OC 2 H 2 Br 2 OC 2 Br 4 OC 2 Br 4 OC 2 H 2 Br 2 ) 4 ] n 、[MgSCNM p ][B(OC 2 H 2 Br 2 OC 2 Br 4 OC 2 Br 4 OC 2 H 2 Br 2 ) 4 ] n 、[MgClM p ][B(OC 2 H 2 I 2 OC 2 I 4 OC 2 I 4 OC 2 H 2 I 2 ) 4 ] n 、[MgBrM p ][B(OC 2 H 2 I 2 OC 2 I 4 OC 2 I 4 OC 2 H 2 I 2 ) 4 ] n 、[MgIM p ][B(OC 2 H 2 I 2 OC 2 I 4 OC 2 I 4 OC 2 H 2 I 2 ) 4 ] n 、[MgFM p ][B(OC 2 H 2 I 2 OC 2 I 4 OC 2 I 4 OC 2 H 2 I 2 ) 4 ] n 、[MgCNM p ][B(OC 2 H 2 I 2 OC 2 I 4 OC 2 I 4 OC 2 H 2 I 2 ) 4 ] n 、[MgSCNM p ][B(OC 2 H 2 I 2 OC 2 I 4 OC 2 I 4 OC 2 H 2 I 2 ) 4 ] n 、[MgClM p ][B(OC 2 H 2 (CN) 2 OC 2 (CN) 4 OC 2 (CN) 4 OC 2 H 2 (CN) 2 ) 4 ] n 、[MgBrM p ][B(OC 2 H 2 (CN) 2 OC 2 (CN) 4 OC 2 (CN) 4 OC 2 H 2 (CN) 2 ) 4 ] n 、[MgIM p ][B(OC 2 H 2 (CN) 2 OC 2 (CN) 4 OC 2 (CN) 4 OC 2 H 2 (CN) 2 ) 4 ] n 、[MgFM p ][B(OC 2 H 2 (CN) 2 OC 2 (CN) 4 OC 2 (CN) 4 OC 2 H 2 (CN) 2 ) 4 ] n 、[MgCNM p ][B(OC 2 H 2 (CN) 2 OC 2 (CN) 4 OC 2 (CN) 4 OC 2 H 2 (CN) 2 ) 4 ] n 、[MgSCNM p ][B(OC 2 H 2 (CN) 2 OC 2 (CN) 4 OC 2 (CN) 4 OC 2 H 2 (CN) 2 ) 4 ] n 、[MgClM p ][B(OC 2 H 2 (SCN) 2 OC 2 (SCN) 4 OC 2 (SCN) 4 OC 2 H 2 (SCN) 2 ) 4 ] n 、[MgBrM p ][B(OC 2 H 2 (SCN) 2 OC 2 (SCN) 4 OC 2 (SCN) 4 OC 2 H 2 (SCN) 2 ) 4 ] n 、[MgIM p ][B(OC 2 H 2 (SCN) 2 OC 2 (SCN) 4 OC 2 (SCN) 4 OC 2 H 2 (SCN) 2 ) 4 ] n 、[MgFM p ][B(OC 2 H 2 (SCN) 2 OC 2 (SCN) 4 OC 2 (SCN) 4 OC 2 H 2 (SCN) 2 ) 4 ] n 、[MgCNM p ][B(OC 2 H 2 (SCN) 2 OC 2 (SCN) 4 OC 2 (SCN) 4 OC 2 H 2 (SCN) 2 ) 4 ] n 、[MgSCNM p ][B(OC 2 H 2 (SCN) 2 OC 2 (SCN) 4 OC 2 (SCN) 4 OC 2 H 2 (SCN) 2 ) 4 ] n One or more of (a).
The electrolyte salt [ MgXM p ][B(ORO) 4 ] n The magnesium ions are provided, the magnesium ions have the function of an electrolytic salt and the function of a polymer, and can further serve as a solvent, so that the magnesium ions also have the property of gel without adding an additional solvent.
In one embodiment, the magnesium battery electrolyte further comprises a non-aqueous solvent.
The nonaqueous solvent and the complexing agent may be the same molecule or different molecules. In one embodiment, the non-aqueous solvent and the complexing agent are the same molecule.
By means of the complexing agent (i.e. ligand), a stable cation [ MgX ] can be obtained] + And a stable anion [ B (ORO) 4 ] n － . In one embodiment, the complexing agent may be selected from the non-aqueous solvent, i.e., molecules of the non-aqueous solvent and the [ MgX ]] + And (4) coordination. Cation [ MgX ] obtained by complexing agent] + Is readily soluble in said waterDissolving in the agent.
In one embodiment, the non-aqueous solvent and the complexing agent may be selected from one or more of an ionic liquid and an organic solvent.
In one embodiment, the ionic liquid comprises one or more of imidazole ionic liquid, piperidine ionic liquid and pyrrole ionic liquid, and the imidazole ionic liquid is selected from one or more of 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonic acid) imide; the pyrrole ionic liquid is selected from N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt, and the piperidine ionic liquid is selected from N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt.
In one embodiment, the organic solvent includes one or more of ether compounds selected from one or more of tetrahydrofuran, glyme, diglyme, triglyme, tetraglyme, dioxane, and glyme; the ester compound is selected from ethyl acetate; the aromatic compound is selected from one or more of pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2, 6-dichloropyridine, 2-aminopyridine and azomethimazole; also comprises one or more of toluene, dimethyl sulfoxide, dimethyl formamide and acetonitrile.
Referring to fig. 1, an embodiment of the present invention further provides a method for preparing an electrolyte for a magnesium battery, including:
s100, mixing an anhydrous magnesium salt, anhydrous polyhydric alcohol and the non-aqueous solvent to obtain a mixture; and
s200, reacting the mixture at 25-200 ℃;
wherein the anhydrous magnesium salt is MgXBH 4 The anhydrous polyalcohol is OH-R-OH, and R is selected from the general formula of- (C) n1 H n2 Y n3 O n4 ) -wherein said Y is selected from one or more of said halide ions and said halide-like ions having a valence of-1, and said n 1 Is selected from any integer between 2 and 10, and n is 2 、n 3 、n 4 Are all integers greater than or equal to 0, n 2 +n 3 ≤2n 1 。
The anhydrous magnesium salt is MgXBH 4 Can be prepared by known synthetic methods. In one embodiment, the anhydrous magnesium salt is MgXBH 4 The preparation method comprises the following steps: mixing Mg (BH) 4 ) 2 And MgX 2 Adding the mixture into the non-aqueous solvent (organic solvent and/or ionic liquid) according to a molar ratio of 1.
Polyols are generally considered to be common alcoholic organics and are not acid-base. Through a large number of experiments, the magnesium battery electrolyte is prepared by creatively using the boron magnesium salt as Lewis base and the anhydrous polyhydric alcohol as Lewis acid, and the boron magnesium salt and the anhydrous polyhydric alcohol respectively obtain coordination cations [ MgXM ] under the action of the coordination agent p ] + And anions [ B (ORO) 4 ] n － ，[B(ORO) 4 ] n － Is a polymer with a spatial network structure, [ MgXM ] p ] + Middle cation [ MgX ]] + Coordinately bound to a complexing agent which is bound by said spatial network and said cation [ MgX ]] + Locked in the electrolyte salt to form a stable non-nucleophilic gel-state electrolyte salt. The preparation method is low in preparation cost and simple in preparation process, and the obtained electrolyte salt is non-nucleophilic gel electrolyte salt, so that the problems of short circuit and electrolyte leakage in the battery can be effectively solved, and the flexibility of the battery is improved. The magnesium battery obtained by using the electrolyte salt as an electrolyte has excellent performance.
In one embodiment, the molar ratio of the anhydrous magnesium salt to the anhydrous polyol may be 1: (4-6) in a range of the ratio of the anhydrous magnesium salt to the anhydrous polyhydric alcohol to ensure sufficient reaction and to reduce the formation of other side reaction products.
In one embodiment, the concentration of the anhydrous magnesium salt in the mixture is 0.1mol/L to 3mol/L. Within this concentration range, the reaction efficiency of the anhydrous magnesium salt and the anhydrous polyol in the nonaqueous solvent is higher.
Preferably, the anhydrous polyol is OH-R-OH, R is of the general formula- (C) n1 H n2 Y n3 O n4 ) Y is F in the-middle, so that the electrolyte salt [ MgXM ] is more easily obtained p ][B(ORO) 4 ] n 。
Further preferably, R is- (R) 1 OR 2 OR 3 OR 4 ) -, said R 1 、R 2 、R 3 、R 4 Each independently selected from the group consisting of m1 H m2 F m3 ) The group of (A), (B) and (C), the group of (A), (B) and (C) 1 Is selected from any integer between 1 and 3, and m is 2 、m 3 Are all integers of 0 or more, m 2 +m 3 ≤2m 1 Thereby more easily obtaining the electrolyte salt [ MgXM ] p ][B(ORO) 4 ] n 。
Preferably, mgXBH in the anhydrous magnesium salt 4 Wherein X is Cl, so that the electrolyte salt [ MgXM ] is more easily obtained p ][B(ORO) 4 ] n 。
The embodiment of the invention also provides a magnesium battery, which comprises the magnesium battery electrolyte.
The magnesium battery includes a positive electrode and a negative electrode. Magnesium in the magnesium battery is mainly deintercalated at the positive electrode, the positive electrode comprises a positive electrode material, and the positive electrode material can be selected from inorganic transition metal oxides, sulfides, borides or phosphates. The negative electrode includes a negative electrode material, which may be selected from metallic magnesium or magnesium alloys.
The magnesium battery is a magnesium ion battery, preferably a magnesium-sulfur battery.
Examples
Preparing the magnesium battery electrolyte:
in a glove box with oxygen and water contents below 1ppm and filled with argon, 108Mg of anhydrous Mg (BH) 4 ) 2 And 190.42mg of anhydrous MgCl 2 Dissolved in 4mL Tetrahydrofuran (THF) and stirred at room temperature for 24h to obtain MgCl (THF) 3 And (3) solution.
3280mg of anhydrous tetraethanol fluoride (C) 8 H 6 F 12 O 5 Abbreviated as PFTEG) in 4mL of tetrahydrofuranIn furan (THF), stirring was carried out at room temperature for 6 hours to obtain a PFTEG solution. MgClBH is added 4 The solution and PFTEG solution (volume ratio 1). And carrying out infrared spectrum analysis and Raman spectrum analysis on the electrolyte.
Referring to FIGS. 3 and 4, IR spectroscopy showed that MgClBH was added 4 Thereafter, the infrared absorption peaks of two-OH groups in PFTEG, i.e., fluorinated tetraol, disappeared (the peak between the two dotted lines in FIG. 3 represents the infrared absorption peak of-OH group). FIG. 4 shows that the Raman spectrum analysis result shows that the peak intensity is 872cm -1 Presence of [ B-O ] at wavelength 4 ]Characteristic peak of (2). The electrolyte synthesized in the examples of the present invention was shown to contain an electrolyte salt [ MgCl (THF) ] in combination with nuclear magnetic and Raman data 3 ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n . Anhydrous MgClBH 4 The reaction formula of anhydrous fluorinated tetraethanol is shown in fig. 5, and the structure of the finally obtained electrolyte salt is shown in fig. 6.
Referring to fig. 7 and 8, in order to examine the performance of the magnesium battery electrolyte for depositing dissolved magnesium and the electrochemical window of the electrolyte, we tested the cyclic voltammetry characteristic curve and the linear scanning curve of the electrolyte on a metal platinum electrode, and the results show that the electrolyte can deposit dissolved magnesium and the electrochemical window of the electrolyte is greater than 4.8V.
Referring to fig. 9 and 10, in order to illustrate the application of the magnesium battery electrolyte to the magnesium-sulfur battery, the magnesium-sulfur battery using magnesium metal as a negative electrode material and sulfur as a positive electrode material is assembled, and the charge and discharge performance of the magnesium-sulfur battery is tested, and the result shows that the specific discharge capacity of the magnesium-sulfur battery assembled by the magnesium battery electrolyte according to the embodiment of the present invention is about 1100mAh g after 50 cycles of cycle -1 . Fig. 10 shows the charge and discharge plateau of the battery, and the magnesium-sulfur battery exhibits good battery performance.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.

Claims (13)

1. The magnesium battery electrolyte is characterized by comprising gel electrolyte salt, wherein the chemical formula of the electrolyte salt is [ MgXM ] p ][B(ORO) 4 ] n Wherein, X is selected from one or more of-1-valent halogen ions and halogen-like ions, M is a complexing agent, p is selected from any integer from 1 to 5, n is selected from any positive integer, R is selected from the general formula- (C) n1 H n2 Y n3 O n4 ) -wherein said Y is selected from one or more of said halide ions and said halide-like ions having a valence of-1, and said n 1 Any integer selected from 2 to 10, wherein n is 2 、n 3 、n 4 Are all integers of 0 or more, n 2 + n 3 ≤2n 1 ；
The cation in the electrolyte salt is [ MgX ] coordinated with the complexing agent M] + The anion being a boron-containing polymer skeleton [ B (ORO) 4 ] n － 。
2. The magnesium battery electrolyte of claim 1, wherein X is selected from F － 、Cl － 、Br － 、I － 、CN － And SCN － One or more of, Y is selected from F － 、Cl － 、Br － 、I － 、CN － And SCN － One or more of (a).
3. The magnesium battery electrolyte according to claim 1 or 2, wherein R is- (R) 1 OR 2 OR 3 OR 4 ) -, said R 1 、R 2 、R 3 、R 4 Each independently selected from the group consisting of m1 H m2 Y m3 ) -wherein said Y is selected from one or more of said halide ions and said halide-like ions having a valence of-1, and m is 1 Any integer selected from 1 to 3, wherein m is 2 、m 3 Are all integers of 0 or more, m 2 + m 3 ≤2m 1 。
4. The magnesium battery electrolyte as claimed in claim 1, further comprising a non-aqueous solvent, wherein the non-aqueous solvent and the complexing agent M are the same molecule.
5. The magnesium battery electrolyte as claimed in claim 4, wherein the non-aqueous solvent and the complexing agent are respectively selected from one or more of ionic liquids and organic solvents.
6. The magnesium battery electrolyte as claimed in claim 5, wherein the ionic liquid comprises one or more of imidazole ionic liquid, piperidine ionic liquid and pyrrole ionic liquid, and the imidazole ionic liquid is selected from one or more of 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonic acid) imide; the pyrrole ionic liquid is selected from N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt, and the piperidine ionic liquid is selected from N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt.
7. The magnesium battery electrolyte as claimed in claim 5, wherein the organic solvent includes one or more of ether compounds selected from one or more of tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dioxane and polyethylene glycol dimethyl ether; the ester compound is selected from ethyl acetate; the aromatic compound is selected from one or more of pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2, 6-dichloropyridine, 2-aminopyridine and azomethimazole; also comprises one or more of toluene, dimethyl sulfoxide, dimethyl formamide and acetonitrile.
8. The magnesium battery electrolyte of claim 1, wherein the electrolyte salt has a chemical formula of [ MgClM ™ ] p ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n 、[MgBrM p ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n 、[MgIM p ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n 、[MgFM p ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n 、 [MgCNM p ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n 、[MgSCNM p ][B(OC 2 H 2 F 2 OC 2 F 4 OC 2 F 4 OC 2 H 2 F 2 ) 4 ] n 、[MgClM p ][B(OC 2 H 2 Cl 2 OC 2 Cl 4 OC 2 Cl 4 OC 2 H 2 Cl 2 ) 4 ] n 、[MgBrM p ][B(OC 2 H 2 Cl 2 OC 2 Cl 4 OC 2 Cl 4 OC 2 H 2 Cl 2 ) 4 ] n 、[MgIM p ][B(OC 2 H 2 Cl 2 OC 2 Cl 4 OC 2 Cl 4 OC 2 H 2 Cl 2 ) 4 ] n 、[MgFM p ][B(OC 2 H 2 Cl 2 OC 2 Cl 4 OC 2 Cl 4 OC 2 H 2 Cl 2 ) 4 ] n 、[MgCNM p ][B(OC 2 H 2 Cl 2 OC 2 Cl 4 OC 2 Cl 4 OC 2 H 2 Cl 2 ) 4 ] n 、[MgSCNM p ][B(OC 2 H 2 Cl 2 OC 2 Cl 4 OC 2 Cl 4 OC 2 H 2 Cl 2 ) 4 ] n 、[MgClMp][B(OC 2 H 2 Br 2 OC 2 Br 4 OC 2 Br 4 OC 2 H 2 Br 2 ) 4 ] n 、[MgBrM p ][B(OC 2 H 2 Br 2 OC 2 Br 4 OC 2 Br 4 OC 2 H 2 Br 2 ) 4 ] n 、[MgIM p ][B(OC 2 H 2 Br 2 OC 2 Br 4 OC 2 Br 4 OC 2 H 2 Br 2 ) 4 ] n 、[MgFM p ][B(OC 2 H 2 Br 2 OC 2 Br 4 OC 2 Br 4 OC 2 H 2 Br 2 ) 4 ] n 、[MgCNM p ][B(OC 2 H 2 Br 2 OC 2 Br 4 OC 2 Br 4 OC 2 H 2 Br 2 ) 4 ] n 、[MgSCNM p ][B(OC 2 H 2 Br 2 OC 2 Br 4 OC 2 Br 4 OC 2 H 2 Br 2 ) 4 ] n 、[MgClM p ][B(OC 2 H 2 I 2 OC 2 I 4 OC 2 I 4 OC 2 H 2 I 2 ) 4 ] n 、 [MgBrM p ][B(OC 2 H 2 I 2 OC 2 I 4 OC 2 I 4 OC 2 H 2 I 2 ) 4 ] n 、[MgIM p ][B(OC 2 H 2 I 2 OC 2 I 4 OC 2 I 4 OC 2 H 2 I 2 ) 4 ] n 、[MgFM p ][B(OC 2 H 2 I 2 OC 2 I 4 OC 2 I 4 OC 2 H 2 I 2 ) 4 ] n 、[MgCNM p ][B(OC 2 H 2 I 2 OC 2 I 4 OC 2 I 4 OC 2 H 2 I 2 ) 4 ] n 、[MgSCNM p ][B(OC 2 H 2 I 2 OC 2 I 4 OC 2 I 4 OC 2 H 2 I 2 ) 4 ] n 、[MgClM p ][B(OC 2 H 2 (CN) 2 OC 2 (CN) 4 OC 2 (CN) 4 OC 2 H 2 (CN) 2 ) 4 ] n 、 [MgBrM p ][B(OC 2 H 2 (CN) 2 OC 2 (CN) 4 OC 2 (CN) 4 OC 2 H 2 (CN) 2 ) 4 ] n 、[MgIM p ][B(OC 2 H 2 (CN) 2 OC 2 (CN) 4 OC 2 (CN) 4 OC 2 H 2 (CN) 2 ) 4 ] n 、[MgFM p ][B(OC 2 H 2 (CN) 2 OC 2 (CN) 4 OC 2 (CN) 4 OC 2 H 2 (CN) 2 ) 4 ] n 、[MgCNM p ][B(OC 2 H 2 (CN) 2 OC 2 (CN) 4 OC 2 (CN) 4 OC 2 H 2 (CN) 2 ) 4 ] n 、 [MgSCNM p ][B(OC 2 H 2 (CN) 2 OC 2 (CN) 4 OC 2 (CN) 4 OC 2 H 2 (CN) 2 ) 4 ] n 、[MgClM p ][B(OC 2 H 2 (SCN) 2 OC 2 (SCN) 4 OC 2 (SCN) 4 OC 2 H 2 (SCN) 2 ) 4 ] n 、 [MgBrM p ][B(OC 2 H 2 (SCN) 2 OC 2 (SCN) 4 OC 2 (SCN) 4 OC 2 H 2 (SCN) 2 ) 4 ] n 、[MgIM p ][B(OC 2 H 2 (SCN) 2 OC 2 (SCN) 4 OC 2 (SCN) 4 OC 2 H 2 (SCN) 2 ) 4 ] n 、[MgFM p ][B(OC 2 H 2 (SCN) 2 OC 2 (SCN) 4 OC 2 (SCN) 4 OC 2 H 2 (SCN) 2 ) 4 ] n 、[MgCNM p ][B(OC 2 H 2 (SCN) 2 OC 2 (SCN) 4 OC 2 (SCN) 4 OC 2 H 2 (SCN) 2 ) 4 ] n 、[MgSCNM p ][B(OC 2 H 2 (SCN) 2 OC 2 (SCN) 4 OC 2 (SCN) 4 OC 2 H 2 (SCN) 2 ) 4 ] n One or more of (a).
9. A method for preparing the magnesium battery electrolyte as defined in any one of claims 1 to 8, comprising: mixing an anhydrous magnesium salt, an anhydrous polyol and the nonaqueous solvent according to any one of claims 4 to 7 to obtain a mixture; and reacting the mixture at 25-200 ℃; wherein the anhydrous magnesium salt is MgXBH 4 The anhydrous polyalcohol is OH-R-OH, and R is selected from the general formula of- (C) n1 H n2 Y n3 O n4 ) -wherein said Y is selected from one or more of-1 valent said halide and said halide-like ion, said n 1 Any integer selected from 2 to 10, wherein n is 2 、n 3 、n 4 Are all integers of 0 or more, n 2 + n 3 ≤2n 1 。
10. The method of claim 9, wherein the molar ratio of the anhydrous magnesium salt to the anhydrous polyol is 1: (4 to 6).
11. The method of claim 9, wherein the concentration of the anhydrous magnesium salt in the mixture is 0.1 to 3mol/L.
12. A magnesium battery, characterized in that the magnesium battery comprises the magnesium battery electrolyte according to any one of claims 1 to 8.
13. The magnesium battery according to claim 12, wherein the magnesium battery is a magnesium-sulfur battery.
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