CN111320761B - Metal organic framework nano composite material and preparation method and application thereof - Google Patents

Metal organic framework nano composite material and preparation method and application thereof Download PDF

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CN111320761B
CN111320761B CN202010147621.8A CN202010147621A CN111320761B CN 111320761 B CN111320761 B CN 111320761B CN 202010147621 A CN202010147621 A CN 202010147621A CN 111320761 B CN111320761 B CN 111320761B
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organic framework
metal organic
polypyrrole
terephthalic acid
metal
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CN111320761A (en
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李奇
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Nantong University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

Abstract

The invention relates to the field of nano materials, and discloses a metal organic framework nano composite material, and a preparation method and application thereof. The metal organic framework nano composite material has the advantages of light weight, strong chemical polarity, good thermodynamic stability and corrosion resistance, shows porous characteristic, has high specific surface area and porosity, can be compatible with the volume change of an active sulfur intermediate product in the charging and discharging process, and ensures the safety of a lithium sulfur battery; the electrode has extremely strong polarity, can effectively adsorb soluble polysulfide generated in the discharging process, inhibits the polysulfide from shuttling to the negative electrode to generate chemical reaction, and avoids the loss of active substances, thereby improving the specific capacity and the cycling stability of the battery.

Description

Metal organic framework nano composite material and preparation method and application thereof
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a metal organic framework nano composite material as well as a preparation method and application thereof.
Background
The lithium-sulfur battery is a lithium battery with sulfur as the positive electrode and metal lithium as the negative electrode. The elemental sulfur has rich reserves in the earth, and has the characteristics of low price, environmental friendliness and the like. The lithium-sulfur battery using sulfur as the anode material has higher material theoretical specific capacity and battery theoretical specific energy which respectively reach 1675mAh g-1And 2600Wh kg-1Much higher than the capacity of commercially widely used lithium cobaltate batteries (<150mA g-1). And the sulfur is an element which is friendly to the environment, basically has no pollution to the environment, and is a lithium battery with very prospect. However, there are still problems to be solved in the lithium-sulfur battery, mainly: (1) elemental sulfur has poor electronic and ionic conductivity, and sulfur materials have very low conductivity at room temperature (5.0X 10)-30S cm-1) End product of the reaction Li2S2And Li2S is also an electronic insulator, which is not conducive to high rate performance of the battery; (2) the intermediate discharge product of the lithium-sulfur battery is dissolved in the organic electrolyte, the viscosity of the electrolyte is increased, and the ionic conductivity is reduced. Polysulfide ions can migrate between the positive and negative electrodes, resulting in loss of active material and waste of electrical energy (the Shuttle effect). The dissolved polysulfide can cross the diaphragm and diffuse to the negative electrode to react with the negative electrode, so that a solid electrolyte interface film (SEI film) of the negative electrode is damaged, and the rapid decline of the battery capacity is caused; (3) final discharge product of lithium sulfur battery, Li2Sn(n-1-2) is electrically insulating and insoluble in an electrolyte, and is deposited on the surface of the conductive skeleton; part of lithium sulfide is separated from the conductive framework and can not react through a reversible charging processTo sulfur or higher order polysulfides, causing a significant capacity fade; (4) the densities of sulfur and lithium sulfide were 2.07 and 1.66g cm, respectively-3During charging and discharging, the volume expansion/contraction is up to 79%, and the expansion can cause the change of the appearance and the structure of the positive electrode, cause the separation of sulfur and a conductive framework and further cause the attenuation of capacity; the volume effect is not significant under the button cell, but the volume effect is amplified in a large cell, so that significant capacity attenuation is generated, the cell can be damaged, and the electrode structure can be damaged by huge volume change; (5) the lithium-sulfur battery uses the metal lithium as the negative electrode, and except the high activity of the metal lithium, the volume of the metal lithium negative electrode can be changed in the charging and discharging process, and dendrite is easy to form; (6) the laboratory scale research of the lithium-sulfur battery is carried out more, and the sulfur capacity per unit area is generally 3.0mg cm-2The research on the high-load pole piece has important value for obtaining the high-performance lithium-sulfur battery.
In order to solve the problems of the lithium-sulfur battery, designing and preparing a high-efficiency positive electrode carrier to improve the conductivity of active sulfur, compatible with volume change caused by different product densities and inhibiting polysulfide shuttling is one of promising solutions. The metal organic framework material has ultrahigh specific surface area and porosity, high stability and polarity, and has wide application prospect in the positive electrode material of the lithium-sulfur battery. However, the metal organic framework is not conductive, and the arrangement is irregular, so that the ion transmission is hindered, and the application of the metal organic framework in the lithium sulfur battery anode is limited.
Disclosure of Invention
In view of the above, the present invention aims to provide a metal organic framework nanocomposite, and a preparation method and an application thereof, wherein the prepared metal organic framework nanocomposite has a high specific surface area, a high porosity and a very strong polarity, shows a good conductive performance when applied to a lithium sulfur battery positive electrode carrier, can inhibit shuttling of polysulfide, and improves the specific capacity and the cycling stability of a battery.
In order to achieve the purpose, the invention adopts the technical scheme that:
a metal-organic framework nanocomposite comprising:
polypyrrole nanotubes;
and a metal organic framework structure material which grows on the surface of the polypyrrole nanotube orderly by chemical grafting of 2-amino-1, 4-terephthalic acid;
the metal organic framework structure material is a crystal with a regular octahedron structure, the center of the metal organic framework structure material is metal ions, and a crosslinking ligand is terephthalic acid;
the specific surface area of the metal organic framework nano composite material is 820-900 m2 g-1。
Preferably, the polypyrrole nanotube is of a hollow structure, the wall thickness of the polypyrrole nanotube is 20-30 nm, and the outer diameter of the polypyrrole nanotube is 150-200 nm.
Preferably, the particle size of the metal organic framework structure material is 50-60 nm.
Preferably, the metal ion is selected from Zr4+、V4+、Ti4+、Cr4+、Fe3+、Al3+、Mn2+And Cu2+One or more of them.
The invention also provides a preparation method of the metal organic framework nano composite material, which comprises the following steps:
1) preparing polypyrrole nanotubes: dissolving ferric trichloride and methyl orange in deionized water to obtain a mixed solution, then adding pyrrole monomer, reacting for 24 hours at room temperature, filtering out a solid product, washing, and drying to obtain a polypyrrole nanotube;
2) preparing a bromobutyl modified polypyrrole nanotube: dispersing potassium hydroxide, 1, 4-dibromobutane and the polypyrrole nanotube prepared in the step 1) into N, N-dimethylformamide, stirring and reacting for 24 hours at the temperature of 60 ℃, filtering out a solid product after the reaction is finished, washing, and vacuum drying for 12 hours at the temperature of 60 ℃ to obtain the bromobutyl modified polypyrrole nanotube;
3) preparing 2-amino-1, 4-terephthalic acid chemically grafted polypyrrole nanotubes: dispersing potassium carbonate, 2-amino methyl terephthalate and the bromobutyl modified polypyrrole nanotube prepared in step 2) into N, N-dimethylformamide, stirring and reacting for 24h at 80 ℃, filtering out a solid product after the reaction is finished, washing, vacuum drying for 12h at 60 ℃, then placing the dried product into dilute sulfuric acid for ultrasonic treatment for 5min, stirring and reacting for 24h at 80 ℃, filtering after the reaction is finished, washing, and vacuum drying for 12h at 60 ℃ to obtain the 2-amino-1, 4-terephthalic acid chemically grafted polypyrrole nanotube;
4) preparing an ordered metal organic framework structure material: adding a metal compound, glacial acetic acid and the 2-amino-1, 4-terephthalic acid chemically-grafted polypyrrole nanotube prepared in the step 3) into N, N-dimethylformamide, performing ultrasonic treatment for 10min, then adding terephthalic acid, transferring the obtained mixture into a polytetrafluoroethylene reaction kettle, reacting for 24h at 120 ℃, filtering out a solid product after the reaction is finished, washing, and performing vacuum drying at 80 ℃ for 12h to obtain the ordered metal organic framework nanocomposite.
Preferably, in the mixed solution in step 1): the concentration of ferric trichloride is 0.05mol/L, and the concentration of methyl orange is 0.005 mol/L.
Preferably, the molar ratio of the ferric trichloride, the methyl orange and the pyrrole monomer in the step 1) is 1.5:0.15: 1.5.
Preferably, the metal compound in step 4) is one or more of zirconium chloride, chromium nitrate, vanadyl sulfate, isopropyl titanate, aluminum nitrate, ferric chloride, manganese chloride and copper chloride.
The invention also provides an application of the metal organic framework nano composite material or the metal organic framework nano composite material prepared by the preparation method in a lithium-sulfur battery cathode material.
Compared with the prior art, the metal-organic framework nanocomposite material is obtained by chemically grafting 2-amino-1, 4-terephthalic acid molecules on the surfaces of the polypyrrole nanotubes, then complexing metal ions and assembling the metal ions and the terephthalic acid molecules into a metal-organic framework crystal. The metal organic framework nano composite material has the advantages of light weight, strong chemical polarity, good thermodynamic stability and corrosion resistance, shows the porous characteristic, has high specific surface area and porosity, can adsorb more polysulfide in unit mass, thereby increasing the energy density and the volume density of the lithium-sulfur battery, being compatible with the volume change of an active sulfur intermediate product in the charging and discharging process and ensuring the safety of the lithium-sulfur battery; the electrode has extremely strong polarity, can effectively adsorb soluble polysulfide generated in the discharging process, inhibits the polysulfide from shuttling to the negative electrode to generate chemical reaction, and avoids the loss of active substances, thereby improving the specific capacity and the cycling stability of the battery.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a metal organic framework nanocomposite according to the present invention;
FIG. 2 is a scanning electron micrograph and a transmission electron micrograph of the metal organic framework nanocomposite provided in example 1;
FIG. 3 is an X-ray diffraction pattern of the metal-organic framework nanocomposite (PPyNTs @ UIO-66) provided in example 1, the polypyrrole nanotubes (PPyNTs) provided in comparative example 1, and the zirconium-based metal-organic framework material (UIO-66) provided in comparative example 2;
FIG. 4 is an X-ray photoelectron spectrum of the metal-organic framework nanocomposite (PPyNTs @ UIO-66) provided in example 1, the polypyrrole nanotubes (PPyNTs) provided in comparative example 1, and the zirconium-based metal-organic framework material (UIO-66) provided in comparative example 2;
FIG. 5 is a nitrogen sorption and desorption curve for the metal organic framework nanocomposite (PPyNTs @ UIO-66) provided in example 1, the polypyrrole nanotubes (PPyNTs) provided in comparative example 1, and the zirconium-based metal organic framework material (UIO-66) provided in comparative example 2;
FIG. 6 is a transmission electron micrograph of PPyNTs @ UIO-66-S in the test example;
FIG. 7 is an open circuit voltage versus time curve for the positive electrode of a lithium sulfur battery using PPyNTs @ UIO-66-S as the positive electrode in the test example;
FIG. 8 is a graph showing the charge and discharge performance of the positive electrode of the lithium sulfur battery using PPyNTs @ UIO-66-S as the positive electrode in the test example;
FIG. 9 is a graph of rate performance of the positive electrode of a lithium sulfur battery using PPyNTs @ UIO-66-S as the positive electrode in the test example;
FIG. 10 is a graph showing the cycle performance of the positive electrode of the lithium sulfur battery using PPyNTs @ UIO-66-S as the positive electrode in the test example;
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the present invention and is not intended to limit the scope of the claims which follow.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
The invention provides a metal organic framework nano composite material, which comprises the following components: the polypyrrole nanotube and a metal organic framework structure material which grows on the surface of the polypyrrole nanotube orderly through chemical grafting of 2-amino-1, 4-terephthalic acid. The metal organic framework structure material is a crystal with a regular octahedron structure, preferably a metal organic framework structure material with the particle size of 50-60 nm, wherein the center of the metal organic framework structure material is metal ions and a crosslinking ligand is terephthalic acid. The specific surface area of the metal organic framework nano composite material provided by the invention is 820-900 m2g-1. The polypyrrole nanotube is preferably a polypyrrole nanotube which has a hollow structure and a wall thickness of 20-30 nm and has an outer diameter of 150-200 nm. The metal ion in the metal-organic framework material is preferably selected from Zr4+、V4+、Ti4+、Cr4+、Fe3+、Al3+、Mn2+And Cu2+One or more of them.
The invention also provides a preparation method of the metal organic framework nano composite material, which comprises the following steps:
1) preparing polypyrrole nanotubes: dissolving ferric trichloride and methyl orange in deionized water to obtain a mixed solution, then adding pyrrole monomer, reacting for 24 hours at room temperature, filtering out a solid product, washing, and drying to obtain a polypyrrole nanotube;
2) preparing a bromobutyl modified polypyrrole nanotube: dispersing potassium hydroxide, 1, 4-dibromobutane and the polypyrrole nanotube prepared in the step 1) into N, N-dimethylformamide, stirring and reacting for 24 hours at the temperature of 60 ℃, filtering out a solid product after the reaction is finished, washing, and vacuum drying for 12 hours at the temperature of 60 ℃ to obtain the bromobutyl modified polypyrrole nanotube;
3) preparing 2-amino-1, 4-terephthalic acid chemically grafted polypyrrole nanotubes: dispersing potassium carbonate, 2-amino methyl terephthalate and the bromobutyl modified polypyrrole nanotube prepared in step 2) into N, N-dimethylformamide, stirring and reacting for 24h at 80 ℃, filtering out a solid product after the reaction is finished, washing, vacuum drying for 12h at 60 ℃, then placing the dried product into dilute sulfuric acid for ultrasonic treatment for 5min, stirring and reacting for 24h at 80 ℃, filtering after the reaction is finished, washing, and vacuum drying for 12h at 60 ℃ to obtain the 2-amino-1, 4-terephthalic acid chemically grafted polypyrrole nanotube;
4) preparing an ordered metal organic framework structure material: adding a metal compound, glacial acetic acid and the 2-amino-1, 4-terephthalic acid chemically-grafted polypyrrole nanotube prepared in the step 3) into N, N-dimethylformamide, performing ultrasonic treatment for 10min, then adding terephthalic acid, transferring the obtained mixture into a polytetrafluoroethylene reaction kettle, reacting for 24h at 120 ℃, filtering out a solid product after the reaction is finished, washing, and performing vacuum drying at 80 ℃ for 12h to obtain the metal-organic framework nanocomposite.
Specifically, ferric trichloride and methyl orange are dissolved in deionized water to obtain a mixed solution, then pyrrole monomers are added, the reaction is carried out for 24 hours at room temperature, a solid product is filtered, and the solid product is washed and dried to obtain the polypyrrole nanotube. In the invention, the concentration of ferric trichloride in the mixed solution is preferably 0.05mol/L, the concentration of methyl orange in the mixed solution is preferably 0.005mol/L, and the molar ratio of ferric trichloride, methyl orange and pyrrole monomer is preferably 1.5:0.15: 1.5.
After the polypyrrole nanotube is obtained, dispersing potassium hydroxide, 1, 4-dibromobutane and the polypyrrole nanotube into N, N-dimethylformamide, stirring for 5 minutes, then heating and stirring for reacting for 24 hours at 60 ℃, filtering out a solid product after the reaction is finished, washing, and drying in vacuum for 12 hours at 60 ℃; in the process, 1, 2-dibromobutane is used for replacing active hydrogen of pyrrole molecules in an alkaline environment, and end group bromine is generated on the surface of the polypyrrole nanotube to obtain the bromobutyl modified polypyrrole nanotube for chemically grafting a 2-amino-1, 4-terephthalic acid ligand.
After obtaining the bromobutyl modified polypyrrole nanotube, the invention disperses potassium carbonate, 2-amino methyl terephthalate and bromobutyl modified polypyrrole nanotube into N, N-dimethylformamide, stirs and reacts for 24h under the condition of 80 ℃, filters and washes after the reaction is finished, and dries in vacuum for 12h under the condition of 60 ℃, then puts the dried product into dilute sulphuric acid for ultrasonic treatment for 5min, stirs and reacts for 24h under the condition of 80 ℃, filters out solid product after the reaction is finished, washes, and dries in vacuum for 12h under the condition of 60 ℃; in the process, the terminal bromine of the bromobutyl modified polypyrrole nanotube is used for replacing amino hydrogen in 2-amino-1, 2-terephthalic acid, and finally 2-amino-1, 2-terephthalic acid molecules are grafted, so that the chemically grafted polypyrrole nanotube, namely the chemically grafted polypyrrole nanotube of 2-amino-1, 4-terephthalic acid is obtained.
After 2-amino-1, 4-terephthalic acid chemically grafted polypyrrole nanotubes are obtained, adding a metal compound, glacial acetic acid and the 2-amino-1, 4-terephthalic acid chemically grafted polypyrrole nanotubes into N, N-dimethylformamide, carrying out ultrasonic treatment for 10min, then adding terephthalic acid, then transferring the obtained mixture into a polytetrafluoroethylene reaction kettle, reacting for 24h at 120 ℃, filtering out a solid product after the reaction is finished, washing, and carrying out vacuum drying for 12h at 80 ℃; in the process, metal ions and terephthalic acid molecules on the surface of the polypyrrole nanotube chemically grafted by the 2-amino-1, 4-terephthalic acid form a complex, and the complex is assembled into a metal organic framework crystal under the promotion of the terephthalic acid, so that the metal organic framework nanocomposite material is obtained. In the present invention, the metal compound used is one selected from the group consisting of zirconium chloride, chromium nitrate, vanadyl sulfate, isopropyl titanate, aluminum nitrate, ferric chloride, manganese chloride and copper chloride.
The preparation method takes 2-amino-1, 4-terephthalic acid chemically grafted polypyrrole nanotubes as a substrate, and orderly grafts a metal organic framework structure material on the surface of the polypyrrole nanotubes by using an original growth method, and the preparation flow chart is shown in figure 1.
The invention also provides an application of the metal organic framework nano composite material or the metal organic framework nano composite material prepared by the preparation method in a lithium-sulfur battery cathode material. The metal organic framework nano composite material can be used as an active sulfur carrier of the positive electrode of a lithium sulfur battery.
The metal organic framework nanocomposite material, the preparation method and the application thereof provided by the invention will be further described with reference to the following examples.
Example 1
The embodiment provides a preparation method of a zirconium-based metal organic framework nano composite material (PPyNTs @ UIO-66), which comprises the following steps:
(1) and (3) synthesizing polypyrrole nanotubes: FeCl is added3(0.243g, 1.5mmol) and methyl orange (0.049g, 0.15mmol) were dissolved in 30mL deionized water; adding 0.105mL of pyrrole monomer (200-mesh 300-mesh neutral aluminum oxide is used for removing the polymerization inhibitor by passing through a column before use so as to initiate pyrrole polymerization), and reacting for 24h at room temperature; cooling to room temperature, washing with deionized water, and vacuum drying at 60 deg.C for 12 hr;
(2) synthesizing a bromobutyl modified polypyrrole nanotube: dispersing 0.03g of polypyrrole nanotube, 0.05g of potassium hydroxide and 1.43g of 1, 4-dibromobutane into 25mL of N, N-dimethylformamide, stirring for 5 minutes, stirring at 60 ℃ for reaction for 24 hours, filtering and washing after the reaction is finished, and vacuum-drying at 60 ℃ for 12 hours;
(3) synthesizing 2-amino-1, 4-terephthalic acid chemically grafted polypyrrole nanotubes: dispersing 0.025g of bromobutyl modified polypyrrole nanotube, 0.05g of potassium carbonate and 0.05g of methyl 2-aminoterephthalate into 25mL of N, N-dimethylformamide, stirring for 5 minutes, stirring at 80 ℃ for reaction for 24 hours, filtering and washing after the reaction is finished, and vacuum-drying at 60 ℃ for 12 hours; the resulting product was placed in dilute sulfuric acid (1mol L)-125mL) sonicationTreating for 5min, stirring at 80 deg.C for 24 hr, filtering, washing, and vacuum drying at 60 deg.C for 12 hr;
(4) adding 0.050g of 2-amino-1, 4-terephthalic acid chemically-grafted polypyrrole nanotubes, 0.028g of zirconium chloride and 0.34mL of glacial acetic acid into 5mL of N, N-dimethylformamide, and carrying out ultrasonic treatment for 10 min; terephthalic acid (0.02g) was then added. And transferring the obtained mixture into a polytetrafluoroethylene reaction kettle, reacting at 120 ℃ for 24 hours, filtering and washing after the reaction is finished, and drying in vacuum at 80 ℃ for 12 hours to obtain the polypyrrole nanotube-loaded zirconium-based metal organic framework nanocomposite (PPyNTs @ UIO-66), namely the metal organic framework nanocomposite of the embodiment.
Fig. 2 is a scanning electron microscope image and a transmission electron microscope image of the metal-organic framework nanocomposite provided in this embodiment, a left image in fig. 2 is a scanning electron microscope image of the metal-organic framework nanocomposite ppyts @ UIO-66 provided in this embodiment, and a right image in fig. 2 is a transmission electron microscope image of the metal-organic framework nanocomposite ppyts @ UIO-66 provided in this embodiment. FIG. 2 shows that the polypyrrole nanotube is of a hollow structure, the wall thickness is 20-30 nm, the outer diameter of the polypyrrole nanotube is 150-200 nm, the metal organic framework nanocomposite (UIO-66) is a crystal of a regular octahedral structure, the particle size of the metal organic framework nanocomposite is 50-60 nm, the metal organic framework nanocomposite grows on the surface of the polypyrrole nanotube uniformly and orderly, and the specific surface area and the porosity of the composite are increased.
Example 2
This example provides a method for preparing a chromium-based metal organic framework composite material (MIL-101), in which 2-amino-1, 4-terephthalic acid chemically grafted polypyrrole nanotubes are prepared according to the steps (1) to (3) in example 1, and then 0.028g of zirconium chloride is changed to 0.048g of chromium nitrate in the step (4) in example 1, so as to prepare the chromium-based metal organic framework composite material (MIL-101).
Example 3
This example provides a method for preparing a vanadium-based metal organic framework composite material (ppyts @ V-BDC), which comprises preparing polypyrrole nanotubes chemically grafted with 2-amino-1, 4-terephthalic acid according to the steps (1) to (3) of example 1, and then changing 0.028g of zirconium chloride to 0.054g of vanadyl sulfate in the step (4) of example 1 to prepare the vanadium-based metal organic framework composite material (ppyts @ V-BDC).
Example 4
This example provides a method for preparing a titanium-based metal organic framework composite material (ppyts @ MOF-125), which comprises steps (1) to (3) of example 1 to obtain 2-amino-1, 4-terephthalic acid chemically grafted polypyrrole nanotubes, and then step (4) of example 1 to change 0.028g of zirconium chloride to 0.042g of isopropyl titanate to obtain the titanium-based metal organic framework composite material (ppyts @ MOF-125).
Example 5
This example provides a method for preparing an aluminum-based metal organic framework composite material (ppyts @ MIL-53), which comprises steps (1) to (3) of example 1 to obtain 2-amino-1, 4-terephthalic acid chemically grafted polypyrrole nanotubes, and then 0.028g of zirconium chloride in step (4) of example 1 is replaced by 0.058g of aluminum nitrate to obtain the aluminum-based metal organic framework composite material (ppyts @ MIL-53).
Example 6
This example provides a method for preparing an iron-based metal organic framework composite material (ppyts @ MIL-100), which comprises steps (1) to (3) of example 1 to obtain 2-amino-1, 4-terephthalic acid chemically grafted polypyrrole nanotubes, and then steps (4) of example 1 to change 0.028g of zirconium chloride to 0.038g of ferric chloride to obtain the iron-based metal organic framework composite material (ppyts @ MIL-100).
Example 7
This example provides a preparation method of metal organic frameworks composite material (ppyts @ Mn-BDC), which comprises preparing polypyrrole nanotubes chemically grafted with 2-amino-1, 4-terephthalic acid according to the steps (1) to (3) of example 1, and then changing 0.028g of zirconium chloride to 0.042g of manganese chloride in the step (4) of example 1 to prepare metal organic frameworks composite material (ppyts @ Mn-BDC).
Example 8
This example provides a method for preparing copper-based metal organic framework composite material (ppyts @ Cu-BDC), which comprises steps (1) to (3) of example 1 to obtain 2-amino-1, 4-terephthalic acid chemically grafted polypyrrole nanotubes, and then step (4) of example 1 to change 0.028g of zirconium chloride to 0.028g of copper chloride to obtain copper-based metal organic framework composite material (ppyts @ Cu-BDC).
Comparative example 1
And (3) synthesizing polypyrrole nanotubes: FeCl is added3(0.243g, 1.5mmol) and methyl orange (0.049g, 0.15mmol) were dissolved in 30mL deionized water; adding 0.105mL of pyrrole monomer (200-mesh 300-mesh neutral aluminum oxide is used for removing the polymerization inhibitor through a column before use), and reacting for 24h at room temperature; cooling to room temperature, washing with deionized water, and vacuum drying at 60 deg.C for 12h to obtain polypyrrole nanotubes (PPyNTs).
Comparative example 2
Adding zirconium chloride 0.028g and glacial acetic acid 0.34mL into N, N-dimethylformamide 5mL, and performing ultrasonic treatment for 10 min; terephthalic acid (0.02g) was then added. And transferring the obtained mixture into a polytetrafluoroethylene reaction kettle, reacting at 120 ℃ for 24 hours, filtering and washing after the reaction is finished, and vacuum-drying at 80 ℃ for 12 hours to obtain the zirconium-based metal organic framework material (UIO-66) of the comparative example.
Test example
(1) The metal organic framework nanocomposite (PPyNTs @ UIO-66) obtained in example 1, the polypyrrole nanotubes (PPyNTs) obtained in comparative example 1 and the zirconium-based metal organic framework material (UIO-66) obtained in comparative example 2 are compared in morphology and structure characterization, and an X-ray diffraction spectrum (figure 3), an X-ray photoelectron spectrum (figure 4) and a nitrogen adsorption and desorption curve (figure 5) are respectively obtained, and as can be seen from figure 3, three strong peaks of UIO-66 appear in the PPyNTs @ UIO-66 composite, which indicates that the UIO-66 and the PPy nanotubes form the composite and are consistent with a transmission electron microscope photograph. In FIG. 4, the left image is an X-ray photoelectron spectrum, and the right image is a Zr high-resolution spectrum. As can be seen from FIG. 4, signals of C, N, O and Zr can be seen in PPyNTs @ UIO-66, which indicates that the four elements exist in the composite material, and Zr and O form an O-Zr-O bond as can be seen from a Zr3d high-resolution photoelectron spectrum, thereby indicating that the UIO-66 crystal is generated. As can be seen from FIG. 5, the specific surface area of PPy is only 23m2 g-1Ratio of UIO-66The surface area is 549m2 g-1And the specific surface area of the PPyNTs @ UIO-66 composite material is 850m2 g-1It was shown that the small sized UIO-66 nanocrystals had a larger specific surface area and that the composite material was more suitable for use as an electrode material than the single UIO-66. As fully illustrated in FIGS. 3 to 5, the composite material obtained in example 1 was PPyNTs @ UIO-66 and had a large specific surface area.
(2) The metal organic framework nano composite material (PPyNTs @ UIO-66) obtained in the example 1 is applied to an active sulfur carrier of a positive electrode of a lithium-sulfur battery, and specifically comprises the following steps: PPyNTs @ UIO-66 and active sulfur are subjected to heat treatment at 155 ℃ for 20 hours according to the proportion of 85:15 to obtain the PPyNTs @ UIO-66-S positive electrode, wherein the active sulfur loading is 75.7 wt%, a transmission electron microscope image of the material is shown in figure 6, and figure 6 shows that the active sulfur uniformly permeates into a PPyNTs @ UIO-66 framework. The PPyNTs @ UIO-66 composite sulfur material is used as the positive electrode to be assembled into the lithium-sulfur battery, the open-circuit voltage-time curve of the lithium-sulfur battery is shown in figure 7, and the open-circuit voltage-time curve shows that the lithium-sulfur battery has stable voltage and can be stabilized at 2.4V for a long time; FIG. 8 shows the charge/discharge performance of the positive electrode of the lithium-sulfur battery, and it can be seen from FIG. 8 that the specific discharge capacity of the lithium-sulfur battery reaches 1225mAh g at a current density of 0.1C-1Still maintain 827mAh g at 2.0C current density-1Discharge specific capacity, and shows good oxidation reduction peak.
(3) The metal organic framework nanocomposite PPyNTs @ UIO-66 obtained in example 1, the polypyrrole nanotubes (PPyNTs) obtained in comparative example 1 and the zirconium-based metal organic framework material (UIO-66) obtained in comparative example 2 were respectively subjected to heat treatment with active sulfur at 155 ℃ for 20 hours in a ratio of 85:15, and then the three obtained composites were respectively used as positive electrode materials to assemble lithium sulfur batteries having positive electrodes of PPyNTs @ UIO-66, PPyNTs or UIO-66, and the performances of the three lithium sulfur batteries were tested. Wherein, the multiplying power performance test result is shown in figure 9, and the cycle performance test result is shown in figure 10. As can be seen from the rate performance of FIG. 9, the PPyNTs @ UIO-66-S positive electrode has the highest rate performance, that is, the discharge capacity of the PPyNTs @ UIO-66-S is far larger than that of a single PPy-S positive electrode and a single UIO-66-S positive electrode at a current density of 2.0C, which indicates that the PPyNTs @ UIO-66-S positive electrode has the best rate performance. As can be seen from fig. 10, the results of 200 charge-discharge cycles at 0.1C show that: the capacity decline of the lithium-sulfur battery with the positive electrode PPyNTs @ UIO-66 in a single charge-discharge cycle is only 0.093%, and compared with the lithium-sulfur battery with the positive electrode PPyNTs or UIO-66, the performance of the lithium-sulfur battery is greatly improved.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (8)

1. A metal organic framework nanocomposite, comprising:
polypyrrole nanotubes;
and a metal organic framework structure material which grows on the surface of the polypyrrole nanotube orderly by chemical grafting of 2-amino-1, 4-terephthalic acid;
the metal organic framework structure material is a crystal with a regular octahedron structure, the center of the metal organic framework structure material is metal ions, and a crosslinking ligand is terephthalic acid; the particle size of the metal organic framework structure material is 50-60 nm;
the specific surface area of the metal organic framework nano composite material is 820-900 m2g-1；
The metal organic framework nano composite material is prepared by adopting a preparation method comprising the following steps:
1) preparing polypyrrole nanotubes: dissolving ferric trichloride and methyl orange in deionized water to obtain a mixed solution, then adding pyrrole monomer, reacting for 24 hours at room temperature, filtering out a solid product, washing, and drying to obtain a polypyrrole nanotube;
2) preparing a bromobutyl modified polypyrrole nanotube: dispersing potassium hydroxide, 1, 4-dibromobutane and the polypyrrole nanotube prepared in the step 1) into N, N-dimethylformamide, stirring and reacting for 24 hours at the temperature of 60 ℃, filtering out a solid product after the reaction is finished, washing, and vacuum drying for 12 hours at the temperature of 60 ℃ to obtain the bromobutyl modified polypyrrole nanotube;
3) preparing 2-amino-1, 4-terephthalic acid chemically grafted polypyrrole nanotubes: dispersing potassium carbonate, 2-amino methyl terephthalate and the bromobutyl modified polypyrrole nanotube prepared in step 2) into N, N-dimethylformamide, stirring and reacting for 24h at 80 ℃, filtering out a solid product after the reaction is finished, washing, vacuum drying for 12h at 60 ℃, then placing the dried product into dilute sulfuric acid for ultrasonic treatment for 5min, stirring and reacting for 24h at 80 ℃, filtering after the reaction is finished, washing, and vacuum drying for 12h at 60 ℃ to obtain the 2-amino-1, 4-terephthalic acid chemically grafted polypyrrole nanotube;
4) preparing an ordered metal organic framework structure material: adding a metal compound, glacial acetic acid and the 2-amino-1, 4-terephthalic acid chemically-grafted polypyrrole nanotube prepared in the step 3) into N, N-dimethylformamide, performing ultrasonic treatment for 10min, then adding terephthalic acid, transferring the obtained mixture into a polytetrafluoroethylene reaction kettle, reacting for 24h at 120 ℃, filtering out a solid product after the reaction is finished, washing, and performing vacuum drying at 80 ℃ for 12h to obtain the metal-organic framework nanocomposite.
2. The metal organic framework nanocomposite material of claim 1, wherein the polypyrrole nanotubes are hollow and have a wall thickness of 20 to 30nm and an outer diameter of 150 to 200 nm.
3. The metal-organic framework nanocomposite material of claim 1, wherein the metal ion is selected from the group consisting of Zr4+、V4+、Ti4+、Cr4+、Fe3+、Al3+、Mn2+And Cu2+One or more of them.
4. The preparation method of the metal organic framework nano composite material is characterized by comprising the following steps:
1) preparing polypyrrole nanotubes: dissolving ferric trichloride and methyl orange in deionized water to obtain a mixed solution, then adding pyrrole monomer, reacting for 24 hours at room temperature, filtering out a solid product, washing, and drying to obtain a polypyrrole nanotube;
2) preparing a bromobutyl modified polypyrrole nanotube: dispersing potassium hydroxide, 1, 4-dibromobutane and the polypyrrole nanotube prepared in the step 1) into N, N-dimethylformamide, stirring and reacting for 24 hours at the temperature of 60 ℃, filtering out a solid product after the reaction is finished, washing, and vacuum drying for 12 hours at the temperature of 60 ℃ to obtain the bromobutyl modified polypyrrole nanotube;
3) preparing 2-amino-1, 4-terephthalic acid chemically grafted polypyrrole nanotubes: dispersing potassium carbonate, 2-amino methyl terephthalate and the bromobutyl modified polypyrrole nanotube prepared in step 2) into N, N-dimethylformamide, stirring and reacting for 24h at 80 ℃, filtering out a solid product after the reaction is finished, washing, vacuum drying for 12h at 60 ℃, then placing the dried product into dilute sulfuric acid for ultrasonic treatment for 5min, stirring and reacting for 24h at 80 ℃, filtering after the reaction is finished, washing, and vacuum drying for 12h at 60 ℃ to obtain the 2-amino-1, 4-terephthalic acid chemically grafted polypyrrole nanotube;
4) preparing an ordered metal organic framework structure material: adding a metal compound, glacial acetic acid and the 2-amino-1, 4-terephthalic acid chemically-grafted polypyrrole nanotube prepared in the step 3) into N, N-dimethylformamide, performing ultrasonic treatment for 10min, then adding terephthalic acid, transferring the obtained mixture into a polytetrafluoroethylene reaction kettle, reacting for 24h at 120 ℃, filtering out a solid product after the reaction is finished, washing, and performing vacuum drying at 80 ℃ for 12h to obtain the metal-organic framework nanocomposite.
5. The method according to claim 4, wherein: step 1) in the mixed solution: the concentration of ferric trichloride is 0.05mol/L, and the concentration of methyl orange is 0.005 mol/L.
6. The method according to claim 4, wherein: the molar ratio of the ferric trichloride, the methyl orange and the pyrrole monomer in the step 1) is 1.5:0.15: 1.5.
7. The method according to claim 4, wherein: and 4) the metal compound is one or more of zirconium chloride, chromium nitrate, vanadyl sulfate, isopropyl titanate, aluminum nitrate, ferric chloride, manganese chloride and copper chloride.
8. Use of the metal organic framework nanocomposite material according to any one of claims 1 to 3 or the metal organic framework nanocomposite material prepared by the preparation method according to any one of claims 4 to 7 in a positive electrode material of a lithium-sulfur battery.
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