WO2022252533A1 - 一种孔内限域聚合有机单体的金属-有机框架基材料及其制备方法和应用 - Google Patents

一种孔内限域聚合有机单体的金属-有机框架基材料及其制备方法和应用 Download PDF

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WO2022252533A1
WO2022252533A1 PCT/CN2021/135951 CN2021135951W WO2022252533A1 WO 2022252533 A1 WO2022252533 A1 WO 2022252533A1 CN 2021135951 W CN2021135951 W CN 2021135951W WO 2022252533 A1 WO2022252533 A1 WO 2022252533A1
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metal
organic
organic framework
acid
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张琪
欧阳远
黄少铭
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Guangdong University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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 present invention relates to the technical field of all-solid-state electrolyte materials, and more specifically, relates to a metal-organic framework-based material for confinement polymerization of organic monomers in pores, as well as its preparation method and application.
  • Lithium metal (Li) has high theoretical specific capacity (3860mAh/g), low density and extremely low electrode potential, so it is considered as an ideal battery negative electrode material.
  • the metal lithium anode also avoids the use of current collectors, which can significantly increase the energy density of the battery.
  • lithium metal anodes are prone to safety problems due to the non-uniform deposition of lithium metal during charging and discharging, leading to the growth of lithium dendrites, which hinders the application of lithium metal anodes.
  • high-energy-density lithium batteries have a series of safety hazards such as easy leakage, fire, and explosion due to the use of organic electrolytes.
  • One of the effective ways to improve the above problems and improve battery safety is to use all-solid polymer electrolytes instead of traditional organic electrolytes.
  • Chinese patent CN111180791A discloses a preparation method based on metal-organic framework-ionic liquid composite all-solid electrolyte, in which the lithium-ion liquid is poured into the pores of the metal-organic framework material, and coated on the template to form a composite all-solid electrolyte ;
  • the ionic conductivity of the prepared composite all-solid electrolyte is still low (1.20 ⁇ 10 -4 S/cm), so the preparation of an all-solid electrolyte material with high ionic conductivity is still a huge technical challenge at this stage .
  • the technical problem to be solved by the present invention is to overcome the defects and deficiencies of the low ionic conductivity of the existing all-solid electrolyte materials, and provide a method for preparing a metal-organic framework-based material for confinement polymerization of organic monomers in the pores.
  • the in-situ confinement polymerization of organic monomers in the pores of the organic framework that is, the use of organic monomers to solidify in the pores to obtain metal-organic framework material-based materials
  • the prepared materials can be used as all-solid electrolytes with high ionic conductivity, It can effectively inhibit the growth of lithium dendrites, and the interface impedance is low.
  • the all-solid-state electrolyte based on the metal-organic framework material is applied to the all-solid-state lithium metal battery, the battery capacity is large, and the cycle performance and rate performance are excellent.
  • Another object of the present invention is to provide a metal-organic framework-based material for confinement polymerization of organic monomers in pores.
  • Another object of the present invention is to provide an application of a metal-organic framework-based material for confinement polymerization of organic monomers in pores.
  • a method for preparing a metal-organic framework-based material for confined polymerization of organic monomers in pores comprising the steps of:
  • metal-organic framework materials organic monomers, lithium salts, and initiators, and react at 85-95°C for 20-24 hours to obtain metal-organic framework-based materials for confined polymerization of organic monomers in pores, wherein the The molar ratio of the metal-organic framework material, organic monomer, lithium salt, and initiator is 1:1-8:0.1-50:0.1-5, and the organic monomer is an ionic liquid containing a carbon-carbon double bond and/or Or small organic molecules containing carbon-carbon double bonds.
  • the organic monomers selected in the present invention are materials with high intrinsic ionic conductivity, and the organic monomers are placed in the pores of the metal-organic framework material for in-situ confinement polymerization, and the conductive ions are encapsulated in the metal-organic framework In the pores of the material, the organic monomer is solidified in the pores to obtain a metal-organic framework material.
  • the material provided by the invention as an all-solid electrolyte achieves the effect of high ion conduction efficiency and can avoid the leakage problem of traditional electrolytes.
  • the molar ratio of the metal-organic framework material, organic monomer, lithium salt, and initiator is 1:1 ⁇ 6:1 ⁇ 20:0.1 ⁇ 1.
  • the ionic liquid containing a carbon-carbon double bond is 1-allyl-3-methylimidazolium salt, 1-vinyl-3-ethylimidazolium salt, 1-vinyl-3-butylimidazolium bis One or more of salt, 1-vinyl-3-hexylimidazolium salt, 1-allyl-3-vinylimidazolium salt.
  • the ionic liquid containing a carbon-carbon double bond is 1-allyl-3-methylimidazole bis(trifluoromethylsulfonyl)imide salt, 1-vinyl-3-ethylimidazole bis (Trifluoromethylsulfonyl) salt, 1-vinyl-3-butylimidazole bis(trifluoromethylsulfonyl) salt, 1-vinyl-3-hexylimidazole bis(trifluoromethylsulfonyl) salt , 1-allyl-3-vinylimidazole bis(trifluoromethylsulfonyl) salt or one or more of them.
  • the small organic molecule containing a carbon-carbon double bond is one of ethylene carbonate, vinylene carbonate, ethyl 2-cyanoacrylate, ethyl ⁇ -cyanoacrylate, acrylic acid, and acrylonitrile or several.
  • the metal-organic framework material is prepared by coordination self-assembly of metal salts and organic ligands, wherein the molar ratio of metal salts and organic ligands is 1:0.5-3.
  • the metal salt is anhydrous zirconium chloride, ferric chloride hexahydrate, chromium nitrate nonahydrate, aluminum chloride hexahydrate, zirconium oxychloride octahydrate, ammonium cerium nitrate, isopropyl titanate, nitric acid trihydrate One or more of copper and zinc nitrate hexahydrate.
  • the organic ligand is 2-vinyl terephthalic acid, terephthalic acid, 2-sulfonic acid terephthalic acid monosodium salt, p-mercapto terephthalic acid, 2,5-dihydroxy terephthalic acid Dicarboxylic acid, 2-hydroxyterephthalic acid, 2-aminoterephthalic acid, 2-methyl-1,4-benzenedicarboxylic acid, 2,2'-bipyridine-5,5'-dicarboxylic acid, 1 ,4-naphthalene dicarboxylic acid, trimesic acid, 4,4-azopyridine, 1,2-bis(4-pyridyl)ethylene, medium-tetrakis(4-carboxyphenyl)porphine, 5,10, One or more of 15,20-tetrakis(4-aminophenyl)porphyrin, tetrakis(4-fluorophenyl)porphyrin and imidazolephenyl
  • the temperature of the coordination self-assembly is 20-200° C.
  • the reaction time is 12-15 hours.
  • the solvent is one or more of N,N-dimethylformamide, acetone, N-methylpyrrolidone, propylene carbonate, acetonitrile, and N,N-dimethylacetamide.
  • the lithium salt is lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bisoxalate borate, lithium difluorooxalate borate, lithium bisdifluorosulfonimide, bistrifluoromethane
  • lithium perchlorate lithium tetrafluoroborate
  • lithium hexafluoroarsenate lithium hexafluorophosphate
  • lithium bisoxalate borate lithium difluorooxalate borate
  • lithium bisdifluorosulfonimide bistrifluoromethane
  • the initiator is azobisisobutyronitrile.
  • the present invention protects the metal-organic framework-based material of intrapore confinement polymerization of organic monomers prepared by the above preparation method.
  • the present invention also protects the application of the above-mentioned metal-organic framework-based material of confinement-polymerized organic monomers in pores in the preparation of all-solid-state lithium batteries.
  • the present invention also protects the application of the metal-organic framework-based material of the above-mentioned confinement-polymerized organic monomer in the pores as an all-solid-state electrolyte for an all-solid-state lithium battery.
  • lithium iron phosphate is used as the positive electrode material
  • metal lithium is used as the negative electrode material
  • the metal-organic framework-based material of the confined polymerized organic monomer in the pores is used as the all-solid electrolyte and the polymer to form a film, and then assembled into a button-type all-solid lithium metal battery.
  • the metal-organic framework-based material is used as a method for preparing a film composed of an all-solid electrolyte and a polymer, comprising the following steps:
  • step S2 Soak the flexible all-solid membrane prepared in step S1 in an acetonitrile solution of lithium bistrifluoromethanesulfonimide, take it out after 12-24 hours, and dry it to prepare an all-solid electrolyte membrane.
  • the concentration of the acetonitrile solution is 0.5-5 mol/L.
  • the present invention uses a certain ratio of metal-organic framework materials, organic monomers, lithium salts, and initiators to prepare metal-organic framework-based materials for confinement polymerization of organic monomers in pores, and the selected organic monomers are intrinsic ions
  • organic monomers, lithium salts, and initiators are placed in nanocages of metal-organic framework materials for in-situ confinement polymerization, and conductive ions are encapsulated in the pores of metal-organic framework materials.
  • the prepared material achieve the effect of high ion conduction efficiency, and then further use the prepared material as an all-solid electrolyte, which can not only avoid the leakage problem of traditional electrolytes, but also improve the electrochemical window of the material, showing high ion conductance
  • the rate can effectively inhibit the growth of lithium dendrites.
  • Fig. 2 is a scanning electron micrograph of the metal-organic framework-based material prepared by confinement polymerization of organic monomers in pores prepared in Example 1 of the present invention.
  • Fig. 3 is a room temperature ionic conductivity diagram of the metal-organic framework-based material prepared by confinement polymerization of organic monomers in pores prepared in Example 1 of the present invention.
  • Fig. 4 is an electrochemical window diagram of the metal-organic framework-based material prepared by confinement polymerization of organic monomers in the pores in Example 1 of the present invention.
  • Fig. 5 is a rate performance diagram of an all-solid-state lithium metal battery assembled as an all-solid-state electrolyte membrane using a metal-organic framework-based material for confinement-polymerized organic monomers in pores prepared in Example 2 of the present invention.
  • Fig. 6 is a cycle performance diagram of an all-solid-state lithium metal battery assembled as an all-solid-state electrolyte membrane using a metal-organic framework-based material prepared by confinement polymerization of organic monomers in the pores in Example 2 of the present invention.
  • the raw material reagents used in the examples of the present invention are conventionally purchased raw material reagents.
  • a method for preparing a metal-organic framework-based material for confined polymerization of organic monomers in pores comprising the steps of:
  • the molar ratio is 1:5.7:13.5:0.7.
  • the preparation method of this example is the same as that of Example 1, except that the 2-vinyl terephthalic acid in step S1 is replaced with terephthalic acid.
  • the preparation method of this example is the same as that of Example 1, except that the 2-vinyl terephthalic acid in step S1 is replaced with 2-sulfonic acid terephthalic acid monosodium salt.
  • the preparation method of this example is the same as that of Example 1, except that the reaction temperature of the metal-organic framework material in step S1 is replaced by 150°C.
  • the preparation method of this example is the same as that of Example 1, except that the molar ratio of metal-organic framework material, organic monomer, lithium salt, and initiator is replaced by 1:1:0.1:0.1.
  • the preparation method of this example is the same as that of Example 1, except that the molar ratio of metal-organic framework material, organic monomer, lithium salt, and initiator is replaced by 1:8:50:5.
  • the preparation method of this example is the same as that of Example 1, except that the organic monomer is replaced by ethylene carbonate.
  • the metal-organic framework material preparation method of this comparative example comprises the following steps:
  • the preparation method of the metal-organic framework material of this comparative example comprises the following steps:
  • the preparation method of the metal-organic framework material of this comparative example comprises the following steps:
  • the metal-organic framework-based material prepared above is used as an all-solid-state electrolyte membrane in an all-solid-state lithium metal battery, including the following steps:
  • SN 20-LITFSI is a solution of succinonitrile and lithium bistrifluoromethanesulfonimide in a molar ratio of 20:1.
  • a 2032-type lithium iron phosphate/lithium button battery is assembled in the order of the positive electrode case, positive electrode, electrolyte, negative electrode, gasket, shrapnel, and negative electrode case.
  • Example 2 The metal-organic framework-based material prepared in Example 1 for confinement polymerization of organic monomers in the pores was tested by X-ray diffraction using Rigaku Smartlab 9kW.
  • the all-solid-state lithium metal battery was subjected to a rate performance test and a cycle performance test in a Xinwei test cabinet.
  • the structure of metal-organic framework-based materials is conducive to the conduction of metal ions in the crystal.
  • the materials synthesized in Examples 2-4 all showed good crystallinity.
  • the above results show that the pore limit prepared in Example 1 Metal-organic framework-based materials of domain-polymerized organic monomers exhibit high ionic conductivity at 300K.
  • the data in Figure 5 shows that the discharge specific capacity can reach 152mAh/g, 150mAh/g, 140mAh/g, 118mAh/g and 160mAh/g at the rate of 0.5C, 1C, 2C, 5C and 0.2C, which shows that its capacity is high , showing that the all-solid-state lithium metal battery obtained by the product assembly of Example 1 has excellent rate performance, and the charge-discharge specific capacity and rate performance are significantly better than the all-solid-state lithium metal battery based on the metal-organic framework material in Comparative Example 1 .
  • the data in Figure 6 shows that the all-solid-state lithium metal battery based on the all-solid-state electrolyte prepared by the product of Example 1 is charged and discharged at a rate of 1C, and the capacity after 500 cycles at a high rate of 1C can reach 140mAh/g, proving Its cycle stability is good, the battery has high capacity and slow decay at high rates, and its cycle stability is significantly better than that of the all-solid-state lithium metal battery based on the metal-organic framework material in Comparative Example 1. It has high safety performance and has a wide electrochemical window. long lasting.
  • the metal-organic framework materials MIL-101-SO 3 H and Zr-MOF-SH prepared in Comparative Example 2 and Comparative Example 3 did not have such high ionic conductivity as Example 1 at 300K; the ionic liquid perfusion obtained in Comparative Example 4 Metal-organic framework materials belong to the semi-solid state, and there is leakage under high pressure.

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Abstract

本发明公开了一种孔内限域聚合有机单体的金属-有机框架基材料及其制备方法和应用，将有机单体、锂盐、引发剂置于金属有机框架材料的孔内进行原位限域聚合，将传导离子封装在金属-有机框架材料的孔内，使其达到高离子传导效率的效果，利用本发明提供的材料作为全固态电解质，可以避免传统电解质存在的漏液问题，并且提高了材料的电化学窗口，表现出高离子电导率，进一步将全固态电解质组装成电池后可减少电池内部的极化，副反应少，循环性能稳定，电池高倍率下容量高且衰减慢，延长电池使用寿命，可以广泛应用于锂电池体系，大幅提升现有锂电池的能量密度和安全性能。

Description

一种孔内限域聚合有机单体的金属-有机框架基材料及其制备方法和应用 技术领域
本发明涉及全固态电解质材料技术领域，更具体地，涉及一种孔内限域聚合有机单体的金属-有机框架基材料及其制备方法和应用。
背景技术
储能设备是现代人类社会的关键技术。由于锂离子二次电池具有工作电压高、循环寿命长、环境污染小等诸多优点，当今业已广泛服务于各种便携式数码产品，成为应用极为普遍的绿色化学电源。然而，目前其能量密度(<200Wh/kg)仍难以满足电动汽车等实用需要。新一代高比能量锂电池是未来储能器件的发展方向，而其发展取决于高容量电极材料的开发及电池安全性问题的解决。金属锂(Li)具有高理论比容量(3860mAh/g)、低密度和极低的电极电位，因而被认为是理想的电池负极材料。金属锂负极还避免了集流体的使用，因而可显著提高电池能量密度。不幸的是，锂金属负极在充放电过程中易因锂金属的非均匀沉积导致锂枝晶生长而带来安全问题，阻碍了锂金属负极的应用。此外，高能量密度锂电池因使用有机电解液而存在易漏液、着火、爆炸等一系列安全隐患。改善以上问题，提升电池安全性的有效途径之一是使用全固态聚合物电解质取代传统有机电解液。如中国专利CN111180791A公开了一种基于金属有机框架-离子液体复合全固态电解质的制备方法，将含锂离子液体灌注到金属有机框架材料的孔道内，涂覆在模板上成膜得到复合全固态电解质；然而，所制得的复合全固态电解质的离子电导率仍然较低(1.20×10 -4S/cm)，因此制备出具有高离子电导率的全固态电解质材料仍是现阶段巨大的技术挑战。
发明内容
本发明要解决的技术问题是克服现有全固态电解质材料离子电导率低的缺陷和不足，提供一种孔内限域聚合有机单体的金属-有机框架基材料的制备方法，通过在金属-有机框架的孔内原位限域聚合有机单体，即利用有机单体在孔内固化制得金属-有机框架材料基材料，所制得的材料可以作为全固态电解质，其离子电导率高，能有效抑制锂枝晶的生长，界面阻抗低，将该基于金属-有机框架 材料的全固态电解质应用于全固态锂金属电池后，电池容量大，循环性能和倍率性能优异。
本发明的又一目的是提供一种孔内限域聚合有机单体的金属-有机框架基材料。
本发明的另一目的是提供一种孔内限域聚合有机单体的金属-有机框架基材料的应用。
本发明上述目的通过以下技术方案实现：
一种孔内限域聚合有机单体的金属-有机框架基材料的制备方法，包括如下步骤：
将金属-有机框架材料、有机单体、锂盐、引发剂混合研磨，并在85～95℃反应20～24h后，得到孔内限域聚合有机单体的金属-有机框架基材料，其中所述金属-有机框架材料、有机单体、锂盐、引发剂的摩尔比为1：1～8：0.1～50：0.1～5，所述有机单体为含碳碳双键的离子液体和/或含碳碳双键的有机小分子。
本发明所选用的有机单体为本征离子电导率较高的材料，并将有机单体置于金属有机框架材料的孔内进行原位限域聚合，并将传导离子封装在金属-有机框架材料的孔内，有机单体在孔内固化制得金属-有机框架材料基材料，利用本发明提供的材料作为全固态电解质，达到高离子传导效率的效果，可以避免传统电解质存在的漏液问题，并且提高了材料的电化学窗口；进一步将全固态电解质组装成电池后可减少电池内部的极化，副反应少，界面阻抗低，循环性能稳定，电池高倍率下容量高且衰减慢，延长电池使用寿命。
优选地，所述金属-有机框架材料、有机单体、锂盐、引发剂的摩尔比为1：1～6：1～20：0.1～1。
优选地，所述含碳碳双键的离子液体为1-烯丙基-3-甲基咪唑盐、1-乙烯基-3-乙基咪唑盐、1-乙烯基-3-丁基咪唑双盐、1-乙烯基-3-己基咪唑盐、1-烯丙基-3-乙烯基咪唑盐中的一种或几种。
更优选地，所述含碳碳双键的离子液体为1-烯丙基-3-甲基咪唑双(三氟甲基磺酰)亚胺盐、1-乙烯基-3-乙基咪唑双(三氟甲基磺酰)盐、1-乙烯基-3-丁基咪唑双(三氟甲基磺酰)盐、1-乙烯基-3-己基咪唑双(三氟甲基磺酰)盐、1-烯丙基-3-乙烯基咪唑双(三氟甲基磺酰)盐中的一种或几种。
优选地，所述含碳碳双键的有机小分子为碳酸乙烯亚乙酯、碳酸亚乙烯酯、2-氰基丙烯酸乙酯、α-氰基丙烯酸乙酯、丙烯酸、丙烯腈中的一种或几种。
优选地，所述金属-有机框架材料由金属盐和有机配体通过配位自组装制得，其中金属盐和有机配体的摩尔比为1：0.5～3。
优选地，所述金属盐为无水氯化锆、六水氯化铁、九水硝酸铬、六水氯化铝、八水合氯氧化锆、硝酸铈铵、钛酸异丙酯、三水硝酸铜、六水硝酸锌中的一种或几种。
优选地，所述有机配体为2-乙烯基对苯二甲酸、对苯二甲酸、2-磺酸对苯二甲酸单钠盐、对巯基对苯二甲酸、2,5-二羟基对苯二甲酸、2-羟基对苯二甲酸、2-氨基对苯二甲酸、2-甲基-1,4-苯二甲酸、2,2'-联吡啶-5,5'-二羧酸、1,4-萘二甲酸、均苯三甲酸、4,4-偶氮吡啶、1,2-二(4-吡啶基)乙烯、中-四(4-羧基苯基)卟吩、5,10,15,20-四(4-氨基苯基)卟啉、四(4-氟苯基)卟啉、咪唑苯基卟啉中的一种或几种。
优选地，所述配位自组装的温度为20～200℃，反应时间为12～15h。
优选地，所述溶剂为N,N-二甲基甲酰胺、丙酮、N-甲基吡咯烷酮、碳酸丙烯酯、乙腈、N,N-二甲基乙酰胺中的一种或几种。
优选地，所述锂盐为高氯酸锂、四氟硼酸锂、六氟砷酸锂、六氟磷酸锂、双草酸硼酸锂、二氟草酸硼酸锂、双二氟磺酰亚胺锂、双三氟甲基磺酰亚胺锂的一种或几种。
优选地，所述引发剂为偶氮二异丁腈。
本发明保护上述制备方法制得的孔内限域聚合有机单体的金属-有机框架基材料。
本发明还保护上述孔内限域聚合有机单体的金属-有机框架基材料在制备全固态锂电池的应用。
本发明还保护上述孔内限域聚合有机单体的金属-有机框架基材料在作为全固态锂电池的全固态电解质的应用。
优选地，以磷酸铁锂为正极材料，金属锂为负极材料，孔内限域聚合有机单体的金属-有机框架基材料作为全固态电解质与聚合物组成膜，然后组装成纽扣式全固态锂金属电池。
优选地，所述金属-有机框架基材料作为全固态电解质与聚合物组成膜的制备方法，包括如下步骤：
S1.将金属-有机框架基材料的全固态电解质与聚(偏二氟乙烯-co-六氟丙烯)溶解于N-甲基吡咯烷酮中，混合均匀，涂覆于模具上，在60～100℃干燥，得到柔性全固态膜；
S2.将步骤S1制得的柔性全固态膜浸润在双三氟甲基磺酰亚胺锂的乙腈溶液中，12～24h后取出，干燥，制得全固态电解质膜。
优选地，所述乙腈溶液的浓度为0.5～5mol/L。
与现有技术相比，本发明的有益效果是：
本发明利用一定配比的金属-有机框架材料、有机单体、锂盐、引发剂制得孔内限域聚合有机单体的金属-有机框架基材料，所选用的有机单体为本征离子电导率较高的材料，然后将有机单体、锂盐、引发剂置于金属有机框架材料的纳米笼内进行原位限域聚合，同时将传导离子封装在金属-有机框架材料的孔内，使制得的材料达到高离子传导效率的效果，然后进一步将制得的材料作为全固态电解质，不仅可以避免传统电解质存在的漏液问题，并且提高了材料的电化学窗口，表现出高离子电导率，能有效抑制锂枝晶的生长，将全固态电解质组装成电池后可减少电池内部的极化，副反应少，界面阻抗低，循环性能稳定，电池高倍率下容量高且衰减慢，延长电池使用寿命，可以广泛应用于锂电池体系，大幅提升现有锂电池的能量密度和安全性能。
附图说明
图1为本发明实施例1制备的金属-有机框架材料UIO-66-C＝C的X射线衍射图。
图2为本发明实施例1制备的孔内限域聚合有机单体的金属-有机框架基材料的扫描电镜图。
图3为本发明实施例1制备的孔内限域聚合有机单体的金属-有机框架基材料的室温离子电导率图。
图4为本发明实施例1制备的孔内限域聚合有机单体的金属-有机框架基材料的电化学窗口图。
图5为本发明实施例2制备的孔内限域聚合有机单体的金属-有机框架基材 料作为全固态电解质膜组装的全固态锂金属电池的倍率性能图。
图6本发明实施例2制备的孔内限域聚合有机单体的金属-有机框架基材料作为全固态电解质膜组装的全固态锂金属电池的循环性能图。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明，但实施例并不对本发明做任何形式的限定。除非另有说明，本发明实施例采用的原料试剂为常规购买的原料试剂。
实施例1
一种孔内限域聚合有机单体的金属-有机框架基材料的制备方法，包括如下步骤：
S1.称取摩尔比为1：0.71的氯化锆和2-乙烯基对苯二甲酸，将其置于0.255mol的N,N-二甲基甲酰胺和0.043mol的盐酸中于80℃加热12h后用无水乙醇进行洗涤并离心得到金属有机框架材料乙烯基二甲酸锆(UIO-66-CH＝CH 2)；
S2.称取2g的1-甲基咪唑和2g的氯丙烯在5mL的乙腈中搅拌均匀，将溶液置于在100mL的圆底烧瓶中，85℃恒温24h，待反应冷却后，通过旋转蒸发将溶剂去除得到咪唑类离子液体A；将7g的双三氟甲磺酰亚胺锂和离子液体A混合，加入30mL的去离子水搅拌均匀至分层，将上清液倒掉，反复洗涤数次收集下层溶液得到离子液体B(1-烯丙基-3-甲基咪唑双(三氟甲基磺酰)亚胺盐)；
S3.将UIO-66-CH＝CH 2、离子液体B、高氯酸锂、偶氮二异丁腈置于研钵中充分研磨至无液体状态，将材料收集至玻璃瓶中加热至60℃保温24h，再将材料置于N 2氛围下加热至105℃反应24h得到孔内限域聚合有机单体的金属-有机框架基材料，并在85℃反应24h后，得到孔内限域聚合有机单体的金属-有机框架基材料(UIO-66-CH＝CH 2-IL)，其中所述UIO-66-CH＝CH 2、离子液体B、高氯酸锂、偶氮二异丁腈的摩尔比为1：5.7：13.5：0.7。
实施例2
本实施例的制备方法与实施例1相同，区别在于，将步骤S1的2-乙烯基对苯二甲酸替换为对苯二甲酸。
实施例3
本实施例的制备方法与实施例1相同，区别在于，将步骤S1的2-乙烯基对苯二甲酸替换为2-磺酸对苯二甲酸单钠盐。
实施例4
本实施例的制备方法与实施例1相同，区别在于，将步骤S1的金属有机框架材料的反应温度替换为150℃。
实施例5
本实施例的制备方法与实施例1相同，区别在于，将金属-有机框架材料、有机单体、锂盐、引发剂的摩尔比替换为1：1：0.1：0.1。
实施例6
本实施例的制备方法与实施例1相同，区别在于，将金属-有机框架材料、有机单体、锂盐、引发剂的摩尔比替换为1：8：50：5。
实施例7
本实施例的制备方法与实施例1相同，区别在于，将有机单体替换为碳酸乙烯亚乙酯。
对比例1
本对比例的金属-有机框架材料制备方法，包括如下步骤：
称取19.33g的八水合氯氧化锆和11.89g的2,5-二羟基对苯二甲酸在150mL的去离子水和150mL的醋酸混合溶液中搅拌均匀，后采用加热回流法将溶液置于95℃环境下恒温4h，待反应冷却后，用无水乙醇进行洗涤并离心，再进行真空干燥，制得金属-有机框架材料UIO-66-(OH) 2。
对比例2
本对比例的金属-有机框架材料的制备方法，包括如下步骤：
称取0.2g九水合硝酸锆和0.268g的2-磺酸对苯二甲酸单钠盐在3mL的去离子水中搅拌均匀，将溶液置于在25mL的反应釜中，采用水热法将反应釜置于190℃恒温24h，待反应冷却后，用无水乙醇进行洗涤并离心，再真空干燥，制得金属-有机框架材料MIL-101-SO 3H。
对比例3
本对比例的金属-有机框架材料的制备方法，包括如下步骤：
称取0.75g的氯化锆和2.4g的巯基琥珀酸在3mL的去离子水中搅拌均匀，将溶液置于在25mL的圆底烧瓶中，采用溶剂热回流，在138℃恒温15min，待反应冷却后，用无水乙醇进行洗涤并离心，再真空干燥，制得金属-有机框架材 料Zr-MOF-SH。
对比例4
本对比例的金属-有机框架材料的制备方法与实施例1的区别在于，直接将离子液体灌注到金属有机框架材料UIO-66-CH＝CH 2的孔道内，再向其中加入聚合物基体和锂盐，搅拌均匀，形成溶胶。
应用
将上述制得的金属-有机框架基材料作为全固态电解质膜在全固态锂金属电池中的应用，包括如下步骤：
称取0.4g的上述各实施例和对比例制得的金属-有机框架基材料、0.1g聚(偏二氟乙烯-co-六氟丙烯)与2mL的N-甲基吡咯烷酮，搅拌12小时，得到均匀的混合浆料；将混合浆料涂在聚四氟乙烯模具中，然后置于60℃的烘烤箱中干燥12小时，并去除残余有机溶剂；用镊子将薄膜从模具中撕下来得到柔性全固态膜。将柔性全固态膜浸润在双三氟甲磺酰亚胺锂的乙腈溶液(1mol/L)中，12小时后取出置于60℃的烘烤箱中干燥12小时，并去除残余有机溶剂，得到柔性全固态电解质膜。
将磷酸铁锂、聚偏氟乙烯和导电剂按照质量比为8：1：1溶解在N-甲基吡咯烷酮溶剂中，其中磷酸铁锂与N-甲基吡咯烷酮质量比为1：4.4，磁力搅拌12h，使用刮刀将其涂敷在铝箔的表面。在60℃烘箱中干燥8h，裁成直径为12mm的圆片备用。将柔性全固态电解质膜浸泡在60℃下的SN 20-LITFSI，用无尘纸将膜擦干。其中SN 20-LITFSI为丁二腈与双三氟甲磺酰亚胺锂按照摩尔比为20:1的溶液。在手套箱中，按照正极壳、正极、电解质、负极、垫片、弹片、负极壳的顺序组装为成2032型磷酸铁锂/锂扣式电池。
性能测试
1、测试方法
(1)将实施例1制备的UIO-66-CH＝CH 2，使用SU8010-日立新型高分辨场发射扫描电镜进行微观形貌测试。
(2)将实施例1制得的孔内限域聚合有机单体的金属-有机框架基材料，使用理学Rigaku Smartlab 9kW进行X-射线衍射测试。
(3)将制得的全固态锂金属电池在新威测试柜中分别进行倍率性能测试和循环 性能测试。倍率性能测试是依次在0.5C、1C、2C、5C、0.2C的倍率(1C＝170mAh/g)下充放电进行。循环性能测试是在1C倍率(1C＝170mAh/g)下恒流充放电进行。
2、测试结果
图1的数据表明，实施例1中得到的UIO-66-CH＝CH 2结晶性好，且有机单体在孔内限域聚合后得到的UIO-66-CH＝CH 2-IL，未破坏金属-有机框架基材料的结构，有利于金属离子在晶体内的传导。实施例2～4中合成的材料都表现出较好的结晶性。
图2的结果表明，实施例1中得到的UIO-66-CH＝CH 2-IL结构均一，尺寸较小，有利于优化金属离子在晶体界面之间的传导，界面阻抗低，且金属-有机框架材料在发生有机单体孔内原位限域聚合后，形貌和结构保存完整。
图3的数据经过拟合并套用离子电导率计算公式σ＝L/(R×S)可得，在300K下离子电导率达到3.2mS/cm，以上结果表明，实施例1制备的孔内限域聚合有机单体的金属-有机框架基材料在300K下具有高的离子电导率。
图4的数据表明，实施例1制备的柔性全固态电解质膜具有4.95V宽的电化学窗口，具有优异的电化学稳定性，使之能够应用于高电压电池体系中。
图5的数据表明，在0.5C、1C、2C、5C和0.2C的倍率下放电比容量可达到152mAh/g、150mAh/g、140mAh/g、118mAh/g和160mAh/g，可见其容量高，显示出了实施例1的产品组装得到的全固态锂金属电池具备优异的倍率性能，充放电比容量以及倍率性能都明显优于基于对比例1中金属-有机框架材料的全固态锂金属电池。
图6的数据表明，基于实施例1的产物制得的全固态电解质的全固态锂金属电池在1C的倍率时充放电，在1C高倍率下循环500圈后的容量可达140mAh/g，证明其循环稳定性良好，电池高倍率下容量高且衰减慢，循环稳定性明显优于基于对比例1中金属-有机框架材料的全固态锂金属电池，安全性能高，具有宽电化学窗口，电池使用寿命长。
对比例2、对比例3制得的金属有机框架材料MIL-101-SO 3H及Zr-MOF-SH在300K下并没有实施例1如此高的离子电导率；对比例4得到的离子液体灌注金属有机框架的材料属于半全固态形式，在高压下存在漏液的情况。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明 的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (10)

  1. 一种孔内限域聚合有机单体的金属-有机框架基材料的制备方法，其特征在于，包括如下步骤：
    将金属-有机框架材料、有机单体、锂盐、引发剂混合研磨，并在85～95℃反应20～24h后，得到孔内限域聚合有机单体的金属-有机框架基材料，其中所述金属-有机框架材料、有机单体、锂盐、引发剂的摩尔比为1：1～8：0.1～50：0.1～5，所述有机单体为含碳碳双键的离子液体和/或含碳碳双键的有机小分子。
  2. 根据权利要求1所述制备方法，其特征在于，所述金属-有机框架材料、有机单体、锂盐、引发剂的摩尔比为1：1～6：1～20：0.1～1。
  3. 根据权利要求1所述制备方法，其特征在于，所述含碳碳双键的离子液体为1-烯丙基-3-甲基咪唑盐、1-乙烯基-3-乙基咪唑盐、1-乙烯基-3-丁基咪唑双盐、1-乙烯基-3-己基咪唑盐、1-烯丙基-3-乙烯基咪唑盐中的一种或几种。
  4. 根据权利要求1所述制备方法，其特征在于，所述含碳碳双键的有机小分子为碳酸乙烯亚乙酯、碳酸亚乙烯酯、2-氰基丙烯酸乙酯、α-氰基丙烯酸乙酯、丙烯酸、丙烯腈中的一种或几种。
  5. 根据权利要求1所述制备方法，其特征在于，所述金属-有机框架材料由金属盐和有机配体通过配位自组装制得，其中金属盐和有机配体的摩尔比为1：0.5～3。
  6. 根据权利要求5所述制备方法，其特征在于，所述金属盐为无水氯化锆、六水氯化铁、九水硝酸铬、六水氯化铝、八水合氯氧化锆、硝酸铈铵、钛酸异丙酯、三水硝酸铜、六水硝酸锌中的一种或几种。
  7. 根据权利要求5所述制备方法，其特征在于，所述有机配体为2-乙烯基对苯二甲酸、对苯二甲酸、2-磺酸对苯二甲酸单钠盐、对巯基对苯二甲酸、2,5-二羟基对苯二甲酸、2-羟基对苯二甲酸、2-氨基对苯二甲酸、2-甲基-1,4-苯二甲酸、2,2'-联吡啶-5,5'-二羧酸、1,4-萘二甲酸、均苯三甲酸、4,4-偶氮吡啶、1,2-二(4-吡啶基)乙烯、中-四(4-羧基苯基)卟吩、5,10,15,20-四(4-氨基苯基)卟啉、四(4-氟苯基)卟啉、咪唑苯基卟啉中的一种或几种。
  8. 权利要求1～7任一项所述制备方法制得的孔内限域聚合有机单体的金属-有机框架基材料。
  9. 权利要求8所述孔内限域聚合有机单体的金属-有机框架基材料在制备全固态锂电池的应用。
  10. 权利要求8所述孔内限域聚合有机单体的金属-有机框架基材料在作为全固态锂电池的全固态电解质的应用。
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