CN115084652A - A composite rechargeable magnesium battery electrolyte and preparation method thereof - Google Patents
A composite rechargeable magnesium battery electrolyte and preparation method thereof Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 96
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000011777 magnesium Substances 0.000 title claims abstract description 53
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 37
- 239000000654 additive Substances 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 claims description 8
- 159000000003 magnesium salts Chemical class 0.000 claims description 8
- 239000012621 metal-organic framework Substances 0.000 claims description 8
- 159000000000 sodium salts Chemical class 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- GVGCUCJTUSOZKP-UHFFFAOYSA-N nitrogen trifluoride Chemical compound FN(F)F GVGCUCJTUSOZKP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- CBEFDCMSEZEGCX-UHFFFAOYSA-N 1,1,2,2,2-pentafluoro-n,n-bis(1,1,2,2,2-pentafluoroethyl)ethanamine Chemical compound FC(F)(F)C(F)(F)N(C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)F CBEFDCMSEZEGCX-UHFFFAOYSA-N 0.000 claims description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 3
- BZQRBEVTLZHKEA-UHFFFAOYSA-L magnesium;trifluoromethanesulfonate Chemical compound [Mg+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F BZQRBEVTLZHKEA-UHFFFAOYSA-L 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 3
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- DMFBPGIDUUNBRU-UHFFFAOYSA-N magnesium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Mg+2].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F DMFBPGIDUUNBRU-UHFFFAOYSA-N 0.000 claims description 2
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- KIAMPLQEZAMORJ-UHFFFAOYSA-N 1-ethoxy-2-[2-(2-ethoxyethoxy)ethoxy]ethane Chemical compound CCOCCOCCOCCOCC KIAMPLQEZAMORJ-UHFFFAOYSA-N 0.000 claims 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000011888 foil Substances 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- 230000009977 dual effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 4
- 229940021013 electrolyte solution Drugs 0.000 description 4
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- 239000000306 component Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- -1 fluorine amine Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical class OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
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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
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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
- H01M10/0567—Liquid materials characterised by the additives
-
- 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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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
Description
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
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,cm2。where 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
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.
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CN117810541A (en) * | 2022-09-23 | 2024-04-02 | 青岛科技大学 | Nonaqueous magnesium electrolyte and preparation method thereof |
Citations (8)
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 |
-
2022
- 2022-07-25 CN CN202210879412.1A patent/CN115084652B/en active Active
Patent Citations (8)
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)
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)
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 |
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