CN115084652A - A composite rechargeable magnesium battery electrolyte and preparation method thereof - Google Patents

A composite rechargeable magnesium battery electrolyte and preparation method thereof Download PDF

Info

Publication number
CN115084652A
CN115084652A CN202210879412.1A CN202210879412A CN115084652A CN 115084652 A CN115084652 A CN 115084652A CN 202210879412 A CN202210879412 A CN 202210879412A CN 115084652 A CN115084652 A CN 115084652A
Authority
CN
China
Prior art keywords
electrolyte
organic solvent
composite
magnesium
salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210879412.1A
Other languages
Chinese (zh)
Other versions
CN115084652B (en
Inventor
李凌杰
黄雪婷
雷惊雷
黄光胜
王敬丰
潘复生
苏建章
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Guoyan Technology Research Center Co ltd
Original Assignee
Guangdong Guoyan Technology Research Center Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong Guoyan Technology Research Center Co ltd filed Critical Guangdong Guoyan Technology Research Center Co ltd
Priority to CN202210879412.1A priority Critical patent/CN115084652B/en
Publication of CN115084652A publication Critical patent/CN115084652A/en
Application granted granted Critical
Publication of CN115084652B publication Critical patent/CN115084652B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0567Liquid materials characterised by the additives
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)

Abstract

The invention provides a composite rechargeable magnesium battery electrolyte and a preparation method thereof. The electrolyte contains an organic solvent, electrolyte salt and an additive; in the preparation process, the raw materials are not subjected to any water removal and impurity removal pretreatment, and are directly stirred and uniformly mixed under the inert atmosphere at room temperature to obtain the electrolyte. The composite electrolyte has the advantages of high conductivity, small overpotential, high magnesium deposition-dissolution efficiency and high tolerance to water and impurities, obviously reduces the cost of the electrolyte, simplifies the preparation process of the electrolyte, provides great convenience for the storage and use of the electrolyte, and is beneficial to commercialization of rechargeable magnesium batteries.

Description

一种复合型可充镁电池电解液及其制备方法A composite rechargeable magnesium battery electrolyte and preparation method thereof

技术领域technical field

本发明属于可充镁电池技术领域,具体涉及一种复合型可充镁电池电解液及其制备方法。The invention belongs to the technical field of rechargeable magnesium batteries, and in particular relates to a composite rechargeable magnesium battery electrolyte and a preparation method thereof.

背景技术Background technique

可充镁电池具有安全性高、原料镁储量丰富、体积比容量高等优点,被认为是“后锂离子电池时代”最具发展潜力的新型储能技术之一。电解液作为可充镁电池的核心组成部分,对电池的性能具有重要影响。可充镁电池电解液主要由有机溶剂和电解质盐组成。与可充锂或钠(离子)电池等的电解液类似,可充镁电池电解液对水和杂质非常敏感,痕量水和杂质的存在都会严重影响电池性能。因此,制备可充镁电池电解液需要预先对有机溶剂进行无水无氧处理并且使用无水高纯电解质盐为原料,这造成电解液成本高昂、制备过程繁琐冗长,还给电解液的储存和使用带来不便,成为可充镁电池发展和商品化应用的严重障碍。Rechargeable magnesium batteries have the advantages of high safety, abundant raw material magnesium reserves, and high volume specific capacity, and are considered to be one of the most promising new energy storage technologies in the "post-lithium-ion battery era". As the core component of rechargeable magnesium batteries, the electrolyte has an important impact on the performance of the battery. The electrolyte of rechargeable magnesium battery is mainly composed of organic solvent and electrolyte salt. Similar to electrolytes such as rechargeable lithium or sodium (ion) batteries, rechargeable magnesium battery electrolytes are very sensitive to water and impurities, and the presence of trace amounts of water and impurities can seriously affect battery performance. Therefore, the preparation of the electrolyte for rechargeable magnesium batteries requires anhydrous and oxygen-free treatment of the organic solvent in advance and the use of anhydrous high-purity electrolyte salts as raw materials, which results in high cost of the electrolyte, cumbersome and lengthy preparation process, and also reduces the storage and storage of the electrolyte. The inconvenience caused by the use has become a serious obstacle to the development and commercial application of rechargeable magnesium batteries.

研发对水和杂质具有高宽容度的电导率大、过电位小、镁沉积-溶出效率高的可充镁电池电解液,既可以保证电解液和电池的优良性能,又可显著降低电解液的成本、简化电解液的制备过程、方便电解液的储存和使用,这对可充镁电池的发展和商业化应用势必具有重要推进作用。The research and development of rechargeable magnesium battery electrolyte with high conductivity, low overpotential and high magnesium deposition-dissolution efficiency with high tolerance to water and impurities can not only ensure the excellent performance of the electrolyte and the battery, but also significantly reduce the electrolyte's performance. Cost, simplifying the preparation process of the electrolyte, and facilitating the storage and use of the electrolyte are bound to play an important role in promoting the development and commercial application of rechargeable magnesium batteries.

发明内容SUMMARY OF THE INVENTION

针对现有技术存在的上述不足,本发明的目的是提供一种对水和杂质具有高宽容度的复合型可充镁电池电解液。In view of the above deficiencies in the prior art, the purpose of the present invention is to provide a composite type rechargeable magnesium battery electrolyte with high tolerance to water and impurities.

本发明还提供所述复合型可充镁电池电解液的制备方法。The present invention also provides a method for preparing the electrolyte for the composite rechargeable magnesium battery.

实现上述目的,本发明采用如下技术方案:To achieve the above object, the present invention adopts the following technical solutions:

一种复合型可充镁电池电解液,其特征在于,含有机溶剂、电解质盐和添加剂,所述电解质盐在有机溶剂中的总摩尔浓度为1.1~1.5mol/L,所述添加剂在有机溶剂中的总质量百分浓度为0.5~2.0wt%。A composite rechargeable magnesium battery electrolyte, characterized in that it contains an organic solvent, an electrolyte salt and an additive, the total molar concentration of the electrolyte salt in the organic solvent is 1.1-1.5 mol/L, and the additive is in the organic solvent. The total mass percentage concentration in 0.5-2.0 wt%.

进一步,所述有机溶剂由链状醚类有机溶剂和全氟胺类有机溶剂按体积比1:0.25~1组成;所述电解质盐由有机镁盐和无机钠盐按物质的量之比1:0.5~1组成;所述添加剂由金属有机框架类物质和羟烷基纤维素类物质按质量比1:1~3组成。Further, the organic solvent is composed of a chain ether organic solvent and a perfluoroamine organic solvent in a volume ratio of 1:0.25 to 1; the electrolyte salt is composed of an organic magnesium salt and an inorganic sodium salt in a ratio of 1:0. The additive is composed of metal organic framework substances and hydroxyalkyl cellulose substances in a mass ratio of 1:1 to 3.

进一步,所述链状醚类有机溶剂为乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚中的任意一种;所述全氟胺类有机溶剂为全氟三乙胺或全氟三丁胺中的任意一种。Further, the chain ether organic solvent is any one of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether; The fluorine amine organic solvent is any one of perfluorotriethylamine or perfluorotributylamine.

进一步,所述电解质盐中的有机镁盐为三氟甲磺酸镁或双(三氟甲烷磺酰亚胺)镁中的任意一种;所述电解质盐中的无机钠盐为氟化钠或溴化钠中的任意一种。Further, the organic magnesium salt in the electrolyte salt is any one of magnesium trifluoromethanesulfonate or magnesium bis(trifluoromethanesulfonimide); the inorganic sodium salt in the electrolyte salt is sodium fluoride or Any of sodium bromide.

进一步,所述添加剂中的金属有机框架类物质为ZIF-8或ZIF-67中的任意一种;所述添加剂中的羟烷基纤维素类物质为羟乙基纤维素或羟丙基纤维素中的任意一种。Further, the metal organic framework substance in the additive is any one of ZIF-8 or ZIF-67; the hydroxyalkyl cellulose substance in the additive is hydroxyethyl cellulose or hydroxypropyl cellulose any of the .

本发明还提供一种复合型可充镁电池电解液的制备方法,包括如下步骤:The present invention also provides a preparation method of a composite rechargeable magnesium battery electrolyte, comprising the following steps:

按上述组份备料;在室温惰性气氛下,量取链状醚类有机溶剂和全氟胺类有机溶剂,将二者混合均匀即得复合有机溶剂;称取有机镁盐、无机钠盐、金属有机框架类添加剂和羟烷基纤维素类添加剂,依次缓慢加入到复合有机溶剂中,磁力搅拌48h~60h,即得电解液。Prepare the materials according to the above components; under an inert atmosphere at room temperature, measure the chain ether organic solvent and the perfluoroamine organic solvent, and mix the two evenly to obtain a composite organic solvent; weigh the organic magnesium salt, inorganic sodium salt, metal Organic framework additives and hydroxyalkyl cellulose additives are slowly added to the composite organic solvent in turn, and magnetically stirred for 48h to 60h to obtain an electrolyte.

进一步,所述原料有机溶剂、电解质盐和添加剂均无需进行任何除水、除杂预处理。Further, the raw material organic solvent, electrolyte salt and additives do not need any pretreatment for water removal and impurity removal.

相比现有技术,本发明具有如下有益效果:Compared with the prior art, the present invention has the following beneficial effects:

1、本发明复合型可充镁电池电解液含双有机溶剂、双电解质盐和双添加剂;由链状醚类溶剂和全氟胺类溶剂组成的双有机溶剂既可以调节溶剂的极性、增大电解质盐的溶解度,又可以增强电解液的稳定性;由有机镁盐和无机钠盐组成的双电解质盐既可以增大电解质盐的浓度、提高电解液的电导率,又有利于改善镁离子的溶剂化环境、促进电极-电解液界面的电荷转移,减少镁沉积-溶出的过电位和提高循环稳定性;由金属有机框架类物质和羟烷基纤维素类物质组成的双添加剂基于限域和吸附效应可以有效阻止水和杂质靠近电极-电解液界面区域,保障了界面的稳定性。1. The electrolyte of the composite rechargeable magnesium battery of the present invention contains dual organic solvents, dual electrolyte salts and dual additives; the dual organic solvents composed of chain ether solvents and perfluorinated amine solvents can not only adjust the polarity of the solvent, increase the The solubility of the large electrolyte salt can also enhance the stability of the electrolyte; the double electrolyte salt composed of organic magnesium salts and inorganic sodium salts can not only increase the concentration of the electrolyte salt, improve the conductivity of the electrolyte, but also help to improve magnesium ions. solvation environment, promoting charge transfer at the electrode-electrolyte interface, reducing magnesium deposition-dissolution overpotential, and improving cycling stability; dual additives composed of metal-organic frameworks and hydroxyalkylcelluloses are based on confinement The adsorption effect can effectively prevent water and impurities from approaching the electrode-electrolyte interface area, ensuring the stability of the interface.

2、本发明复合型电解液各组分之间的协同作用赋予该电解液电导率大、过电位小、镁沉积-溶出效率高的特点,特别是对水和杂质具有很高的宽容度,这显著降低了电解液成本、简化了电解液制备过程,为电解液的储存和使用提供了很大方便,具有良好的应用前景。2. The synergistic effect between the components of the composite electrolyte of the present invention endows the electrolyte with the characteristics of large electrical conductivity, small overpotential, and high magnesium deposition-dissolution efficiency, especially with high tolerance to water and impurities, This significantly reduces the cost of the electrolyte, simplifies the preparation process of the electrolyte, provides great convenience for the storage and use of the electrolyte, and has good application prospects.

3、本发明复合型可充镁电池电解液的制备无需对原料进行任何除水、除杂预处理,仅仅采用室温搅拌方式制备,工艺简单,易于大规模工业化生产。3. The preparation of the composite rechargeable magnesium battery electrolyte of the present invention does not require any dewatering and impurity pretreatment of the raw materials, and only adopts the stirring method at room temperature, the process is simple, and the large-scale industrial production is easy.

附图说明Description of drawings

图1为本发明实施例1所制备的电解液的电化学阻抗谱结果。FIG. 1 is the electrochemical impedance spectroscopy result of the electrolyte prepared in Example 1 of the present invention.

图2为本发明实施例1所制备的电解液以钼箔为工作电极的循环伏安曲线。Fig. 2 is the cyclic voltammetry curve of the electrolyte prepared in Example 1 of the present invention using molybdenum foil as the working electrode.

图3为本发明实施例1所制备的电解液以钼箔为工作电极在0.5mA·cm-2电流密度下的镁可逆沉积-溶出库伦效率。FIG. 3 shows the reversible deposition-dissolution Coulomb efficiency of magnesium in the electrolyte prepared in Example 1 of the present invention with molybdenum foil as the working electrode at a current density of 0.5 mA·cm -2 .

具体实施方式Detailed ways

下面结合具体实施例对本发明作进一步的详细说明。The present invention will be further described in detail below in conjunction with specific embodiments.

一、一种复合型可充镁电池电解液及其制备方法1. A composite rechargeable magnesium battery electrolyte and its preparation method

实施例1:Example 1:

一种复合型可充镁电池电解液,其制备方法具体如下:A composite rechargeable magnesium battery electrolyte, the preparation method of which is as follows:

室温惰性气氛下,分别量取乙二醇二甲醚80mL、全氟三乙胺20mL,将二者混合均匀即得复合有机溶剂;分别称取32.244g三氟甲磺酸镁、2.100g氟化钠、0.520g ZIF-8、1.560g羟乙基纤维素,依次缓慢加入到上述复合有机溶剂中,磁力搅拌48h,即得复合型可充镁电池电解液。Under an inert atmosphere at room temperature, weigh 80 mL of ethylene glycol dimethyl ether and 20 mL of perfluorotriethylamine respectively, and mix the two evenly to obtain a composite organic solvent; weigh 32.244 g of magnesium trifluoromethanesulfonate, 2.100 g of fluorinated trifluoromethanesulfonate, respectively. Sodium, 0.520g ZIF-8, and 1.560g hydroxyethyl cellulose were slowly added to the above-mentioned composite organic solvent in turn, and magnetically stirred for 48 hours to obtain a composite rechargeable magnesium battery electrolyte.

上述原料均购买后直接使用,无需进行任何除水、除杂预处理。The above raw materials are used directly after purchase, without any pretreatment of water removal and impurity removal.

实施例2-4:Example 2-4:

采用与实施例1相同的方法制备复合型可充镁电池电解液,即包括以下步骤:The composite rechargeable magnesium battery electrolyte is prepared by the same method as in Example 1, including the following steps:

室温惰性气氛下,分别量取一定体积的链状醚类有机溶剂和全氟胺类有机溶剂,将二者混合均匀即得复合有机溶剂;分别称取一定质量的有机镁盐、无机钠盐、金属有机框架类添加剂和羟烷基纤维素类添加剂,依次缓慢加入到上述复合有机溶剂中,磁力搅拌一定时间,即得复合型可充镁电池电解液。Under an inert atmosphere at room temperature, measure a certain volume of a chain ether-based organic solvent and a perfluoroamine-based organic solvent, and mix the two evenly to obtain a composite organic solvent; respectively weigh a certain mass of organic magnesium salt, inorganic sodium salt, The metal organic framework additives and the hydroxyalkyl cellulose additives are slowly added to the above-mentioned composite organic solvent in turn, and magnetically stirred for a certain period of time to obtain a composite type rechargeable magnesium battery electrolyte.

所有原料均购买后直接使用,无需进行任何除水、除杂预处理。All raw materials are used directly after purchase, without any pretreatment of water removal and impurity removal.

实施例2-4的电解液(以100mL计)制备条件如下表1所示:The electrolyte (in 100mL) preparation condition of embodiment 2-4 is as shown in Table 1 below:

表1Table 1

Figure BDA0003763634760000041
Figure BDA0003763634760000041

二、所述复合型可充镁电池低温电解液的性能测试方法2. Performance test method for the low-temperature electrolyte of the composite rechargeable magnesium battery

a.电解液的电导率测试a. Conductivity test of electrolyte

电解液的电导率由解析开路电位下的电化学阻抗谱而得到。电化学阻抗谱测试利用Autolab PGSTAT302N电化学工作站完成。采用三电极体系,以清洁的不锈钢箔(14mm厚)为参比电极、工作电极和对电极,所加激励信号为5mV,测试频率范围为105Hz~0.01Hz,测试温度为室温。由测得的阻抗谱得到电解液本体电阻Rs(Ω),进而通过如下电导率的定义式得到电解液电导率(σ,S/cm):The conductivity of the electrolyte was obtained by analyzing the electrochemical impedance spectroscopy at open circuit potential. Electrochemical impedance spectroscopy was performed using an Autolab PGSTAT302N electrochemical workstation. Using a three-electrode system, clean stainless steel foil (14mm thick) was used as the reference electrode, working electrode and counter electrode, the excitation signal was 5mV, the test frequency range was 10 5 Hz ~ 0.01Hz, and the test temperature was room temperature. The bulk resistance R s (Ω) of the electrolyte is obtained from the measured impedance spectrum, and then the conductivity of the electrolyte (σ, S/cm) is obtained by the following definition formula of conductivity:

σ=l/SRs σ=l/SR s

式中l为电解液厚度,cm;S为电解液与电极的接触面积,cm2where l is the thickness of the electrolyte, cm; S is the contact area between the electrolyte and the electrode, cm 2 .

b.电解液的镁可逆沉积-溶出性能测试b. Magnesium reversible deposition-dissolution performance test of electrolyte

电解液的镁可逆沉积-溶出性能通过循环伏安法测试,利用Autolab PGSTAT302N电化学工作站完成。以清洁的镁片电极为参比电极和对电极、钼箔为工作电极,电位范围为-0.8~1.8V,扫速为25mV/s。The magnesium reversible deposition-dissolution properties of the electrolyte were tested by cyclic voltammetry using an Autolab PGSTAT302N electrochemical workstation. The clean magnesium sheet electrode was used as the reference electrode and the counter electrode, and the molybdenum foil was used as the working electrode. The potential range was -0.8~1.8V, and the scanning speed was 25mV/s.

c.镁可逆沉积-溶出库伦效率测试c. Magnesium reversible deposition-dissolution coulombic efficiency test

镁在电解液中的可逆沉积-溶出库伦效率通过组装CR2032扣式电池进行测试。在惰性气氛手套箱中进行组装。工作电极为清洁的钼箔,对电极为清洁的镁片(同时作为参比电极)、隔膜采用GF/A膜、与自制的电解液一起组装成CR2032型扣式电池。电池组装好后在室温下静置12小时,然后利用Neware仪器进行恒电流充放电测试,电流密度为0.5mAcm-2,放电60min,然后充电至0.8V(vs.Mg/Mg2+),由一个循环中沉积镁的电荷量与溶出镁的电荷量之比计算得到库伦效率。The reversible deposition-dissolution coulombic efficiency of magnesium in the electrolyte was tested by assembling a CR2032 coin cell. Assembly was performed in an inert atmosphere glove box. The working electrode is a clean molybdenum foil, the counter electrode is a clean magnesium sheet (also used as a reference electrode), and the diaphragm is made of GF/A membrane, which is assembled with the self-made electrolyte to form a CR2032 button cell. After the battery was assembled, it was left to stand at room temperature for 12 hours, and then a constant current charge-discharge test was carried out using the Neware instrument, the current density was 0.5mAcm -2 , the discharge was 60min, and then charged to 0.8V (vs.Mg/Mg 2+ ), by The Coulombic efficiency was calculated from the ratio of the charge of the deposited magnesium to the charge of the dissolved magnesium in one cycle.

如图1所示,为实施例1所制备的电解液的电化学阻抗谱结果,对其进行解析可以得到该电解液的电导率为5.24mS·cm-1。而目前文献报道的可充镁电池电解液的电导率一般低于5.0mS·cm-1,表明该电解液具有电导率大的特点。As shown in FIG. 1 , which is the electrochemical impedance spectrum result of the electrolyte prepared in Example 1, it can be obtained that the conductivity of the electrolyte is 5.24 mS·cm −1 by analyzing it. However, the conductivity of the electrolyte for rechargeable magnesium batteries reported in the literature is generally lower than 5.0mS·cm -1 , indicating that the electrolyte has the characteristics of high conductivity.

如图2所示,以钼箔为工作电极,电解液循环150圈后的过电位为127mV,表明该电解液具有镁沉积-溶出过电位小的特点。As shown in Figure 2, with molybdenum foil as the working electrode, the overpotential of the electrolyte after 150 cycles of circulation is 127mV, indicating that the electrolyte has the characteristics of small magnesium deposition-dissolution overpotential.

如图3所示,电解液在长期循环1000圈时的镁可逆沉积-溶出(钼箔基底上)库伦效率保持在98.2%,表明该电解液具有镁沉积-溶出效率高的特点。As shown in Fig. 3, the reversible magnesium deposition-dissolution (on molybdenum foil substrate) Coulomb efficiency of the electrolyte maintained at 98.2% when the electrolyte was cycled for 1000 cycles, indicating that the electrolyte has the characteristics of high magnesium deposition-dissolution efficiency.

同样,利用上述方法对实施例2-4所制备的电解液进行性能测试,结果如表2所示。进一步证实了本发明电解液具有电导率大、过电位小、镁沉积-溶出效率高的特点。Similarly, the electrolyte solutions prepared in Examples 2-4 were tested for performance using the above method, and the results are shown in Table 2. It is further confirmed that the electrolyte of the present invention has the characteristics of high electrical conductivity, low overpotential and high magnesium deposition-dissolution efficiency.

表2Table 2

Figure BDA0003763634760000051
Figure BDA0003763634760000051

综上,本发明制备的复合型可充镁电池电解液具有电导率大、过电位小、镁沉积-溶出效率高的特点,特别是对水和杂质具有很高的宽容度,这显著降低了电解液成本、简化了电解液制备过程,为电解液的储存和使用提供了很大方便,具有良好的商业应用前景。并且,本发明电解液的制备无需对原料进行任何除水、除杂预处理,仅仅采用室温搅拌方式制备,工艺简单,易于大规模工业化生产。To sum up, the composite type rechargeable magnesium battery electrolyte prepared by the present invention has the characteristics of high electrical conductivity, low overpotential, high magnesium deposition-dissolution efficiency, especially high tolerance to water and impurities, which significantly reduces the The cost of the electrolyte solution simplifies the preparation process of the electrolyte solution, provides great convenience for the storage and use of the electrolyte solution, and has good commercial application prospects. In addition, the preparation of the electrolyte of the present invention does not require any pretreatment of dewatering and impurity removal on the raw materials, and only adopts a stirring method at room temperature to prepare the electrolyte, and the process is simple and easy for large-scale industrial production.

最后需要说明的是,以上实施例仅用以说明本发明的技术方案而非限制技术方案,本领域的普通技术人员应当理解,那些对本发明的技术方案进行修改或者等同替换,而不脱离本技术方案的宗旨和范围,均应涵盖在本发明的权利要求范围当中。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the technical solutions. Those skilled in the art should understand that those technical solutions of the present invention are modified or equivalently replaced without departing from the present technology. The purpose and scope of the solution should be included in the scope of the claims of the present invention.

Claims (7)

1.一种复合型可充镁电池电解液,其特征在于,含有机溶剂、电解质盐和添加剂,所述电解质盐在有机溶剂中的总摩尔浓度为1.1~1.5 mol/L,所述添加剂在有机溶剂中的总质量百分浓度为0.5~2.0 wt%。1. a composite type rechargeable magnesium battery electrolyte, is characterized in that, contains organic solvent, electrolyte salt and additive, the total molar concentration of described electrolyte salt in organic solvent is 1.1~1.5 mol/L, and described additive is in 1.1~1.5 mol/L. The total mass percentage concentration in the organic solvent is 0.5~2.0 wt%. 2.根据权利要求1所述复合型可充镁电池电解液,其特征在于,所述有机溶剂由链状醚类有机溶剂和全氟胺类有机溶剂按体积比1:0.25~1组成;所述电解质盐由有机镁盐和无机钠盐按物质的量之比1:0.5~1组成;所述添加剂由金属有机框架类物质和羟烷基纤维素类物质按质量比1:1~3组成。2. The composite type rechargeable magnesium battery electrolyte according to claim 1, wherein the organic solvent is composed of a chain ether organic solvent and a perfluoroamine organic solvent in a volume ratio of 1:0.25 to 1; The electrolyte salt is composed of organic magnesium salts and inorganic sodium salts in a ratio of 1:0.5 to 1; the additives are composed of metal organic framework substances and hydroxyalkyl cellulose substances in a mass ratio of 1:1 to 3. . 3.根据权利要求2所述复合型可充镁电池电解液,其特征在于,所述链状醚类有机溶剂为乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚中的任意一种;所述全氟胺类有机溶剂为全氟三乙胺或全氟三丁胺中的任意一种。3. The composite type rechargeable magnesium battery electrolyte according to claim 2, wherein the chain ether organic solvent is ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol diethyl ether Any one of methyl ether and tetraethylene glycol dimethyl ether; the perfluoroamine organic solvent is any one of perfluorotriethylamine or perfluorotributylamine. 4.根据权利要求2所述复合型可充镁电池电解液,其特征在于,所述电解质盐中的有机镁盐为三氟甲磺酸镁或双(三氟甲烷磺酰亚胺)镁中的任意一种;所述电解质盐中的无机钠盐为氟化钠或溴化钠中的任意一种。4. The electrolyte of the composite rechargeable magnesium battery according to claim 2, wherein the organic magnesium salt in the electrolyte salt is in magnesium trifluoromethanesulfonate or magnesium bis(trifluoromethanesulfonimide) any one; the inorganic sodium salt in the electrolyte salt is any one in sodium fluoride or sodium bromide. 5.根据权利要求2所述复合型可充镁电池电解液,其特征在于,所述添加剂中的金属有机框架类物质为ZIF-8或ZIF-67中的任意一种;所述添加剂中的羟烷基纤维素类物质为羟乙基纤维素或羟丙基纤维素中的任意一种。5. The electrolyte for composite rechargeable magnesium battery according to claim 2, wherein the metal organic framework substance in the additive is any one of ZIF-8 or ZIF-67; The hydroxyalkyl cellulose material is any one of hydroxyethyl cellulose or hydroxypropyl cellulose. 6.一种复合型可充镁电池电解液的制备方法,其特征在于,包括如下步骤:6. a preparation method of composite rechargeable magnesium battery electrolyte, is characterized in that, comprises the steps: 按权利要求1至5任一组份备料;室温惰性气氛下,量取链状醚类有机溶剂和全氟胺类有机溶剂,将二者混合均匀即得复合有机溶剂;称取有机镁盐、无机钠盐、金属有机框架类添加剂和羟烷基纤维素类添加剂,依次缓慢加入到复合有机溶剂中,磁力搅拌48 h~60 h,即得电解液。Prepare materials according to any one of claims 1 to 5; under an inert atmosphere at room temperature, measure a chain ether organic solvent and a perfluoroamine organic solvent, and mix the two evenly to obtain a composite organic solvent; weigh the organic magnesium salt, Inorganic sodium salt, metal organic framework additives and hydroxyalkyl cellulose additives are slowly added to the composite organic solvent in turn, and magnetically stirred for 48 h to 60 h to obtain an electrolyte. 7.根据权利要求6所述复合型可充镁电池电解液的制备方法,其特征在于,制备所用有机溶剂、电解质盐和添加剂均无需进行任何除水、除杂预处理。7 . The method for preparing a composite rechargeable magnesium battery electrolyte according to claim 6 , wherein the organic solvent, electrolyte salt and additives used in the preparation do not require any pretreatment for water removal and impurity removal. 8 .
CN202210879412.1A 2022-07-25 2022-07-25 A composite rechargeable magnesium battery electrolyte and preparation method thereof Active CN115084652B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210879412.1A CN115084652B (en) 2022-07-25 2022-07-25 A composite rechargeable magnesium battery electrolyte and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210879412.1A CN115084652B (en) 2022-07-25 2022-07-25 A composite rechargeable magnesium battery electrolyte and preparation method thereof

Publications (2)

Publication Number Publication Date
CN115084652A true CN115084652A (en) 2022-09-20
CN115084652B CN115084652B (en) 2024-12-06

Family

ID=83242002

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210879412.1A Active CN115084652B (en) 2022-07-25 2022-07-25 A composite rechargeable magnesium battery electrolyte and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115084652B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117810541A (en) * 2022-09-23 2024-04-02 青岛科技大学 Nonaqueous magnesium electrolyte and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103794815A (en) * 2014-02-18 2014-05-14 上海交通大学 Electrolytic solution of rechargeable magnesium cell and application method thereof
CN106025331A (en) * 2016-05-27 2016-10-12 浙江大学 Rechargeable magnesium battery and preparation method thereof
CN106384844A (en) * 2016-07-27 2017-02-08 中国科学院苏州纳米技术与纳米仿生研究所 Non-nucleophilic dual-salt-system electrolyte for magnesium cell, and preparation method and application thereof
CN107069116A (en) * 2017-03-01 2017-08-18 东莞市联洲知识产权运营管理有限公司 A kind of preparation method of the zinc-nickel secondary batteries of high power density
WO2017190355A1 (en) * 2016-05-06 2017-11-09 深圳先进技术研究院 Electrolyte solution, secondary battery containing electrolyte solution and preparation method therefor
CN109687027A (en) * 2019-01-17 2019-04-26 上海交通大学 A kind of rechargeable magnesium cell electrolyte and rechargeable magnesium cell
US20200058958A1 (en) * 2016-03-04 2020-02-20 Broadbit Batteries Oy Rechargeable sodium cells for high energy density battery use
CN113258138A (en) * 2021-05-18 2021-08-13 重庆大学 Full-inorganic salt type rechargeable magnesium battery electrolyte and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103794815A (en) * 2014-02-18 2014-05-14 上海交通大学 Electrolytic solution of rechargeable magnesium cell and application method thereof
US20200058958A1 (en) * 2016-03-04 2020-02-20 Broadbit Batteries Oy Rechargeable sodium cells for high energy density battery use
WO2017190355A1 (en) * 2016-05-06 2017-11-09 深圳先进技术研究院 Electrolyte solution, secondary battery containing electrolyte solution and preparation method therefor
CN106025331A (en) * 2016-05-27 2016-10-12 浙江大学 Rechargeable magnesium battery and preparation method thereof
CN106384844A (en) * 2016-07-27 2017-02-08 中国科学院苏州纳米技术与纳米仿生研究所 Non-nucleophilic dual-salt-system electrolyte for magnesium cell, and preparation method and application thereof
CN107069116A (en) * 2017-03-01 2017-08-18 东莞市联洲知识产权运营管理有限公司 A kind of preparation method of the zinc-nickel secondary batteries of high power density
CN109687027A (en) * 2019-01-17 2019-04-26 上海交通大学 A kind of rechargeable magnesium cell electrolyte and rechargeable magnesium cell
CN113258138A (en) * 2021-05-18 2021-08-13 重庆大学 Full-inorganic salt type rechargeable magnesium battery electrolyte and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王瑛;王雅丽;赵成龙;陈良;徐守冬;张鼎;: "基于金属有机骨架氧化物模板法的空心NiO的制备及其储钠电化学性能", 广东化工, no. 19, 15 October 2016 (2016-10-15), pages 27 - 30 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117810541A (en) * 2022-09-23 2024-04-02 青岛科技大学 Nonaqueous magnesium electrolyte and preparation method thereof

Also Published As

Publication number Publication date
CN115084652B (en) 2024-12-06

Similar Documents

Publication Publication Date Title
CN106450247B (en) Metal bismuth anodes and ether-based electrolytes for sodium/potassium ion secondary batteries
CN114122513B (en) Functional electrolyte additive, battery electrolyte and sodium ion battery
CN103219542A (en) High-salinity non-aqueous electrolyte and use thereof
CN107069079A (en) A kind of solid state electrolyte and its preparation and application
Jiang et al. Effect of Sn doping on the electrochemical performance of NaTi2 (PO4) 3/C composite
CN106410148B (en) A kind of high-performance kalium ion battery negative electrode material and the electrolyte to match
CN103700842B (en) A kind of NiFe 2o 4/ C lithium ion battery cathode material and its preparation method
CN103606657A (en) Lithium ion battery zinc oxide/porous carbon composite negative electrode material with high capacity and preparation method thereof
CN113270577B (en) Aqueous zinc ion battery and positive electrode material
CN114583281A (en) A high-voltage-resistant ether-based electrolyte for low-temperature lithium metal batteries
CN112768766B (en) A lithium-sulfur battery electrolyte and its application
CN107293791A (en) A kind of tertiary cathode material lithium-ion battery electrolytes and the lithium ion battery comprising the electrolyte
WO2021004259A1 (en) Symmetrical aqueous sodium-ion battery
CN112331919A (en) Electrolyte suitable for silicon-carbon negative electrode material
CN115084652A (en) A composite rechargeable magnesium battery electrolyte and preparation method thereof
CN105428704B (en) A kind of modified oxidized reduced form solid electrolyte and its preparation method and application
CN108550846A (en) Tungsten disulfide negative material for potassium ion secondary cell
CN108232302A (en) A kind of high concentration lithium salt electrolyte suitable for silicon-based anode lithium ion battery
CN117766304A (en) Water-based double-electric-layer supercapacitor electrolyte and preparation method and application thereof
CN111477977B (en) Water-ether mixed electrolyte for lithium ion battery and preparation method thereof
CN106898744A (en) The preparation method and application of prussian blue nanoporous frame material
CN116666628A (en) Novel negative electrode material for water-based battery, water-based battery and preparation method of novel negative electrode material
CN106785023B (en) An electrolyte system for lithium-ion battery silicon-based/silicon-carbon composite negative electrode material
CN113140791A (en) Pyrazine electrolyte of lithium-air battery
CN115000513B (en) A wide potential window rechargeable magnesium battery electrolyte and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant