WO2017113053A1 - 单核镁阳离子化盐、其制备方法及应用 - Google Patents

单核镁阳离子化盐、其制备方法及应用 Download PDF

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WO2017113053A1
WO2017113053A1 PCT/CN2015/099184 CN2015099184W WO2017113053A1 WO 2017113053 A1 WO2017113053 A1 WO 2017113053A1 CN 2015099184 W CN2015099184 W CN 2015099184W WO 2017113053 A1 WO2017113053 A1 WO 2017113053A1
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magnesium
salt
dimethyl ether
cationized
glycol dimethyl
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张跃钢
李宛飞
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Priority to PL15911685T priority patent/PL3399583T3/pl
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/02—Magnesium compounds
    • 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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
    • 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
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • 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
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
    • 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

Definitions

  • the invention particularly relates to a mononuclear magnesium cationized salt, a preparation method thereof and application thereof, and belongs to the field of electrochemical energy.
  • lithium-ion battery energy storage system has attracted the attention and attention of energy departments and energy companies in various countries, and it has a core position in the field of energy storage industry.
  • the global lithium resource reserves are limited and the spatial distribution is uneven (mainly distributed in South America), which not only causes high cost of raw materials for lithium-ion batteries, but also has the risk of being restricted by other countries' export restrictions in the future, and lithium-ion batteries are large in automobiles and energy storage.
  • magnesium Compared with lithium, magnesium has higher capacity, richer reserves, lower cost and higher safety. It has been widely recognized as the candidate for the most promising post-lithium ion battery, and it is expected to replace lithium ion in the future.
  • the battery is used as a green battery in electric vehicles and large-scale energy storage.
  • magnesium batteries still have many challenges compared to mature lithium-ion battery energy storage technologies.
  • magnesium electrolyte salts with simple structure, high synthesis method and excellent electrochemical performance is of great significance for the commercialization of rechargeable magnesium batteries.
  • the main object of the present invention is to provide a mononuclear magnesium cationized salt, a preparation method thereof and application thereof to overcome the deficiencies in the prior art.
  • the technical solution adopted by the present invention includes:
  • Embodiments of the present invention provide a mononuclear magnesium cationized salt having the chemical formula MgR n MX 4-m Y m , wherein R is a nonaqueous solvent molecule, and M includes Al 3+ and/or B 3+ , X, Y includes a halogen ion or a halogen-like ion, n is selected from any of 0 to 6, and m is selected from any of 0 to 4.
  • halogen ion comprises F - , Cl - , Br - or I - .
  • R may preferably be, but not limited to, tetrahydrofuran, toluene, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dioxane, Pyridine, dimethyl sulfoxide, dimethylformamide, nitrogen methylimidazole, acetonitrile or polyethylene glycol dimethyl ether.
  • Embodiments of the present invention also provide a method for synthesizing a mononuclear magnesium cationized salt, which comprises: subjecting a Mg 2+ -containing Lewis acid to a Lewis base containing Al 3+ and/or B 3+ in a nonaqueous solvent The reaction produces the mononuclear magnesium cationized salt.
  • the synthesis method employs a reaction temperature of 30 to 200 ° C and a reaction time of 3 to 48 hours.
  • the Lewis acid includes an inorganic magnesium salt such as MgX 2 , wherein X includes a halogen ion or a halogen-like ion.
  • the Lewis base comprises an inorganic aluminum salt and/or a boron salt, such as AlY 3 , BY 3 , wherein Y includes a halogen ion or a halogen-like ion.
  • halogen ion includes F - , Cl - , Br - or I - .
  • the class includes a halogen ion CN - or SCN -.
  • nonaqueous solvent may be preferably selected from an ionic liquid and/or an organic solvent, for example, may be selected from an imidazole-based ionic liquid such as 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3.
  • an imidazole-based ionic liquid such as 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3.
  • a methylimidazolium bis(trifluoromethanesulfonyl)imide salt a pyrrole ionic liquid such as N-butyl-N-methylpyrrolidine bis(trifluoromethanesulfonyl)imide salt, a piperidine ionic liquid such as N-butyl-N-methylpiperidine bis(trifluoromethanesulfonyl)imide salt, and tetrahydrofuran, toluene, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether Any one of organic solvents such as tetraethylene glycol dimethyl ether, dioxane, pyridine, dimethyl sulfoxide, dimethylformamide, nitrogen methylimidazole, acetonitrile or polyethylene glycol dimethyl ether or A variety of, and is not limited to this.
  • the method of synthesis comprises: utilizing a high boiling point and a high chemical and electrochemical stability of a green solvent ionic liquid or a high boiling organic solvent (eg 1-butyl-1-methylpyrrole) Alkane bis(trifluoromethanesulfonate Acyl)imide salt, N-butyl-N-methylpiperidine bis(trifluoromethanesulfonyl)imide salt, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol Methyl ether, polyethylene glycol dimethyl ether, etc.
  • a green solvent ionic liquid or a high boiling organic solvent eg 1-butyl-1-methylpyrrole
  • Alkane bis(trifluoromethanesulfonate Acyl)imide salt eg 1-butyl-1-methylpyrrole
  • N-butyl-N-methylpiperidine bis(trifluoromethanesulfonyl)imide salt e
  • the mononuclear magnesium cationized salt (also referred to as a mononuclear magnesium cation pure inorganic electrolyte salt) is prepared by partially reacting with a Lewis base of an inorganic magnesium salt.
  • Embodiments of the present invention also provide an electrolyte comprising: a nonaqueous solvent comprising an organic solvent and/or an ionic liquid; and the mononuclear magnesium cationized salt dissolved in the nonaqueous solvent.
  • the mononuclear magnesium cationized salt is used as an electrolyte.
  • the electrolyte concentration in the electrolyte is from 0.1 to 1.5 mol/L.
  • the ionic liquid and/or organic solvent includes an imidazole-based ionic liquid such as 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium (trifluoromethanesulfonate)
  • An acyl imide salt such as N-butyl-N-methylpyrrolidine bis(trifluoromethanesulfonyl)imide salt, a piperidine ionic liquid such as N-butyl-N-methylpiperidin Pyridinium (trifluoromethanesulfonyl)imide salt, and tetrahydrofuran, toluene, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, two One or more of an organic solvent such as hexacyclic, pyridine, dimethyl sulfoxide, di
  • Embodiments of the present invention also provide the use of the mononuclear magnesium cationized salt or the electrolyte described in the preparation of a magnesium battery.
  • the magnesium battery includes a magnesium primary battery or a magnesium secondary battery, etc., for example, a magnesium-sulfur secondary battery, but is not limited thereto.
  • the mononuclear magnesium cationized salt provided has a simple structure, the cationic portion is a mononuclear magnesium ion, and is easy to conduct magnesium ions; the anion portion does not contain an organic group, and the electrochemical property is relatively stable and performs better.
  • the mononuclear magnesium cationized salt provided has high ionic conductivity, high magnesium reversible deposition-dissolution efficiency, excellent cycle performance and high when applied to an electrolyte of a rechargeable magnesium battery.
  • the anodizing decomposition potential for example, when the electrolytic solution is applied to a magnesium-sulfur secondary battery, the initial discharge capacity can be 700 mAh/g or more, and can be circulated for 20 or more cycles.
  • Example 1 is a crystal structure diagram of [Mg(THF) 6 ][AlCl 4 ] 2 obtained in Example 1 of the present invention
  • Figure 2 is a cyclic voltammogram of [Mg(THF) 6 ][AlCl 4 ] 2 in Example 7 of the present invention
  • Figure 3 is a linear sweep voltammogram of [Mg(THF) 6 ][AlCl 4 ] 2 in Example 7 of the present invention
  • Figure 4 is a cyclic voltammogram of [Mg(DMSO) 6 ][AlCl 4 ] 2 in Example 8 of the present invention
  • Figure 5 is a cyclic voltammogram of [Mg(DMSO) 6 ][AlF 4 ] 2 in Example 9 of the present invention.
  • Figure 6 is a graph showing the first charge and discharge of a magnesium-sulfur battery in Embodiment 10 of the present invention.
  • Figure 7 is a graph showing the cycle performance test of a magnesium-sulfur battery in Example 10 of the present invention.
  • Example 1 56mg of anhydrous magnesium chloride (MgCl 2) and 158mg of anhydrous aluminum chloride (AlCl 3) in 1mL ionic liquid 1-butyl-1-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide (n-methyl-(n-butyl)pyrrolidinium bis(trifluoromethanesulfonyl)imide, PYR14TFSI) was reacted at 95 ° C for 24 hours to obtain a pale yellow solution, cooled to room temperature, and 1 mL of THF was added to obtain a 0.3 M magnesium-rich electrolyte.
  • MgCl 2 anhydrous magnesium chloride
  • AlCl 3 anhydrous aluminum chloride
  • the electrolyte salt was characterized as [Mg(THF) 6 ][AlCl 4 ] 2 , and its crystal structure is shown in FIG. 1 .
  • the theoretical value of elemental analysis is C 36.28, H 6.09; the measured value is C 36.27%, N 6.10%.
  • the Raman spectroscopy test results showed that 350 cm -1 was a characteristic peak of an anionic AlCl 4 - , and no Raman peak of other aluminum chloride anions was observed.
  • Example 2 56mg of anhydrous magnesium chloride (MgCl 2) and 158mg of anhydrous aluminum chloride (AlCl 3) in 1mL triethylene glycol dimethyl ether (TEGDME) reaction 30 °C 24 hours to give a pale yellow solution was cooled to room temperature A 0.6 M magnesium-fillable electrolyte was obtained, and its crystal structure was characterized by [Mg(TEGDME) 2 ][AlCl 4 ] 2 . The theoretical value of elemental analysis is C 22.87, H 4.48; the measured value is C, 22.89%; N 4.47%. The Raman spectroscopy test results showed that 350 cm -1 was a characteristic peak of an anionic AlCl 4 - , and no Raman peak of other aluminum chloride anions was observed.
  • MgCl 2 anhydrous magnesium chloride
  • AlCl 3 anhydrous aluminum chloride
  • Example 3 56 mg of anhydrous magnesium chloride (MgCl 2 ) and 158 mg of anhydrous aluminum chloride (AlCl 3 ) were reacted in 1 mL of toluene at 100 ° C for 24 hours to obtain a pale yellow solution, which was cooled to room temperature to obtain a 0.6 M magnesium-fillable electrolyte.
  • the crystal structure is characterized by the electrolyte salt being [Mg(toluene) 6 ][AlCl 4 ] 2 .
  • the theoretical value of elemental analysis is C 55.15, H 5.29; the measured value is C, 55.10%; H 5.30%.
  • the Raman spectroscopy test results showed that 350 cm -1 was a characteristic peak of an anionic AlCl 4 - , and no Raman peak of other aluminum chloride anions was observed.
  • Example 4 56 mg of anhydrous magnesium chloride (MgCl 2 ) and 158 mg of anhydrous aluminum chloride (AlCl 3 ) were reacted in 1 mL of polyethylene glycol dimethyl ether at 95 ° C for 24 hours to obtain a pale yellow solution, which was cooled to room temperature to obtain 0.6. M can be filled with magnesium electrolyte. The Raman spectroscopy test results showed that 350 cm -1 was a characteristic peak of an anionic AlCl 4 - , and no Raman peak of other aluminum chloride anions was observed.
  • MgCl 2 anhydrous magnesium chloride
  • AlCl 3 anhydrous aluminum chloride
  • Example 5 56 mg of anhydrous magnesium chloride (MgCl 2 ) and 158 mg of anhydrous aluminum chloride (AlCl 3 ) were reacted in 1 mL of dimethyl sulfoxide (DMSO) at 120 ° C for 24 hours to obtain a pale yellow solution, which was cooled to room temperature to obtain 0.6M magnesium secondary electrolyte, an electrolyte salt which is characterized by the structure [Mg (DMSO) 6] [ AlCl 4] 2.
  • the theoretical value of elemental analysis is C 17.35, H 4.37; the measured value is C 17.36%, H 4.37%.
  • the Raman spectroscopy test results showed that 350 cm -1 was a characteristic peak of an anionic AlCl 4 - , and no Raman peak of other aluminum chloride anions was observed.
  • Example 6 56 mg of anhydrous magnesium chloride (MgCl 2 ) and 100.8 mg of anhydrous aluminum fluoride (AlF 3 ) in 1 mL of ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide
  • the salt n-methyl-(n-butyl)pyrrolidinium bis(trifluoromethanesulfonyl)imide, PYR14TFSI
  • THF 1 mL of THF was added to obtain a 0.3 M magnesium-fillable electrolyte.
  • test structures electrolyte salt is [Mg (THF) 6] [ AlClF 3] 2.
  • the theoretical value of elemental analysis is C 41.43, H 6.95; the measured value is C 41.40%, H 6.97%.
  • Example 7 19 mg of anhydrous magnesium chloride (MgF 2 ) and 100.8 mg of anhydrous aluminum fluoride (AlF 3 ) were reacted in 1 mL of dimethyl sulfoxide (DMSO) at 200 ° C for 24 hours to obtain a pale yellow solution, which was cooled to room temperature. A 0.6 M magnesium-fillable electrolyte was obtained, and its electrolyte salt was characterized as [Mg(DMSO) 6 ][AlF 4 ] 2 . The theoretical value of elemental analysis was C 20.62, H 5.19; the measured value was C 20.61%, H 5.20%.
  • DMSO dimethyl sulfoxide
  • Example 8 56 mg of anhydrous magnesium chloride (MgCl 2 ) and 69 mg of anhydrous boron chloride (BCl 3 ) in 1 mL of ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide salt (n-methyl-(n-butyl)pyrrolidinium bis(trifluoromethanesulfonyl)imide, PYR14TFSI) was reacted at 95 ° C for 24 hours to obtain a colorless solution, cooled to room temperature, and 1 mL of THF was added to obtain a 0.3 M magnesium-rich electrolyte. Crystal structure characterization Its electrolyte salt is [Mg(THF) 6 ][BCl 4 ] 2 . The theoretical value of elemental analysis is C 37.82, H 6.35; the measured value is C 37.82%, H 6.34%.
  • Example 9 using platinum as a working electrode, 0.3 M magnesium salt ([Mg(THF) 6 ][AlCl 4 ] 2 ) PYR14TFSI/THF solution as electrolyte, metal magnesium as counter electrode and reference electrode, assembled into three
  • the electrode system was subjected to cyclic voltammetry in an argon glove box at a scanning speed of 25 mV/s. Cyclic voltammetry and linear sweep voltammetry results are shown in Fig. 2 and Fig. 3. As can be seen from Fig. 2, at 0.2 V and - The reduction oxidation process occurring near 0.2V vs. Mg corresponds to the deposition and dissolution of magnesium, and the anodization potential can reach 2.5V vs. Mg.
  • Example 10 using copper as a working electrode, 0.3 M magnesium salt ([Mg(DMSO) 6 ][AlCl 4 ] 2 ) PYR14TFSI/THF solution as electrolyte, metal magnesium as counter electrode and reference electrode, assembled into three
  • the electrode system was subjected to cyclic voltammetry in an argon glove box at a scanning speed of 25 mV/s.
  • the cyclic voltammetry results are shown in Fig. 4. As can be seen from Fig. 4, it appeared near 0.2 V and -0.2 V vs. Mg.
  • the reduction oxidation process corresponds to the deposition and dissolution of magnesium.
  • Example 11 do platinum working electrode, 0.3M magnesium salt of ([Mg (DMSO) 6] [AlF 4] 2) in DMSO solution as the electrolyte, magnesium metal electrode and a reference electrode against assembled into a three-electrode system
  • the cyclic voltammetry test was carried out in an argon glove box at a scanning speed of 25 mV/s.
  • the cyclic voltammetry results are shown in Fig. 5.
  • the reduction oxidation occurred in the vicinity of 0.2 V and -0.2 V vs. Mg.
  • the process corresponds to the deposition and dissolution of magnesium, and the anodization potential can reach 2.6V vs. Mg.
  • Example 12 using a sulfur-carbon composite (S/C) as an electrolyte, a magnesium salt of 0.3 M ([Mg(THF) 6 ][AlCl 4 ] 2 ) in PYR14TFSI/THF as an electrolyte, and magnesium metal as a negative electrode
  • S/C sulfur-carbon composite
  • Mg(THF) 6 a magnesium salt of 0.3 M
  • AlCl 4 a magnesium salt of 0.3 M
  • PYR14TFSI/THF magnesium metal as a negative electrode
  • the charge-discharge curve and the cycle performance test are shown in Fig. 6 and Fig. 7.
  • the initial discharge capacity of the magnesium-sulfur battery is about 700 mAh/g, which can be circulated for 20 times. the above.

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Abstract

本发明公开了一种单核镁阳离子化盐、其制备方法及应用。所述单核镁阳离子化盐的化学式为MgRnMX4-mYm，其中R为非水溶剂分子，M包括Al3+和/或B3+，X、Y包括卤素离子或类卤素离子，n选自0～6中的任一整数，m选自0～4中的任一整数。本发明提供的单核镁阳离子化盐结构简单，电化学性质优异，且其制备方法为低成本一步合成工艺，原料易得，制备过程简单，易规模化生产，该单核镁阳离子化盐在应用于可充镁电池的电解液时，所形成的电解液具有高的离子电导率、高的镁可逆沉积-溶出效率、优异的循环性能和高的阳极氧化分解电位，例如在将该电解液应用于镁电池时，其初始放电容量可以达到700mAh/g以上，而且能够循环20圈以上。

Description

单核镁阳离子化盐、其制备方法及应用 技术领域
本发明具体涉及一种单核镁阳离子化盐、其制备方法及应用，属于电化学能源领域。
背景技术
面向21世纪新阶段对高效、清洁、经济和安全能源体系的要求，发展新型的绿色、高性能、大规模储能技术并高效利用新能源，已成为全球共同关注的问题和发展的必然趋势。锂离子电池储能系统作为有效的储能方式备受各国能源部门和能源企业的关注和重视，在当今储能工业领域占据核心地位。但全球锂资源储量有限，空间分布不均匀(主要分布在南美)，这不但造成锂离子电池原材料成本高，且将来存在受制于他国出口限制的风险，并且锂离子电池在汽车、储能等大型电池领域应用仍然存在严重的安全问题，如特斯拉电动汽车多起着火事故、波音787飞机安全事故频发等，安全问题已成为未来锂离子电池产业与市场发展的主要瓶颈。
与锂相比，镁具有更高的容量、更丰富的储量以及更低廉的价格和更高的安全性，已经被广泛认为是最具潜力的后锂离子电池的候选者，未来有望替代锂离子电池作为绿色蓄电池应用于电动汽车和大型储能领域。但是，镁电池与成熟的锂离子电池储能技术相比，仍然存在很多挑战。
其中制约可充镁电池发展的关键因素主要是在绝大多数非质子电解质溶液中金属镁表面极易形成一层致密的钝化膜，该钝化膜是镁离子的不良导体，致使镁离子无法穿过，最终导致电池不能正常工作。到目前为止，电解质仍然是阻碍可充镁电池发展的最大瓶颈。
大量实验证明，与商用锂离子电池中常用的简单锂离子盐(LiClO4，LiPF6、Li(CF3SO3)2等)不同的是，在简单的单核镁阳离子化盐(如MgCl2、Mg(ClO4)2、Mg(CF3SO3)2等)的非质子极性溶剂电解液中容易形成一层不导镁离子的致密钝化膜，致使镁离子无法实现可逆沉积和溶解(Journal of Electroanalytical Chemistry,1999,466(2):203-217)，因此不能用于可充镁电池。尽管研究发现镁在格氏试剂的醚溶液中能够可逆沉积和溶解，但由于普通格氏试剂电化学窗口太窄及高活泼性，而无法直接用于可充镁电池电解液。随后，有机硼镁盐和有机铝镁盐的醚溶液也被发现可以实现可逆镁沉积和溶解，使得可充镁电池向实用化迈出一大步，但是此类电解质盐阳离子部分通常为双核镁阳离子，体积比较大，不利于离子传导；且阴离子部分含有有机基团，电化学稳定性差；另外它们的制备过程比较复杂，成本比较高。
因此发展结构简单、合成方法高效、电化学性能优异的镁电解质盐对于可充镁电池的商业化具有重要的意义。
发明内容
本发明的主要目的在于提供一种单核镁阳离子化盐、其制备方法及应用，以克服现有技术中的不足。
为实现前述发明目的，本发明采用的技术方案包括：
本发明的实施例提供了一种单核镁阳离子化盐，其化学式为MgRnMX4-mYm，其中R为非水溶剂分子，M包括Al3+和/或B3+，X、Y包括卤素离子或类卤素离子，n选自0～6中的任一整数，m选自0～4中的任一整数。
其中，所述卤素离子包括F－、Cl－、Br－或I－。
其中，所述类卤素离子包括CN-或SCN－。
进一步的，R可优选自但不限于四氢呋喃、甲苯、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、二氧六环、吡啶、二甲亚砜、二甲基甲酰胺、氮甲基咪唑、乙腈或聚乙二醇二甲醚。
本发明的实施例还提供了一种单核镁阳离子化盐的合成方法，其包括：将含Mg2+的路易斯酸与含Al3+和/或B3+的路易斯碱在非水溶剂中反应，制得所述单核镁阳离子化盐。
较为优选的，所述合成方法采用的反应温度为30～200℃，反应时间为3～48h。
进一步的，所述路易斯酸包括无机镁盐，例如MgX2，其中X包括卤素离子或类卤素离子。
进一步的，所述路易斯碱包括无机铝盐和/或硼盐，例如AlY3、BY3，其中Y包括卤素离子或类卤素离子。
进一步的，所述卤素离子包括F－、Cl－、Br－或I－。
进一步的，所述类卤素离子包括CN-或SCN－。
进一步的，所述非水溶剂可优选自离子液体和/或有机溶剂，例如可选自咪唑类离子液体如1-乙基-3-甲基咪唑四氟硼酸盐和1-乙基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐，吡咯类离子液体如N-丁基-N-甲基吡咯烷双(三氟甲烷磺酰)亚胺盐，哌啶类离子液体如N-丁基-N-甲基哌啶双(三氟甲烷磺酰)亚胺盐，以及四氢呋喃、甲苯、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、二氧六环、吡啶、二甲亚砜、二甲基甲酰胺、氮甲基咪唑、乙腈或聚乙二醇二甲醚等有机溶剂中的任意一种或多种，且不限于此。
在一较为优选的具体实施方案之中，所述合成方法包括：利用高沸点以及高化学和电化学稳定性的绿色溶剂离子液体或高沸点有机溶剂(例如1-丁基-1-甲基吡咯烷鎓双(三氟甲磺 酰)亚胺盐、N-丁基-N-甲基哌啶双(三氟甲烷磺酰)亚胺盐、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、聚乙二醇二甲醚等)作为无机镁盐及无机铝盐和/或无机硼盐的反应溶剂，通过利用无机铝盐和/或无机硼盐的路易斯酸性在加热的条件下完全和无机镁盐的路易斯碱部分反应，制得所述单核镁阳离子化盐(亦可称为单核镁阳离子纯无机电解质盐)。
本发明的实施例还提供了一种电解液，其包含：非水溶剂，包括有机溶剂和/或离子液体；以及，溶于所述非水溶剂内的所述单核镁阳离子化盐。在所述电解液中，所述单核镁阳离子化盐系作为电解质。
较为优选的，所述电解液中的电解质浓度为0.1～1.5mol/L。
进一步的，所述离子液体和/或有机溶剂包括咪唑类离子液体如1-乙基-3-甲基咪唑四氟硼酸盐和1-乙基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐，吡咯类离子液体如N-丁基-N-甲基吡咯烷双(三氟甲烷磺酰)亚胺盐，哌啶类离子液体如N-丁基-N-甲基哌啶双(三氟甲烷磺酰)亚胺盐，以及四氢呋喃、甲苯、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、二氧六环、吡啶、二甲亚砜、二甲基甲酰胺、氮甲基咪唑、乙腈或聚乙二醇二甲醚等有机溶剂中的一种或多种，且不限于此。
本发明的实施例还提供了所述的单核镁阳离子化盐或所述的电解液于制备镁电池中的用途。其中，所述镁电池包括镁一次电池或镁二次电池等，例如镁硫二次电池，但不限于此。
与现有技术相比，本发明的优点包括：
(1)提供了一种低成本一步合成单核镁阳离子化盐的方法，其原料易得，制备过程简单，易规模化生产，克服了现有可充镁电池的电解质盐合成方法繁琐、成本高等不足。
(2)提供的单核镁阳离子化盐结构简单，其阳离子部分为单核的镁离子，易于镁离子传导；阴离子部分不含有机基团，电化学性质相对比较稳定，表现更优异，一方面克服了简单镁电解质盐不能实现可逆沉积和溶解的问题，另一方面可克服了现有能够可逆实现镁沉积和溶解的镁电解质盐结构复杂，难以合成等缺陷，对推动可充镁电池的发展起着重要的作用。
(3)提供的单核镁阳离子化盐在应用于可充镁电池的电解液时，所形成的电解液具有高的离子电导率、高的镁可逆沉积-溶出效率、优异的循环性能和高的阳极氧化分解电位，例如在将该电解液应用于镁硫二次电池时，其初始放电容量可以达到700mAh/g以上，而且能够循环20圈以上。
附图说明
图1是本发明实施例1中所获[Mg(THF)6][AlCl4]2的晶体结构图；
图2是本发明实施例7中[Mg(THF)6][AlCl4]2的循环伏安图；
图3是本发明实施例7中[Mg(THF)6][AlCl4]2的线性扫描伏安图；
图4是本发明实施例8中[Mg(DMSO)6][AlCl4]2的循环伏安图；
图5是本发明实施例9中[Mg(DMSO)6][AlF4]2的循环伏安图；
图6是本发明实施例10中镁硫电池的首次充放电曲线图；
图7是本发明实施例10中镁硫电池的循环性能测试图。
具体实施方式
体现本发明特征与优点的典型实施例将在以下的说明中详细叙述。应理解的是本发明能够在不同的实施例上具有各种的变化，其皆不脱离本发明的范围，且其中的说明及图示在本质上是当作说明之用，而非用以限制本发明。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。
实施例1：56mg无水氯化镁(MgCl2)和158mg无水氯化铝(AlCl3)在1mL离子液体1-丁基-1-甲基吡咯烷鎓双(三氟甲磺酰)亚胺盐(n-methyl-(n-butyl)pyrrolidinium bis(trifluoromethanesulfonyl)imide，PYR14TFSI)中95℃反应24小时得到浅黄色的溶液，冷却至室温，另加入1mL THF得到0.3M可充镁电解液，晶体结构表征其电解质盐为[Mg(THF)6][AlCl4]2，其晶体结构如图1所示。元素分析理论值为C 36.28，H 6.09；测量值为C 36.27％，N 6.10％。拉曼光谱测试结果350cm-1为阴离子AlCl4 -的特征峰，未见其它氯化铝阴离子的拉曼峰。
实施例2：56mg无水氯化镁(MgCl2)和158mg无水氯化铝(AlCl3)在1mL三乙二醇二甲醚(TEGDME)中30℃反应24小时得到浅黄色的溶液，冷却至室温，得到0.6M可充镁电解液，晶体结构表征其电解质盐为[Mg(TEGDME)2][AlCl4]2。元素分析理论值为C 22.87，H 4.48；测量值为C，22.89％；N 4.47％。拉曼光谱测试结果350cm-1为阴离子AlCl4 -的特征峰,未见其它氯化铝阴离子的拉曼峰。
实施例3：56mg无水氯化镁(MgCl2)和158mg无水氯化铝(AlCl3)在1mL甲苯中100℃反应24小时得到浅黄色的溶液，冷却至室温，得到0.6M可充镁电解液，晶体结构表征其电解质盐为[Mg(toluene)6][AlCl4]2。元素分析理论值为C 55.15，H 5.29；测量值为C，55.10％；H 5.30％。拉曼光谱测试结果350cm-1为阴离子AlCl4 -的特征峰,未见其它氯化铝阴离子的拉曼峰。
实施例4：56mg无水氯化镁(MgCl2)和158mg无水氯化铝(AlCl3)在1mL聚乙二醇二甲醚中95℃反应24小时得到浅黄色的溶液，冷却至室温，得到0.6M可充镁电解液。拉曼光谱测试结果350cm-1为阴离子AlCl4 -的特征峰，未见其它氯化铝阴离子的拉曼峰。
实施例5：56mg无水氯化镁(MgCl2)和158mg无水氯化铝(AlCl3)在1mL二甲基亚砜(DMSO)中120℃反应24小时得到浅黄色的溶液，冷却至室温，得到0.6M可充镁电解液，结构表征其电解质盐为[Mg(DMSO)6][AlCl4]2。元素分析理论值为C 17.35，H 4.37；测量值为C 17.36％，H 4.37％。拉曼光谱测试结果350cm-1为阴离子AlCl4 -的特征峰，未见其它氯化铝阴离子的拉曼峰。
实施例6：56mg无水氯化镁(MgCl2)和100.8mg无水氟化铝(AlF3)在1mL离子液体1-丁基-1-甲基吡咯烷鎓双(三氟甲磺酰)亚胺盐(n-methyl-(n-butyl)pyrrolidinium bis(trifluoromethanesulfonyl)imide，PYR14TFSI)中150℃反应24小时得到浅黄色的溶液，冷却至室温，另加入1mL THF得到0.3M可充镁电解液，晶体结构测试电解质盐为[Mg(THF)6][AlClF3]2。元素分析理论值为C 41.43，H 6.95；测量值为C 41.40％，H 6.97％。
实施例7：19mg无水氯化镁(MgF2)和100.8mg无水氟化铝(AlF3)在1mL二甲基亚砜(DMSO)中200℃反应24小时得到浅黄色的溶液，冷却至室温，得到0.6M可充镁电解液，结构表征其电解质盐为[Mg(DMSO)6][AlF4]2。元素分析理论值为C 20.62，H 5.19；测量值为C 20.61％，H 5.20％。
实施例8：56mg无水氯化镁(MgCl2)和69mg无水氯化硼(BCl3)在1mL离子液体1-丁基-1-甲基吡咯烷鎓双(三氟甲磺酰)亚胺盐(n-methyl-(n-butyl)pyrrolidinium bis(trifluoromethanesulfonyl)imide，PYR14TFSI)中95℃反应24小时得到无色溶液，冷却至室温，另加入1mL THF得到0.3M可充镁电解液，晶体结构表征其电解质盐为[Mg(THF)6][BCl4]2。元素分析理论值为C 37.82，H 6.35；测量值为C 37.82％，H 6.34％。
实施例9：采用铂做工作电极，0.3M的镁盐([Mg(THF)6][AlCl4]2)的PYR14TFSI/THF溶液作为电解液，金属镁作对电极和参比电极，组装成三电极体系，在氩气手套箱中进行循环伏安测试，扫描速度为25mV/s，循环伏安和线性扫描伏安结果如图2和图3所示，由图2可知，在0.2V和-0.2V vs.Mg附近出现的还原氧化过程对应于镁的沉积与溶出，阳极氧化电位可以达到2.5V vs.Mg。
实施例10：采用铜做工作电极，0.3M的镁盐([Mg(DMSO)6][AlCl4]2)的PYR14TFSI/THF溶液作为电解液，金属镁作对电极和参比电极，组装成三电极体系，在氩气手套箱中进行循环伏安测试，扫描速度为25mV/s，循环伏安结果如图4所示，由图4可知，在0.2V和-0.2V vs.Mg附近出现的还原氧化过程对应于镁的沉积与溶出。
实施例11：采用铂做工作电极，0.3M的镁盐([Mg(DMSO)6][AlF4]2)的DMSO溶液作为电解液，金属镁作对电极和参比电极，组装成三电极体系，在氩气手套箱中进行循环伏安测试，扫描速度为25mV/s，循环伏安结果如图5所示，由图5可知，在0.2V和-0.2V vs.Mg附近出现的还原氧化过程对应于镁的沉积与溶出，阳极氧化电位可以达到2.6V vs.Mg。
实施例12：采用硫碳复合物(S/C)作为电解液，0.3M的镁盐([Mg(THF)6][AlCl4]2)的PYR14TFSI/THF溶液作为电解液，金属镁作负极，组装镁硫电池，充放电曲线和循环性能测试如图6和图7所示，由图6和图7可知，镁硫电池的初放容量在700毫安时/克左右，可以循环20圈以上。
在前述个实施例之中所采用的各种产品结构参数、各种反应参与物及工艺条件均是较为典型的范例，但经过本案发明人大量试验验证，于上文所列出的其它不同结构参数、其它类型的反应参与物及其它工艺条件也均是适用的，并也均可达成本发明所声称的技术效果。
需要说明的是，在本文中，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下，由语句“包括一个……”限定的要素，并不排除在包括所述要素的过程、方法、物品或者设备中还存在另外的相同要素。
以上所述仅是本发明的具体实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (11)

  1. 一种单核镁阳离子化盐，其化学式为MgRnMX4-mYm，其中R为非水溶剂分子，M包括Al3+和/或B3+，X、Y包括卤素离子或类卤素离子，所述类卤素离子包括CN-或SCN－，n选自0～6中的任一整数，m选自0～4中的任一整数。
  2. 根据权利要求1所述的单核镁阳离子化盐，其特征在于：R包括四氢呋喃、甲苯二氧六环、吡啶、二甲亚砜、二甲基甲酰胺、氮甲基咪唑、乙腈、乙二醇二甲醚、三乙二醇二甲醚、或聚乙二醇二甲醚。
  3. 一种单核镁阳离子化盐的合成方法，其特征在于包括：将含Mg2+的路易斯酸与含Al3+和/或B3+的路易斯碱在非水溶剂中反应，制得所述单核镁阳离子化盐。
  4. 根据权利要求3所述的合成方法，其特征在于：所述合成方法采用的反应温度为30～200℃，反应时间为3～48h。
  5. 根据权利要求3所述的合成方法，其特征在于：所述路易斯酸包括无机镁盐，所述无机镁盐包括MgX2，X包括卤素离子或类卤素离子；和/或，所述路易斯碱包括无机铝盐和/或硼盐，所述无机铝盐包括AlY3，所述硼盐包括BY3，Y包括卤素离子或类卤素离子；所述类卤素离子包括CN-或SCN－。
  6. 根据权利要求3所述的合成方法，其特征在于：所述非水溶剂选自离子液体和/或有机溶剂；所述离子液体包括咪唑类离子液体、吡咯类离子液体或哌啶类离子液体；所述有机溶剂包括四氢呋喃、甲苯、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、二氧六环、吡啶、二甲亚砜、二甲基甲酰胺、氮甲基咪唑、乙腈或聚乙二醇二甲醚。
  7. 一种电解液，其特征在于包含：非水溶剂，包括有机溶剂和/或离子液体；以及，溶于所述非水溶剂内的、如权利要求1-2中任一项所述的单核镁阳离子化盐。
  8. 根据权利要求7所述的电解液，其特征在于：所述电解液中的电解质浓度为0.1～1.5mol/L。
  9. 根据权利要求7所述的电解液，其特征在于：所述离子液体包括咪唑类离子液体、吡咯类离子液体或哌啶类离子液体；和/或，所述有机溶剂包括四氢呋喃、甲苯、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、二氧六环、吡啶、二甲亚砜、二甲基甲酰胺、氮甲基咪唑、乙腈或聚乙二醇二甲醚。
  10. 权利要求1-2中任一项所述的单核镁阳离子化盐或权利要求7-9中任一项所述的电解液于制备镁电池中的用途。
  11. 根据权利要求10所述的用途，其特征在于：所述镁电池包括镁一次电池或镁二次电池。
PCT/CN2015/099184 2015-12-28 2015-12-28 单核镁阳离子化盐、其制备方法及应用 Ceased WO2017113053A1 (zh)

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