CN110336079B - Magnesium battery electrolyte, preparation method thereof and magnesium battery - Google Patents
Magnesium battery electrolyte, preparation method thereof and magnesium battery Download PDFInfo
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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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
- H01M10/058—Construction or manufacture
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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
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
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- 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
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- 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 discloses a magnesium battery electrolyte, which comprises a non-aqueous solvent and electrolyte salt dissolved in the non-aqueous solvent, wherein the chemical formula of the electrolyte salt is [ Mg2X3Mp][LiY2Nq]Wherein X is selected from one or more of-1-valent halogen ions and halogen-like ions, Y is selected from one or more of-1-valent halogen ions and halogen-like ions, M and N are same or different coordination agents, p is selected from any integer from 1 to 6, and q is selected from any integer from 1 to 6. The invention also discloses a preparation method of the magnesium battery electrolyte, which comprises the following steps: mixing anhydrous magnesium salt, anhydrous lithium salt and the non-aqueous solvent to obtain a mixture; and reacting the mixture at 25-200 ℃; wherein the anhydrous magnesium salt is MgX2The anhydrous lithium salt is LiY; and/or the anhydrous magnesium salt is MgY2And the anhydrous lithium salt is LiX. The invention also discloses a magnesium battery which comprises the magnesium battery electrolyte.
Description
Technical Field
The invention relates to the technical field of energy, in particular to magnesium battery electrolyte, a preparation method thereof and a magnesium battery.
Background
In recent years, magnesium batteries have attracted much attention in the industry because they have higher volumetric energy density than lithium batteries. However, the development of magnesium batteries is still very slow, and one of the main reasons is the lack of suitable electrolyte and cathode materials.
At present, the synthesis of the magnesium battery electrolyte is mainly based on the Lewis acid-base reaction in an ether solvent. Lewis bases are typically magnesium salts with non-nucleophilic properties, lewis acids are compounds containing aluminum or boron. Unfortunately, when the aluminum-based magnesium-sulfur battery electrolyte is used, magnesium and aluminum co-deposition can occur due to the proximity of electrochemical reduction potentials of metal magnesium and metal aluminum, and the coulomb efficiency in the magnesium deposition and dissolution process is influenced. In the boron-based magnesium-sulfur battery electrolyte, the used boron salt is expensive, the stability is poor, the synthesis process is complex, and the aluminum-based and boron-based magnesium-sulfur battery electrolyte can hardly meet the requirements of future commercialization at present.
Disclosure of Invention
Accordingly, there is a need for a magnesium battery electrolyte solution having good stability and high magnesium solubility, a method for preparing the same, and a magnesium battery.
A magnesium battery electrolyte comprises a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent, wherein the chemical formula of the electrolyte salt is [ Mg2X3Mp][LiY2Nq]Wherein X is selected from one or more of-1-valent halogen ions and halogen-like ions, Y is selected from one or more of-1-valent halogen ions and halogen-like ions, M and N are same or different coordination agents, p is selected from any integer from 1 to 6, and q is selected from any integer from 1 to 6.
In one embodiment, the cation in the electrolyte salt is [ Mg ] coordinated to the complexing agent M2X3]+The anion is [ LiY ] coordinated with the complexing agent N2]-。
In one embodiment, X and Y are selected from the same species of ion.
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, said M and N are selected from the same said complexing agent.
In one embodiment, the non-aqueous solvent and the complexing agents M and N 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 includes one or more of imidazole ionic liquid, piperidine ionic liquid and pyrrole ionic liquid.
In one embodiment, the imidazole-based ionic liquid is selected from one or more of 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonate) 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 ethers, lipids and aromatics.
In one embodiment, the ether compound is 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 pyridine compound is selected from one or more of pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2, 6-dichloropyridine and 2-aminopyridine.
In one embodiment, the electrolyte salt has the formula [ Mg2F3Mp][LiF2Nq]、[Mg2F3Mp][LiCl2Nq]、[Mg2F3Mp][LiBr2Nq]、[Mg2F3Mp][LiI2Nq]、[Mg2F3Mp][LiCN2Nq]、[Mg2F3Mp][LiSCN2Nq]、[Mg2Cl3Mp][LiF2Nq]、[Mg2Cl3Mp][LiCl2Nq]、[Mg2Cl3Mp][LiBr2Nq]、[Mg2Cl3Mp][LiI2Nq]、[Mg2Cl3Mp][LiCN2Nq]、[Mg2Cl3Mp][LiSCN2Nq]、[Mg2Br3Mp][LiF2Nq]、[Mg2Br3Mp][LiCl2Nq]、[Mg2Br3Mp][LiBr2Nq]、[Mg2Br3Mp][LiI2Nq]、[Mg2Br3Mp][LiCN2Nq]、[Mg2Br3Mp][LiSCN2Nq]、[Mg2I3Mp][LiF2Nq]、[Mg2I3Mp][LiCl2Nq]、[Mg2I3Mp][LiBr2Nq]、[Mg2I3Mp][LiI2Nq]、[Mg2I3Mp][LiCN2Nq]、[Mg2I3Mp][LiSCN2Nq]、[Mg2CN3Mp][LiF2Nq]、[Mg2CN3Mp][LiCl2Nq]、[Mg2CN3Mp][LiBr2Nq]、[Mg2CN3Mp][LiI2Nq]、[Mg2CN3Mp][LiCN2Nq]、[Mg2CN3Mp][LiSCN2Nq]、[Mg2SCN3Mp][LiF2Nq]、[Mg2SCN3Mp][LiCl2Nq]、[Mg2SCN3Mp][LiBr2Nq]、[Mg2SCN3Mp][LiI2Nq]、[Mg2SCN3Mp][LiCN2Nq]And [ Mg)2SCN3Mp][LiSCN2Nq]One or more of (a).
The preparation method of the magnesium battery electrolyte comprises the following steps:
mixing anhydrous magnesium salt, anhydrous lithium salt and the non-aqueous solvent to obtain a mixture; and
reacting the mixture at 25-200 ℃;
wherein the anhydrous magnesium salt is MgX2The anhydrous lithium salt is LiY; and/or the anhydrous magnesium salt is MgY2And the anhydrous lithium salt is LiX.
In one embodiment, the molar ratio of the anhydrous magnesium salt to the anhydrous lithium salt is 1: (0.1-5).
In one embodiment, the molar ratio of the anhydrous magnesium salt to the anhydrous lithium salt is 1: (1-2).
In one embodiment, the molar ratio of the anhydrous magnesium salt to the anhydrous lithium salt is 1: 2.
in one embodiment, the reaction time is 3 hours to 48 hours.
In one embodiment, the concentration of the anhydrous magnesium salt and/or the anhydrous lithium salt in the mixture is 0.1mol/L to 5 mol/L.
In one embodiment, the concentration of the anhydrous magnesium salt and/or the anhydrous lithium salt in the mixture is 0.5mol/L to 2.5 mol/L.
A magnesium battery comprises the magnesium battery electrolyte.
In one embodiment, the magnesium battery is a magnesium-sulfur battery.
The electrolyte of the magnesium battery is double-salt electrolyte of lithium base and magnesium base, and stable cation [ Mg ] is obtained by a coordination agent2X3]+And anions [ LiY ]2]-The cation [ Mg2X3]+And anions [ LiY ]2]-Relative to Mg2+And Li+The electrolyte is easier to dissolve in the non-aqueous solvent, and compared with cations and anions obtained by aluminum base and boron base, the electrolyte prepared by using lithium base has stronger performance of depositing and dissolving magnesium, and the phenomenon of co-deposition of magnesium and other metals can not occur, thereby improving the battery performance of the magnesium battery.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing a magnesium battery electrolyte according to an embodiment of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum photograph of a magnesium battery electrolyte according to an embodiment of the present invention;
FIG. 3 is a Raman spectrum photograph of an electrolyte salt according to an embodiment of the present invention;
FIG. 4 is a photograph of a cyclic voltammetry curve of a magnesium battery electrolyte on a platinum electrode according to an embodiment of the present invention;
FIG. 5 is a photograph of a linear scan curve of a magnesium battery electrolyte on a platinum electrode according to an embodiment of the present invention;
fig. 6 is a photograph of a charge-discharge cycle-specific capacity map of a magnesium-sulfur battery according to an embodiment of the present invention;
fig. 7 is a photograph of a charge-discharge specific capacity-voltage map of a magnesium-sulfur battery according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the magnesium battery electrolyte, the preparation method thereof and the magnesium battery of the present invention are further described in detail by the following embodiments with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a magnesium battery electrolyte, which comprises a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent, wherein the chemical formula of the electrolyte salt is [ Mg2X3Mp][LiY2Nq]Wherein X is selected from one or more of halogen ions and halogen-like ions, Y is selected from one or more of halogen ions and halogen-like ions, M and N are same or different coordination agents, p is selected from any integer from 1 to 6, and q is selected from any integer from 1 to 6.
The magnesium battery electrolyte of the embodiment of the invention is a double-salt electrolyte of lithium base and magnesium base, and stable cation [ Mg ] is obtained through a coordination agent2X3]+And anions [ LiY ]2]-The cation [ Mg2X3]+And anions [ LiY ]2]-Relative to Mg2+And Li+The electrolyte is easier to dissolve in the non-aqueous solvent, and compared with cations and anions obtained by aluminum base and boron base, the electrolyte prepared by using lithium base in the embodiment of the invention has stronger performance of depositing and dissolving magnesium, and the phenomenon of co-deposition of magnesium and other metals can not occur, thereby improving the battery performance of the magnesium battery.
The cation in the electrolyte salt is [ Mg ] coordinated with a complexing agent M2X3]+The anion being [ LiY ] coordinated to the complexing agent N2]-. By means of the complexing agent (i.e. ligand), a stable cation [ Mg ] can be obtained2X3]+And a stable anion [ LiY2]-。
X, Y are respectively selected from one or more of the halogen ion and the halogen-like ion, and the halogen ion 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).
The chemical formula of the electrolyte salt is [ Mg2F3Mp][LiF2Nq]、[Mg2F3Mp][LiCl2Nq]、[Mg2F3Mp][LiBr2Nq]、[Mg2F3Mp][LiI2Nq]、[Mg2F3Mp][LiCN2Nq]、[Mg2F3Mp][LiSCN2Nq]、[Mg2Cl3Mp][LiF2Nq]、[Mg2Cl3Mp][LiCl2Nq]、[Mg2Cl3Mp][LiBr2Nq]、[Mg2Cl3Mp][LiI2Nq]、[Mg2Cl3Mp][LiCN2Nq]、[Mg2Cl3Mp][LiSCN2Nq]、[Mg2Br3Mp][LiF2Nq]、[Mg2Br3Mp][LiCl2Nq]、[Mg2Br3Mp][LiBr2Nq]、[Mg2Br3Mp][LiI2Nq]、[Mg2Br3Mp][LiCN2Nq]、[Mg2Br3Mp][LiSCN2Nq]、[Mg2I3Mp][LiF2Nq]、[Mg2I3Mp][LiCl2Nq]、[Mg2I3Mp][LiBr2Nq]、[Mg2I3Mp][LiI2Nq]、[Mg2I3Mp][LiCN2Nq]、[Mg2I3Mp][LiSCN2Nq]、[Mg2CN3Mp][LiF2Nq]、[Mg2CN3Mp][LiCl2Nq]、[Mg2CN3Mp][LiBr2Nq]、[Mg2CN3Mp][LiI2Nq]、[Mg2CN3Mp][LiCN2Nq]、[Mg2CN3Mp][LiSCN2Nq]、[Mg2SCN3Mp][LiF2Nq]、[Mg2SCN3Mp][LiCl2Nq]、[Mg2SCN3Mp][LiBr2Nq]、[Mg2SCN3Mp][LiI2Nq]、[Mg2SCN3Mp][LiCN2Nq]And [ Mg)2SCN3Mp][LiSCN2Nq]One or more of (a).
Preferably, p may be 0 to 6. The q may be 0 to 2.
Preferably, X and Y are selected from the same ion, and when X and Y are the same ion, the Mg is2+And Li+The formation of coordinating cations and coordinating anions is easier and the formation of the coordinating cations and coordinating anions is more stable. Preferably, X and Y are selected from Cl-。
Preferably, said M and N may be selected from the same species of said complexing agent, said complexing agent for said cation and said anion being the same, said complexing cation and said complexing anion being more easily formed, and said complexing cation and said complexing anion being formed more stably.
The complexing agent may be derived from the non-aqueous solvent, i.e., the molecules of the non-aqueous solvent and the [ Mg ]2X3]+And [ LiY2]-And (4) coordination.
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 may include one or more of imidazole-based ionic liquids, piperidine-based ionic liquids, and pyrrole-based ionic liquids. Preferably, the imidazole ionic liquid can be selected from one or more of 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonic acid) imide. The pyrrole ionic liquid can be selected from N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt, and the piperidine ionic liquid can be selected from N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt.
In one embodiment, the organic solvent may include one or more of an ether compound, a lipid compound, and an aromatic compound. Preferably, the ether compound may be 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 may be selected from ethyl acetate. The pyridine compound may be selected from one or more of pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2, 6-dichloropyridine and 2-aminopyridine.
Referring to fig. 1, an embodiment of the present invention further provides a method for preparing the magnesium battery electrolyte, including:
s100, mixing an anhydrous magnesium salt, an anhydrous lithium salt and the non-aqueous solvent to obtain a mixture; and
s200, reacting the mixture at 25-200 ℃;
wherein, the anhydrous magnesium salt is MgX2The anhydrous lithium salt is LiY; and/or the anhydrous magnesium salt is MgY2And the anhydrous lithium salt is LiX.
Lithium salts are generally considered to be common salts and are not acid-base. According to the invention, through a large number of experiments, the magnesium battery electrolyte is creatively prepared by using an inorganic magnesium salt as a Lewis base and an inorganic lithium salt as a Lewis acid, the Lewis acid can absorb electrons, the Lewis base provides electrons, and the Lewis acid and the Lewis base respectively obtain coordination anions and coordination cations under the action of a coordination agent, so that stable electrolyte salt is formed. The magnesium battery obtained by using the electrolyte has excellent performance.
In one embodiment, the molar ratio of the anhydrous magnesium salt to the anhydrous lithium salt may be 1: (0.1-5). Preferably, the molar ratio of the anhydrous magnesium salt to the anhydrous lithium salt may be 1: (1-2). The Lewis acid-base reaction of the inorganic magnesium salt and the inorganic lithium salt in the coordination agent is a reversible reaction, and the mole number of the anhydrous magnesium salt is set to be smaller than that of the anhydrous lithium salt, so that the reversible reaction is favorably moved to the direction of generating the electrolyte salt, and the preparation efficiency of the electrolyte salt is improved. More preferably, the molar ratio of the anhydrous magnesium salt to the anhydrous lithium salt may be 1: 2.
in one embodiment, the reaction time of step S200 may be 3 hours to 48 hours.
In one embodiment, the concentration of the anhydrous magnesium salt and/or the anhydrous lithium salt in the mixture may be 0.1mol/L to 5 mol/L. In this concentration range, the reaction efficiency of the anhydrous magnesium salt and the anhydrous lithium salt in the nonaqueous solvent is higher. Preferably, the concentration of the anhydrous magnesium salt and/or the anhydrous lithium salt in the mixture may be 0.5mol/L to 2.5 mol/L.
Preferably, the anions X and Y in the anhydrous magnesium salt and the anhydrous lithium salt are the same ion, so that the coordination cation [ Mg ] is more easily obtained2Cl3]+And a coordinating anion [ LiY2]-。
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. The magnesium in the magnesium battery is mainly extracted from 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 content below 1ppm and filled with argon, 285.63mg of anhydrous magnesium chloride (MgCl)2) And 254.34mg of anhydrous lithium chloride (LiCl) (the molar ratio of anhydrous magnesium chloride to anhydrous lithium chloride is 1:2) in 10mL of Tetrahydrofuran (THF), and reacted at 25 ℃ for 24 hours to obtain a magnesium battery electrolyte. And carrying out nuclear magnetic analysis and Raman spectrum analysis on the electrolyte.
Referring to FIGS. 2 and 3, the NMR results show that MgCl was added2Thereafter, the coordination environment of LiCl is significantly changed, i.e. anhydrous MgCl2And anhydrous LiCl in THF, and the chemical shift shifted by 0.1ppm, demonstrating that [ LiCl ]2]-And (4) generating. The Raman spectrum analysis result shows that the depth of the sample is 242cm-1Presence of [ Mg ] at wavelength2Cl3]+Characteristic peak of (2). The electrolyte synthesized by the embodiment of the invention contains electrolyte salt [ Mg ] by combining nuclear magnetism and Raman data2Cl3Mp][LiCl2Nq]。
Referring to fig. 4 and 5, 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 3V.
Referring to fig. 6 and 7, 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 first discharge specific capacity of the magnesium-sulfur battery assembled by the magnesium battery electrolyte of the embodiment of the invention is about 1500mAh g-1The specific capacity after 200 cycles is about 1100mAh g-1The magnesium-sulfur battery shows 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 present 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 shall be subject to the appended claims.
Claims (15)
1. The electrolyte for the magnesium battery is characterized by comprising a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent, wherein the chemical formula of the electrolyte salt is [ Mg [ ]2X3Mp][LiY2Nq]Wherein X is selected from one or more of-1-valent halogen ions and halogen-like ions, and Y is selected from-1-valent halogen ionsOne or more of the halogen ions and the halogen-like ions, wherein M and N are same or different coordination agents, p is selected from any integer from 1 to 6, and q is selected from any integer from 1 to 6.
2. The magnesium battery electrolyte of claim 1, wherein the cation in the electrolyte salt is [ Mg ] coordinated to the complexing agent M2X3]+The anion is [ LiY ] coordinated with the complexing agent N2]－。
3. The magnesium battery electrolyte of claim 1, wherein X and Y are selected from the same ion.
4. 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).
5. The magnesium battery electrolyte as claimed in claim 1, wherein the nonaqueous solvent and the complexing agents M and N are the same kind of molecule.
6. The magnesium battery electrolyte according to any one of claims 1 to 5, wherein the nonaqueous solvent and the complexing agent are each selected from one or more of an ionic liquid and an organic solvent.
7. The magnesium battery electrolyte as claimed in claim 6, 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.
8. The magnesium battery electrolyte according to claim 6, wherein the organic solvent comprises one or more of an ether compound, an ester compound, and a pyridine compound; the ether compound is 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 pyridine compound is selected from one or more of pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2, 6-dichloropyridine and 2-aminopyridine.
9. The magnesium battery electrolyte of claim 1, wherein the electrolyte salt has the formula [ Mg [ ]2F3Mp][LiF2Nq]、[Mg2F3Mp][LiCl2Nq]、[Mg2F3Mp][LiBr2Nq]、[Mg2F3Mp][LiI2Nq]、[Mg2F3Mp][LiCN2Nq]、[Mg2F3Mp][LiSCN2Nq]、[Mg2Cl3Mp][LiF2Nq]、[Mg2Cl3Mp][LiCl2Nq]、[Mg2Cl3Mp][LiBr2Nq]、[Mg2Cl3Mp][LiI2Nq]、[Mg2Cl3Mp][LiCN2Nq]、[Mg2Cl3Mp][LiSCN2Nq]、[Mg2Br3Mp][LiF2Nq]、[Mg2Br3Mp][LiCl2Nq]、[Mg2Br3Mp][LiBr2Nq]、[Mg2Br3Mp][LiI2Nq]、[Mg2Br3Mp][LiCN2Nq]、[Mg2Br3Mp][LiSCN2Nq]、[Mg2I3Mp][LiF2Nq]、[Mg2I3Mp][LiCl2Nq]、[Mg2I3Mp][LiBr2Nq]、[Mg2I3Mp][LiI2Nq]、[Mg2I3Mp][LiCN2Nq]、[Mg2I3Mp][LiSCN2Nq]、[Mg2CN3Mp][LiF2Nq]、[Mg2CN3Mp][LiCl2Nq]、[Mg2CN3Mp][LiBr2Nq]、[Mg2CN3Mp][LiI2Nq]、[Mg2CN3Mp][LiCN2Nq]、[Mg2CN3Mp][LiSCN2Nq]、[Mg2SCN3Mp][LiF2Nq]、[Mg2SCN3Mp][LiCl2Nq]、[Mg2SCN3Mp][LiBr2Nq]、[Mg2SCN3Mp][LiI2Nq]、[Mg2SCN3Mp][LiCN2Nq]And [ Mg)2SCN3Mp][LiSCN2Nq]One or more of (a).
10. A method of preparing a magnesium battery electrolyte as claimed in any one of claims 1 to 9, comprising: mixing anhydrous magnesium salt, anhydrous lithium salt and the non-aqueous solvent to obtain a mixture; and mixing the mixtureReacting at 25-200 ℃; wherein the anhydrous magnesium salt is MgX2The anhydrous lithium salt is LiY; and/or the anhydrous magnesium salt is MgY2And the anhydrous lithium salt is LiX.
11. The method of claim 10, wherein the molar ratio of the anhydrous magnesium salt to the anhydrous lithium salt is 1: (0.1-5).
12. The method of claim 10, wherein the molar ratio of the anhydrous magnesium salt to the anhydrous lithium salt is 1: (1-2).
13. The method of claim 10, wherein the concentration of the anhydrous magnesium salt and/or the anhydrous lithium salt in the mixture is 0.1 to 5 mol/L.
14. A magnesium battery comprising the magnesium battery electrolyte according to any one of claims 1 to 9.
15. The magnesium battery of claim 14, wherein the magnesium battery is a magnesium-sulfur battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201910548453.0A CN110336079B (en) | 2019-06-24 | 2019-06-24 | Magnesium battery electrolyte, preparation method thereof and magnesium battery |
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| CN102916220A (en) * | 2011-08-05 | 2013-02-06 | 丰田自动车株式会社 | Magnesium battery electrolyte |
| CN104428940A (en) * | 2012-08-02 | 2015-03-18 | 丰田自动车工程及制造北美公司 | Magnesium borohydride and its derivatives as magnesium ion transfer media |
| CN106916173A (en) * | 2015-12-28 | 2017-07-04 | 中国科学院苏州纳米技术与纳米仿生研究所 | Monokaryon magnesium cation salt dissolving, its preparation method and application |
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| US8541133B2 (en) * | 2010-10-27 | 2013-09-24 | Toyota Motor Engineering & Manufacturing North America, Inc. | Electrochemical device with a magnesium anode and a stable, safe electrolyte compatible with sulfur |
| US8361661B2 (en) * | 2011-03-08 | 2013-01-29 | Pellion Technologies Inc. | Rechargeable magnesium ion cell components and assembly |
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| CN106532111B (en) * | 2015-09-15 | 2019-01-08 | 中国科学院上海硅酸盐研究所 | A kind of magnesium cell of the high-energy density based on conversion reaction |
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| CN109755553B (en) * | 2019-03-20 | 2021-09-24 | 北京航空航天大学 | Magnesium-lithium double-ion battery composite positive electrode material, preparation method and application thereof, and battery system |
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| CN102916220A (en) * | 2011-08-05 | 2013-02-06 | 丰田自动车株式会社 | Magnesium battery electrolyte |
| CN104428940A (en) * | 2012-08-02 | 2015-03-18 | 丰田自动车工程及制造北美公司 | Magnesium borohydride and its derivatives as magnesium ion transfer media |
| CN106916173A (en) * | 2015-12-28 | 2017-07-04 | 中国科学院苏州纳米技术与纳米仿生研究所 | Monokaryon magnesium cation salt dissolving, its preparation method and application |
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