CN117013058A - Solid electrolyte based on metal-organic framework, and preparation method and application thereof - Google Patents

Solid electrolyte based on metal-organic framework, and preparation method and application thereof Download PDF

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CN117013058A
CN117013058A CN202311265662.7A CN202311265662A CN117013058A CN 117013058 A CN117013058 A CN 117013058A CN 202311265662 A CN202311265662 A CN 202311265662A CN 117013058 A CN117013058 A CN 117013058A
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organic framework
solid electrolyte
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CN117013058B (en
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谢玉峰
李迪雄
张琪
黄少铭
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Guangdong University of Technology
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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
    • 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
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • 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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Abstract

The invention discloses a solid electrolyte based on a metal-organic framework, a preparation method and application thereof, belonging to the technical field of lithium battery materials, wherein the preparation method comprises the following steps: modifying amino groups on a metal-organic framework structure to obtain a product A, mixing the product A with a polymer precursor and an initiator, carrying out oil bath heating reaction to obtain a product B after the reaction is finished, soaking the product B in a mixed solution of an organic solvent and lithium salt, and carrying out suction filtration and drying to obtain the solid electrolyte based on the metal-organic framework, wherein the preparation method provided by the invention is suitable for various NH-containing batteries 2 The MOFs material with functional groups has a simple and easy preparation method, and the prepared MOFs-based composite solid electrolyte material has a three-dimensional structure, obviously reduces specific surface area, constructs a high-density ion-conducting network in holes, and has the advantages ofThe electrochemical cell has the characteristics of high conductivity and wide electrochemical window, and shows higher specific capacity and good rate capability.

Description

Solid electrolyte based on metal-organic framework, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium battery materials, and particularly relates to a solid electrolyte based on a metal-organic framework, and a preparation method and application thereof.
Background
Secondary batteries, typified by lithium ion batteries, are becoming the first choice for new energy batteries due to their advantages such as high energy density and stable discharge cycles. However, lithium ion batteries still face significant challenges, with potential safety hazards and cycle degradation problems being the biggest two. In lithium ion batteries, the use of a metal anode will inevitably accelerate the formation of Li dendrites, which may puncture the separator during the battery cycle, eventually leading to a short circuit. More seriously, if the electrolyte is a flammable liquid, leakage and overheating may occur in the battery, resulting in a catastrophic fire. In order to alleviate the problems, the battery components are optimally selected and improved, and the solid electrolyte is adopted to replace the traditional liquid electrolyte, so that the method is important to preparing the metal anode battery with higher safety and better electrochemical performance.
Metal-organic framework materials (Metal-organic frameworks, MOFs) are a class of porous crystalline inorganic organic materials assembled from Metal ions/clusters and organic ligands. Is recognized as an excellent platform for designing various functional materials through host-guest chemistry or reaction transformation, and is widely studied in the fields of gas adsorption, drug delivery, catalysis, energy storage, and the like. In recent years, the application of MOFs in the field of solid-state electrolytes has become a new research hot spot, wherein MOFs composite polymers consist of metal salts, a polymer matrix, MOFs and liquid plasticizers, and the addition of MOFs can effectively increase the dissociation of the metal salts and the segment mobility of the polymers, and the enhanced mobile ions and migration paths help to improve the ionic conductivity. However, since the ionic conductivity of a polymer depends on its segment mobility, how to reduce the degree of polymerization is critical to enhance mobile ion and migration.
In order to solve the above problems, the prior art CN202210992319.1 discloses a method for preparing solid electrolyte by compounding MOFs with PEO, which comprises blending MOFs as polymer filler with polyethylene oxide (PEO) to reduce the polymerization degree of the polymer, but the MOFs-based solid electrolyte material prepared by the above prior art method has low conductivity and migrationThe number is low, the electrochemical window is narrow, so that the charge and discharge performance of MOFs solid electrolyte material is not ideal, and the rate performance of the MOFs solid electrolyte material still cannot meet the use requirements in certain cases. For example, chinese patent 202210344962.3 discloses a method for preparing PEO-MOF composite solid electrolyte based on 3D printing, wherein the conductivity of the PEO-MOF composite solid electrolyte is 10 at room temperature -6 S/cm; as another example, chinese patent 202210281595.7 discloses a solid electrolyte based on MOF-based ionic conductor, and preparation method and application thereof, wherein the room temperature conductivity is only 2×10 -4 S/cm; as well as a preparation method and application thereof, as disclosed in Chinese patent 202111682358.3, the conductivity of the polyurethane solid electrolyte is still less than 10 -4 S/cm。
Disclosure of Invention
In order to solve the technical problems, the invention provides a metal-organic framework (MOFs) based solid electrolyte, a preparation method and application thereof.
To achieve the above object, the present invention provides a method for preparing a metal-organic framework-based solid electrolyte, comprising reacting amino groups (-NH) on metal-organic frameworks (MOFs) structure 2 ) Carrying out modification to obtain a product A, mixing the product A with a polymer precursor and an initiator, carrying out oil bath heating reaction to obtain a product B after the reaction is finished, soaking the product B in a mixed solution of an organic solvent and lithium salt, carrying out suction filtration, and drying to obtain a solid electrolyte based on a metal-organic framework;
the polymer precursor is sodium vinylsulfonate, alpha-sodium alkenylsulfonate or sodium propenyl sulfonate, preferably sodium vinylsulfonate, and has the function of carrying out free radical polymerization with double bonds on the modified MOFs material, and each monomer can carry sulfonic acid groups after polymerization, so that lithium ion conduction can be promoted more quickly.
Further, the method for modifying amino groups of the metal-organic framework is as follows: adding the metal-organic framework into a mixed solvent of an organic solvent and anhydride, standing, centrifuging and drying after the reaction is completed.
Firstly, adding MOFs material into a mixed solvent of anhydride and an organic solvent, soaking for a period of time, and then adding a polymer precursor and a thermal initiator to enable the inside of a hole to undergo domain-limited polymerization; and then soaking the prepared particles in a mixed solution of an organic solvent and lithium salt to exchange sodium ions inside, thereby preparing the MOFs-based solid electrolyte. The preparation method provided by the invention is suitable for various NH-containing products 2 The MOFs material of the ligand is simple and easy to operate in preparation method, the prepared MOFs-based composite solid electrolyte material has a three-dimensional structure, the specific surface area is obviously reduced, a high-density ion conducting network is constructed in the hole, and the MOFs material has the characteristics of high conductivity and wide electrochemical window, and shows higher specific capacity and good rate capability.
In order to solve the problems of low ionic conductivity, narrow electrochemical window and relatively low charge-discharge performance of the existing MOFs solid-state electrolyte material and limit popularization and application of the MOFs solid-state electrolyte material, the invention provides a preparation method of a metal-organic framework-based solid-state electrolyte, wherein in the preparation method, anhydride is adopted to carry out preparation on-NH in the MOFs material 2 Modifying to obtain MOF-NH-M (M is anhydride), and then carrying out free radical polymerization substitution in the hole with the polymer precursor to obtain MOF-NH-M-SO 3 Li, the size of the particles is 100-200 nm. The method can obtain the three-dimensional solid electrolyte material with high conductive ion density, thereby remarkably improving the conductivity and the charge-discharge performance of the MOFs solid electrolyte material.
Further, the volume ratio of the organic solvent to the anhydride is 40:1.
Further, the organic solvent comprises dichloromethane, acetonitrile, methanol, ethanol, acetone or tetrahydrofuran, and the solvents are polar solvents capable of dissolving anhydride;
the anhydride is acrylic anhydride or methacrylic anhydride, preferably methacrylic anhydride, which can undergo an amide reaction with an amino group, thereby providing a double bond on the ligands of the MOFs material for subsequent polymerization.
Further, the metal-organic framework comprises UiO-66-NH 2 、UiO-67-NH 2 、UiO-68-NH 2 、MiL-101(Cr)-NH 2 、MOF-5-NH 2 、MiL-125(Ti)-NH 2 Or MiL-68 (In) -NH 2 。
Further, the metal-organic framework is UiO-66-NH 2 。
Further, the initiator is added in an amount of 2wt% based on the total mass of the material (referring to the total mass of the modified MOFs material and the polymer precursor), and the initiator is a thermal initiator including Azobisisobutyronitrile (AIBN), azobisisoheptonitrile, dimethyl azobisisobutyrate, preferably azobisisobutyronitrile.
Further, the preparation method of the solid electrolyte based on the metal-organic framework specifically comprises the following steps:
(1) Adding dried MOFs into a mixed solvent of an organic solvent and anhydride, sealing in a centrifuge tube, storing at 30 ℃ for 100 h, centrifugally cleaning the generated solid by the organic solvent, and drying at 80 ℃ under vacuum for 12 h to obtain modified MOF-NH-M (M is anhydride);
(2) Adding 100mg of polymer precursor and thermal initiator into each 100mg of MOF-NH-M, continuously grinding to uniformly fill the pores of the MOF-NH-M with the polymer precursor, preserving 2 h under vacuum, placing into a vacuum drying oven (60 ℃) and then heating and reacting 3 h in an oil bath at 80 ℃ to fully react and polymerize to obtain the MOF-NH-M-SO 3 Na material, dried in vacuum at 100deg.C;
(3) To obtain the MOF-NH-M-SO 3 The Na ions in the Na material are completely replaced by lithium ions, and MOF-NH-M-SO is added into acetonitrile 3 Na material and lithium salt are fully contacted with 24 h in a shaking table, and finally the final product is collected by suction filtration with an organic solvent (preferably acetonitrile), and vacuum dried (100 ℃,12 h) to obtain the MOF-NH-M-SO 3 Li。
Further, MOF-NH-M-SO 3 Mass ratio of Na material to lithium saltAt a ratio of 1:2, MOF-NH-M-SO 3 Na in the Na material is fully replaced with Li.
Further, the lithium salt is selected from lithium bis (trifluoromethanesulfonyl) imide (LITFSI), lithium bis (fluorosulfonyl) imide (LIFSI), lithium hydroxide (LiOH), lithium hexafluorophosphate (LiPF) 3 ) Lithium difluorooxalato borate (LiDFOB) and lithium difluorophosphate (LiPO) 2 F 2 ) One of them.
A metal-organic framework-based solid electrolyte prepared according to the above-described preparation method.
The solid electrolyte based on the metal-organic framework is applied to the field of solid batteries.
Further, the metal-organic framework-based solid electrolyte may be used to prepare a solid electrolyte membrane of a lithium metal solid state battery by the following method:
the solid electrolyte based on the metal-organic framework was mixed with 2wt% of a crosslinking agent (i.e., the crosslinking agent accounts for 2wt% of the solid electrolyte based on the metal-organic framework), pressed into a film by a grinding roll, and dried to obtain a solid electrolyte membrane.
Further, the cross-linking agent is Polytetrafluoroethylene (PTFE).
Compared with the prior art, the invention has the following advantages and technical effects:
(1) The solid electrolyte based on MOFs has a three-dimensional framework structure formed by polymerizing modified MOFs and polymer precursors, the polymerization degree of the polymer is reduced through the nano microporous property of the MOFs, the ion-conducting property of the material is obviously improved, and in addition, the rich sulfonic acid groups on the modified MOFs can greatly promote ion conduction, namely Li is promoted through coulomb interaction + While limiting anions. The invention builds the ion conducting network in MOFs pore canal, so that the MOFs-based solid electrolyte material has high ion conductivity and good multiplying power performance.
(2) The solid electrolyte based on MOFs has a three-dimensional stable framework of MOFs, so that the overall electrochemical property can be improved, the electrochemical window of the electrolyte is improved, and the cycle performance and the stability of the performance of the MOFs-based solid electrolyte material are improved.
(3) The preparation method of the solid electrolyte based on MOFs is simple and convenient to operate and suitable for large-scale production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 shows the product UiO-66-NH-M-SO obtained in example 1 of the present invention 3 Li, uiO-66-NH-M and UiO-66-NH 2 X-ray diffraction pattern of (2);
FIG. 2 shows the product UiO-66-NH-M-SO obtained in example 1 of the present invention 3 Scanning electron microscope pictures of Li;
FIG. 3 shows the product UiO-66-NH-M-SO obtained in example 1 of the present invention 3 Li, uiO-66-NH-M and UiO-66-NH 2 Nitrogen adsorption and desorption graph of (2);
FIG. 4 shows the product UiO-66-NH-M-SO obtained in example 1 of the present invention 3 Lithium ion conductivity diagram of Li;
FIG. 5 shows the product UiO-66-NH-M-SO obtained in example 1 of the present invention 3 Electrochemical window plot of Li;
FIG. 6 shows the product UiO-66-NH-M-SO obtained in example 1 of the present invention 3 A lithium ion migration number map of Li;
FIG. 7 shows the UiO-66-NH-M-SO obtained in example 1 of the present invention 3 Li is a graph of the rate performance of a half cell for lithium sheets.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
In the present invention, the term "half cell" refers to a cell in which metallic lithium is used as a negative electrode.
Example 1
Drying UiO-66-NH 2 (300 mg) was mixed with methacrylic anhydride (300. Mu.L) in dichloromethane (12 mL) and then sealed in a centrifuge tube and stored at 30℃for 100 h. The resulting solid was washed 2 times with dichloromethane and then dried under vacuum at 80 ℃ for 12 h to obtain modified MOFs material (UiO-66-NH-M). Adding 100mg sodium vinylsulfonate and 4mg AIBN into each 100mg UiO-66-NH-M, uniformly filling the pores with sodium vinylsulfonate by continuous grinding, preserving under vacuum for 2 h, and then placing under vacuumHeating 2 h in a drying oven (60 ℃) at 80 ℃ in an oil bath to react 3 h, and fully reacting and polymerizing to finally obtain the UiO-66-NH-M-SO 3 Na material was dried in vacuo at 100 ℃.
To completely replace sodium ions in MOFs obtained in the previous step with lithium ions, 1000mg of UiO-66-NH-M-SO was added to 9mL acetonitrile 3 Na and 2 g bis-trifluoromethanesulfonyl imide lithium were fully contacted 24 h in the shaker. Finally, the final product is collected by acetonitrile suction filtration and dried in vacuum (100 ℃ C., 12, h) to obtain the UiO-66-NH-M-SO 3 Li. The solid electrolyte material prepared in this example was subjected to bulk conductivity testing: MOFs powder was pressed into wafers with a diameter of 8 mm using a pressure die at a pressure of 3-4 MPa, and an Electrochemical Impedance Spectroscopy (EIS) test was performed on an electrochemical workstation (Autolab 302N) with a two-sided stainless steel sheet combined symmetric cell (SS|SEs|SS). The frequency range at the time of test is set to be 1 multiplied by 10 6 0.1 to Hz. The conductivity was calculated as:
σ=L/(R×S)
wherein σ is the conductivity (S/cm) of the film; l is the thickness (cm) of the film; s is the area (cm) of the electrolyte sheet 2 ) The method comprises the steps of carrying out a first treatment on the surface of the R is the impedance value (omega) obtained by the test.
UiO-66-NH-M-SO 3 Li and PTFE are mixed according to the mass ratio of 98:2, pressed into a film by a grinding roller, and subjected to an electrochemical window test, a subsequent lithium ion migration number test and a half-cell performance test.
Electrochemical window test: the lithium sheet is used as a negative electrode, the stainless steel sheet is used as a positive electrode, and the CR2032 battery is assembled with an electrolyte membrane, and an electrochemical workstation is used similarly, and the scanning rate is set to be 1 mV s -1 The electrochemical stability window of the electrolyte membrane was tested by the linear sweep voltage method (LSV), from open circuit voltage to 6V.
Lithium ion migration number (t) Li+ ) Calculated from the following formula, which contains DeltaV (DC polarization voltage, 10 mV), I 0 And I s (initial current and steady current during polarization), R 0 And R is s (impedance before and after polarization). The calculation includes the thickness (L) of the membrane in centimeters (cm), the electrolyte area (S) in square centimeters(cm 2 ) Volume resistance (R) in ohms (Ω).
And (3) a positive electrode: liFePO is prepared 4 Uniformly mixing powder, super-conductive carbon black (Super-P) and polyvinylidene fluoride (PVDF) in an N-methyl pyrrolidone solvent according to a mass ratio of 8:1:1, then scraping the mixture on an aluminum foil by using a scraper, and cutting the dried pole piece into uniform round pole pieces (diameter 12 and mm) by using a slicer.
And assembling the anode, the electrolyte, the metal lithium sheet, the gasket and the shrapnel into the CR2032 battery.
FIG. 1 shows the product obtained in example 1 UiO-66-NH-M-SO 3 Li, uiO-66-NH-M and UiO-66-NH 2 All of the X-ray powder diffraction peaks were aligned with UiO-66-NH 2 It can be seen that the crystal structure is not destroyed.
FIG. 2 shows the product obtained in example 1 UiO-66-NH-M-SO 3 From the scanning electron microscope photograph of Li, it can be seen that the MOFs material modified in example 1 has a complete three-dimensional skeleton structure, the structure is not destroyed compared with that before modification, and the particle size is 100-200 nm, which indicates that polymerization in the pores is achieved.
FIG. 3 shows the product obtained in example 1 UiO-66-NH-M-SO 3 Li, uiO-66-NH-M and UiO-66-NH 2 Is a nitrogen adsorption and desorption curve chart of UiO-66-NH 2 Is 606.53 m in specific surface area 2 Specific surface area of UiO-66-NH-M per gram is 547.09M 2 Per g, uiO-66-NH-M-SO 3 The Li holes are occupied by the polymerized ion conducting network, and the specific surface area is reduced to 22.57 and 22.57 m 2 And/g, the specific surface area is obviously reduced, and the construction of the ion-conducting network is indirectly indicated.
FIG. 4 shows the product obtained in example 1 UiO-66-NH-M-SO 3 Li ion conductivity diagram, found to have higher ion conductivity of 6.8X10 -4 S/cm（25℃）。
FIG. 5 shows the product obtained in example 1 UiO-66-NH-M-SO 3 Electrochemical window diagram of Li, found to have higherElectrochemical window, up to 4.8V.
FIG. 6 shows the product obtained in example 1 UiO-66-NH-M-SO 3 The lithium ion migration number diagram of Li is found to have a higher ion migration number, reaching 0.68.
FIG. 7 shows the product obtained in example 1 UiO-66-NH-M-SO 3 The ratio performance of Li to lithium sheet as half cell is shown to be 132 mAh/g at 0.5C, and 84 mAh/g at 5C, which shows excellent ratio performance.
The above results demonstrate that the solid electrolyte of the present invention can obtain higher specific capacity, stable cycle performance and excellent rate performance.
Example 2
Accurately weighing 300mg of MiL-101 (Cr) -NH 2 Mixed with methacrylic anhydride (300 μl) dissolved in dichloromethane (12 mL) and then sealed in a centrifuge tube and stored at 30 ℃ for 100 h. The resulting solid was washed 2 times with dichloromethane and then dried under vacuum at 80 ℃ for 12 h to obtain a modified MOFs material (MiL-101 (Cr) -NH-M). 100mg of sodium vinylsulfonate and 4mg of AIBN were added to 100mg of MiL-101 (Cr) -NH-M, the pores were uniformly filled with sodium vinylsulfonate by grinding, followed by placing in a vacuum oven (60 ℃ C.) for 2 h, and oil-bath heating reaction at 80 ℃ for 3 h, and sufficient reaction polymerization was carried out. Finally, the MOFs material was removed and dried in vacuo at 100deg.C. To completely replace sodium ions in the MOFs material obtained in the previous step with lithium ions, 1000mg of MOFs material and 2 g lithium hydroxide were added to 9mL acetonitrile and contacted thoroughly in a shaker 24 h. Finally, the final product is collected by acetonitrile suction filtration and dried in vacuum (100 ℃ C., 12, h) to obtain MiL-101 (Cr) -NH-M-SO 3 Li. The solid electrolyte material MiL-101 (Cr) -NH-M-SO prepared in this example 3 Li and PTFE are mixed according to the mass ratio of 98:2, pressed into a film by a grinding roller (the same applies to the film forming method), and then the lithium sheet is subjected to electrochemical performance test of a half cell, so that the lithium sheet has higher specific capacity, stable cycle performance and excellent rate capability.
The product obtained in this example has an X-ray powder diffraction peak-to-average ratio of MiL-101 (Cr) -NH 2 Is not destroyed in crystal structure, and has after modificationHas a complete three-dimensional skeleton structure, has no damage to the structure compared with the structure before modification, has a particle size of 200 nm and an ion conductivity of 5.6X10 -4 The electrochemical window is 4.5V, the migration number is 0.61, the migration number is 130mAh/g at 0.5C, and the migration rate is 82 mAh/g at 5C, so that the excellent rate performance is shown.
Example 3
200mg of MiL-125 (Ti) -NH was accurately weighed 2 Mix with methacrylic anhydride (200 μl) dissolved in methanol (8 mL) and then seal in centrifuge tubes and store 80 h at 30 ℃. The resulting solid was washed 2 times with methanol by centrifugation and then dried under vacuum at 80℃for 12 h to obtain a modified MOFs material (MiL-125 (Ti) -NH-M). 100mg of sodium vinylsulfonate and 4mg azodiisoheptonitrile were added to 100mg of MiL-125 (Ti) -NH-M, the pores were uniformly filled with sodium vinylsulfonate by grinding, followed by placing in a vacuum oven (60 ℃ C.) for 2 h, and oil-bath heating reaction at 80 ℃ for 3 h, and sufficient reaction polymerization was carried out. Finally, the MOFs material was removed and dried in vacuo at 100deg.C. To completely replace sodium ions in the MOFs material obtained in the previous step with lithium ions, 1000mg of MOFs material and 2000 mg lithium bis-fluorosulfonyl imide were added to 9mL of acetonitrile and contacted well in a shaker 24 h. Finally, the final product is collected by acetonitrile suction filtration and dried in vacuum (100 ℃ C., 12, h) to obtain MiL-125 (Ti) -NH-M-SO 3 Li. The solid electrolyte material MiL-125 (Ti) -NH-M-SO prepared in this example 3 Li and PTFE are mixed according to the mass ratio of 98:2 to prepare a film, and then the lithium sheet is subjected to electrochemical performance test of a half battery, so that higher specific capacity, stable cycle performance and excellent multiplying power performance can be obtained.
The product obtained in this example has an X-ray powder diffraction peak-to-average ratio of MiL-125 (Ti) -NH 2 The crystal structure was not destroyed, the modified product had a complete three-dimensional skeleton structure, the structure was not destroyed as compared with the structure before modification, the particle size was 250 nm, and the ionic conductivity was 5.1X10 -4 S/cm, electrochemical window is 4.6V, 138 mAh/g at 0.5C, migration number is 0.52, and 83 mAh/g still at 5C, which shows excellent rate capability.
Example 4
200mg of UiO-67-N was accurately weighedH 2 Mix with methacrylic anhydride (200 μl) dissolved in ethanol (8 mL) and then seal in centrifuge tubes and store 100 h at 30 ℃. The resulting solid was washed by centrifugation with ethanol 2 times and then dried under vacuum at 80℃for 12 h to obtain a modified MOFs material (UiO-67-NH-M). 100mg of sodium vinylsulfonate and 4mg of dimethyl azodiisobutyrate were added to 100mg of UiO-67-NH-M, the pores were uniformly filled with sodium vinylsulfonate by grinding, followed by placing in a vacuum oven (60 ℃ C.) for 2 h, and oil-bath for 3 h at 80 ℃ C. For sufficient reaction polymerization. Finally, the MOFs material was removed and dried in vacuo at 100deg.C. To completely replace sodium ions in the MOFs material obtained in the previous step with lithium ions, 1000mg of MOF material and 2 g of lithium difluorophosphate were added to 9mL acetonitrile and contacted thoroughly in a shaker 24 h. Finally, the final product is collected by acetonitrile suction filtration and dried in vacuum (100 ℃ C., 12, h) to obtain the UiO-67-NH-M-SO 3 Li. The solid electrolyte material UiO-67-NH-M-SO prepared in this example 3 Li and PTFE are mixed according to the mass ratio of 98:2 to prepare a film, and then the lithium sheet is subjected to electrochemical performance test of a half battery, so that higher specific capacity, stable cycle performance and excellent multiplying power performance can be obtained.
The product obtained in this example has an X-ray powder diffraction peak-to-average ratio of UiO-67-NH 2 The crystal structure was not destroyed, the modified structure had a complete three-dimensional skeleton structure, the structure was not destroyed compared with the structure before modification, the particle size was 200 nm, and the ionic conductivity was 4.8X10 -4 The electrochemical window is 4.4V, the migration number is 0.53, 128 mAh/g is at 0.5C, and 79 mAh/g is still at 5C, so that the excellent rate capability is shown.
Example 5
200mg of MiL-68 (In) -NH was accurately weighed 2 Mix with methacrylic anhydride (200 μl) dissolved in acetone (8 mL) and then seal in centrifuge tubes and store 100 h at 30 ℃. The resulting solid was washed 2 times with acetone by centrifugation, and then dried under vacuum at 80℃for 12 h to obtain a modified MOFs material (MiL-68 (In) -NH-M). 100mgL of sodium vinylsulfonate and 4mg of AIBN were added to 100mg of MiL-68 (In) -NH-M, and the pores were uniformly filled with sodium vinylsulfonate by grinding, followed byThen the mixture was placed in a vacuum oven (60 ℃) for 2 h, and the mixture was heated in an oil bath at 80℃for 3 h, thereby allowing the mixture to undergo polymerization. Finally, the MOFs material was removed and dried in vacuo at 100deg.C. To completely replace sodium ions in the MOFs material obtained in the previous step with lithium ions, 1000mg of MOFs material and 2 g of lithium difluorooxalato borate were added to 9mL of methanol and contacted thoroughly in a shaking table 24 h. Finally, the final product is collected by suction filtration with methanol and dried In vacuum (100 ℃ C., 12, h) to obtain MiL-68 (In) -NH-M-SO 3 Li. The solid electrolyte material MiL-68 (In) -NH-M-SO prepared In this example 3 Li and PTFE are mixed according to the mass ratio of 98:2 to prepare a film, and then the lithium sheet is subjected to electrochemical performance test of a half battery, so that higher specific capacity, stable cycle performance and excellent multiplying power performance can be obtained.
The product obtained In this example has an X-ray powder diffraction peak-to-average ratio of MiL-68 (In) -NH 2 The crystal structure was not destroyed, the modified structure had a complete three-dimensional skeleton structure, the structure was not destroyed compared with the structure before modification, the particle size was 300 nm, and the ionic conductivity was 4.7X10 -4 The electrochemical window is 4.6V, the migration number is 0.48, the migration number is 126 mAh/g at 0.5C, and the migration number is 79 mAh/g still at 5C, so that the excellent rate performance is shown.
Example 6
Accurately weighing 200mg of MOF-5-NH 2 Mix with methacrylic anhydride (200 μl) dissolved in tetrahydrofuran (8 mL) and then seal in centrifuge tubes and store 100 h at 30 ℃. The resulting solid was washed 2 times with acetone by centrifugation, and then dried under vacuum at 80℃for 12 h to obtain a modified MOFs material (MOF-5-NH-M). 100mg of sodium propenyl sulfonate and 4mg of AIBN are added to each 100mg of MOF-5-NH-M, the pores are uniformly filled with sodium propenyl sulfonate by grinding, then the mixture is placed in a vacuum drying oven (70 ℃) for 2 h, and oil bath heating reaction is carried out for 2 h at 85 ℃ for full reaction polymerization. Finally, the MOFs material was removed and dried in vacuo at 100deg.C. To completely replace sodium ions in the MOFs obtained in the previous step with lithium ions, 1000mg of MOFs material and 2 g lithium hexafluorophosphate were added to 9mL tetrahydrofuran and contacted thoroughly in a shaker 24 h. Finally, the final product was collected by suction filtration using tetrahydrofuran and dried in vacuo (100 ℃,12 DEG Ch) Obtaining the MOF-5-NH-M-SO 3 Li. The solid electrolyte material MOF-5-NH-M-SO prepared in this example 3 Li and PTFE are mixed according to the mass ratio of 98:2 to prepare a film, and then the lithium sheet is subjected to electrochemical performance test of a half battery, so that higher specific capacity, stable cycle performance and excellent multiplying power performance can be obtained.
The product obtained in this example has an X-ray powder diffraction peak-to-average and MOF-5-NH 2 The crystal structure was not destroyed, the modified structure had a complete three-dimensional skeleton structure, the structure was not destroyed compared with the structure before modification, the particle size was 300 nm, and the ionic conductivity was 5.7X10 -4 The electrochemical window is 4.7V, the migration number is 0.47, the migration number is 130mAh/g at 0.5C, and the migration rate is 81 mAh/g at 5C, so that the excellent rate capability is shown.
Example 7
200mg of UiO-68-NH was accurately weighed 2 This was mixed with acrylic anhydride (200 μl) dissolved in tetrahydrofuran (8 mL), then sealed in a centrifuge tube and stored at 30 ℃ for 100 h. The resulting solid was washed 2 times with tetrahydrofuran, and then dried under vacuum at 80℃for 12 h to obtain a modified MOFs material (UiO-68-NH-M). 100mg of sodium alpha-alkenyl sulfonate and 4mg of AIBN are added to 100mg of UiO-68-NH-M, the holes are uniformly filled with the sodium alpha-alkenyl sulfonate by grinding, then the holes are placed in a vacuum drying oven (70 ℃) for 2 h, oil bath heating reaction is carried out at 85 ℃ for 2 h, and full reaction polymerization is carried out. Finally, the MOFs material was removed and dried in vacuo at 100deg.C. To completely replace sodium ions in the MOFs material obtained in the previous step with lithium ions, 1000mg of MOFs material and 2 g bis (trifluoromethanesulfonyl) imide lithium were added to 9mL tetrahydrofuran and contacted thoroughly in a shaker at 24 h. Finally, the final product is collected by suction filtration with tetrahydrofuran and dried in vacuum (100 ℃ C., 12, h) to obtain UiO-68-NH-M-SO 3 Li. The solid electrolyte material UiO-68-NH-M-SO prepared in this example 3 Li and PTFE are mixed according to the mass ratio of 98:2 to prepare a film, and then electrochemical performance tests of half batteries are carried out on lithium sheets, so that higher specific capacity, stable cycle performance and excellent rate capability can be obtained.
X-ray powder diffraction of the product obtained in this examplePeak average and UiO-68-NH 2 The crystal structure was not destroyed, the modified structure had a complete three-dimensional skeleton structure, the structure was not destroyed compared with the structure before modification, the particle size was 200 nm, and the ionic conductivity was 2.5X10 -4 The electrochemical window is 4.6V, the migration number is 0.55, the migration number is 124 mAh/g at 0.5C, and the migration rate is 75 mAh/g even at 5C, so that the excellent rate performance is shown.
Comparative example 1
The procedure is as in example 1, except that methacrylic anhydride is not added.
The product of this comparative example had a particle size of 200 nm and an ionic conductivity of 1.2X10 -5 The electrochemical window was 4.2V at S/cm, and the rate performance cell had 130mAh/g at 0.2C, which subsequently decreased to 0, because fewer oligomers were formed and were not immobilized within the MOF channels, resulting in slower lithium ion migration.
Comparative example 2
The only difference from example 1 is that no sodium vinylsulfonate was added.
The comparative example cannot successfully prepare a solid electrolyte with high conductivity ions, because polymerization is not generated in MOF pore channels, lithium ions cannot be conducted, and in example 1, sodium vinylsulfonate is added to generate a large amount of sulfonate ions in the pores to form-SO 3 Li can not be crosslinked and polymerized without adding sodium vinylsulfonate, so that sulfonate ions are fixed, and lithium ions are directionally conducted.
In conclusion, the method provided by the invention is suitable for preparing various MOFs porous materials with amino groups, the preparation method is simple and feasible, and the prepared product has higher ionic conductivity and higher electrochemical window. Experimental results show that the solid electrolyte based on the metal-organic framework has good battery performance and wide application prospect in the field of solid electrolytes.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims (9)

1. The preparation method of the solid electrolyte based on the metal-organic framework is characterized by comprising the steps of modifying amino groups on the metal-organic framework structure to obtain a product A, mixing the product A with a polymer precursor and an initiator, carrying out oil bath heating reaction to obtain a product B after the reaction is finished, soaking the product B in a mixed solution of an organic solvent and lithium salt, carrying out suction filtration, and drying to obtain the solid electrolyte based on the metal-organic framework;
the polymer precursor is sodium vinyl sulfonate, alpha-sodium alkenyl sulfonate or sodium propenyl sulfonate.
2. The method for preparing a metal-organic framework-based solid electrolyte according to claim 1, wherein the method for modifying amino groups of a metal-organic framework is as follows: adding the metal-organic framework into a mixed solvent of an organic solvent and anhydride, standing, centrifuging and drying after the reaction is completed.
3. The method for preparing a metal-organic framework based solid electrolyte according to claim 2, wherein the volume ratio of the organic solvent to the acid anhydride is 40:1.
4. The method for preparing a metal-organic framework-based solid electrolyte according to claim 3, wherein the organic solvent comprises dichloromethane, acetonitrile, methanol, ethanol, acetone or tetrahydrofuran;
the anhydride is acrylic anhydride or methacrylic anhydride.
5. The method for preparing a metal-organic framework-based solid electrolyte according to claim 2, wherein the metal-organic framework comprises UiO-66-NH 2 、UiO-67-NH 2 、UiO-68-NH 2 、MiL-101(Cr)-NH 2 、MOF-5-NH 2 、MiL-125(Ti)-NH 2 Or MiL-68(In)-NH 2 。
6. The method for producing a metal-organic framework-based solid electrolyte according to claim 5, wherein the metal-organic framework is UiO-66-NH 2 。
7. The method for preparing a metal-organic framework based solid electrolyte according to claim 1, wherein the initiator is added in an amount of 2wt% of the total mass of the material.
8. A metal-organic framework based solid electrolyte, characterized in that it is prepared according to the preparation method of any one of claims 1-7.
9. Use of the metal-organic framework based solid state electrolyte according to claim 8 in the field of solid state batteries.
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