CN115260423A - Long alkyl chain modified covalent organic framework material, preparation method and application - Google Patents
Long alkyl chain modified covalent organic framework material, preparation method and application Download PDFInfo
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Abstract
The invention discloses a long alkyl chain modified covalent organic framework material, a preparation method and application. The long alkyl chain modified covalent organic framework material is a hexagonal topological structure synthesized by connecting three aldehydes in trihydroxy mesitylene aldehyde and two amide groups of an amino compound modified by a long alkyl chain to form a-C = C-NH-NH-covalent bond. After the covalent organic framework material modified by the long alkyl chain is subjected to ball milling and stripping to form a nanosheet, the covalent organic framework nanosheet is compounded on a polyethylene film by a vacuum-assisted self-assembly method to prepare the composite diaphragm. The long alkyl chain modified covalent organic framework composite diaphragm has excellent electrolyte wettability and polysulfide shuttling inhibition effect, and the assembled lithium-sulfur battery has good cycle stability and excellent charge-discharge specific capacity.
Description
Technical Field
The invention belongs to the field of covalent organic framework compounds, and relates to a long alkyl chain modified covalent organic framework material, a preparation method and application.
Background
Lithium sulfur batteries are recognized as one of the most promising advanced energy storage systems due to their high energy density, low cost, and environmentally friendly elemental sulfur. However, the practical application of lithium-sulfur batteries has been plagued by capacity fade and low coulombic efficiency, which is mainly caused by the severe shuttling effect of lithium polysulfides. Many studies have been made on batteries in order to improve the efficiency and cycle stability of the batteries. Among them, a battery separator having an effect of suppressing shuttling of lithium polysulfide has received much attention. Since the pore size of conventional polymer separators cannot be as large as to inhibit the shuttling of lithium polysulfides, it is urgent to develop a nano-sized cell separator having the ability to inhibit the shuttling of lithium polysulfides. However, it is still a challenge to reduce the pore size and ensure the reduction of the overall thickness, thereby improving the specific capacity of the battery, i.e. how to design an ultra-thin lithium-sulfur battery separator.
Covalent Organic Frameworks (COFs) are porous organic framework materials composed of light elements (C, N, O, etc.), and are generally solid powders, and thus are difficult to process into thin films. Chinese patent application 2021107755394 discloses an alkyl chain modified covalent organic framework film, a preparation method and an application thereof, wherein the covalent organic framework film prepared by using an interface method is improved compared with solid powder, but the thickness of the covalent organic framework film is still too thick and exceeds 50 micrometers. The document (Nano Lett. 2021,21,7,2997-3006) reports that a lithium-sulfur battery diaphragm using lithium sulfonate COFs as a modification layer has a thickness of more than 25 μm, a specific capacity reduced to 400mAh/g after 100 cycles of cycling, and a continuous decline trend, and is poor in stability.
Disclosure of Invention
The invention aims to provide a long alkyl chain modified covalent organic framework material, a preparation method and application thereof as a battery diaphragm in a lithium-sulfur battery.
The technical scheme for realizing the purpose of the invention is as follows:
long alkyl chain modifications of the inventionThe covalent organic framework material is an amino compound (NH) modified by three aldehydes in trihydroxy benzenetricarboxylic aldehyde and a long alkyl chain 2 NH-Cx, (x =12,16,20)) is linked to form a hexagonal topology synthesized by covalent bonding of-C = C-NH-, of the formula:
the structural formula of the long alkyl chain modified amino compound is as follows:
the structural formula of trihydroxy mesitylene aldehyde is as follows:
the preparation method of the long alkyl chain modified covalent organic framework material comprises the following steps:
adding trihydroxy-benzenetrialdehyde and an amino compound modified by a long alkyl chain into a mesitylene/1,4-dioxane solution, adding acetic acid after ultrasonic dissolution, performing ultrasonic dissolution again to disperse the mixture into a suspension, performing liquid nitrogen freezing, vacuumizing and degassing treatment on the suspension, sealing a tube by using a flame gun under a vacuum state, reacting 48-168 h at 120 +/-20 ℃ to obtain a crude product, washing and filtering the crude product, performing Soxhlet extraction by using tetrahydrofuran and chloroform, and finally performing vacuum drying to obtain a long alkyl chain modified covalent organic framework material, wherein in the mesitylene/1,4-dioxane solution, the volume ratio of mesitylene to 1,4-dioxane is 1:7 to 7:1.
preferably, the molar ratio of trihydroxybenzenetrialdehyde to the long alkyl chain modified amine compound is 2:3.
Preferably, the times of the liquid nitrogen freezing, vacuumizing and degassing treatment are more than 3 times.
Preferably, the concentration of trihydroxy benzenetrialdehyde is 0.3-3 mol/L, and the concentration of the amino compound modified by the long alkyl chain is 0.2-2 mol/L.
Preferably, the acetic acid concentration is 3 to 12mol/L, more preferably 6mol/L.
Preferably, the reaction temperature is 120 ℃ and the reaction time is 72h.
Preferably, the crude product is washed clean with dichloromethane, ethyl acetate, methanol, acetone in sequence.
The invention also provides a preparation method of the covalent organic framework composite diaphragm based on the long alkyl chain modified covalent organic framework material, which comprises the following steps:
and 2, taking a polyethylene film as a base film, carrying out vacuum filtration on the long alkyl chain modified covalent organic framework nanosheet dispersion, adding ethanol after the filtration, carrying out filtration and cleaning, and finally carrying out vacuum drying to obtain the long alkyl chain modified covalent organic framework composite diaphragm.
Preferably, in step 1, the organic solvent is N-methylpyrrolidone, dimethylformamide or acetonitrile, more preferably N-methylpyrrolidone.
Preferably, in the step 1, the rotation speed of the ball mill is 300-600 rpm, more preferably 400rpm; the ball milling time is 6 to 48h, and more preferably 24h.
Preferably, in step 2, the polyethylene film has a pore size of 50 to 200nm, more preferably 100nm.
Preferably, in the step 2, the thickness of the covalent organic framework nanosheet layer in the composite membrane formed after vacuum filtration is 2-15 μm, and more preferably 5 μm.
Preferably, in the step 2, the vacuum degree adopted in the vacuum filtration process is 0.1MPa.
Preferably, in the step 2, the vacuum drying temperature is 60-80 ℃, and the drying time is more than 10 h.
Further, the invention provides application of the long alkyl chain modified covalent organic framework composite diaphragm in a lithium-sulfur battery.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, the COFs modified by long alkyl chains are used for regulating and controlling the state and the interlayer spacing, so that the ball milling stripping efficiency is improved. The thickness of the diaphragm can be greatly reduced to 9-15 mu m by adopting a nanosheet composite structure, and compared with a covalent organic framework material diaphragm and a pure PE polymer film which are directly subjected to powder tabletting, the long alkyl chain reduces the aperture of a covalent organic framework, so that the shuttle of lithium polysulfide can be inhibited, meanwhile, the alkyl chain has excellent electrolyte wettability, and the lithium polysulfide is blocked from passing through by physical repulsion and chemical adsorption.
(2) The lithium-sulfur battery which is composed of the covalent organic framework composite diaphragm modified by the long alkyl chain as the diaphragm has high specific capacity of 600mAh/g, has excellent cycling stability, can inhibit capacity attenuation, has the specific capacity of more than 550mAh/g after being cycled for 100 circles, and can stably maintain the high specific capacity.
Drawings
FIG. 1 is an XRD pattern of COF-C12, COF-C16 and COF-C20;
FIG. 2 is an IR spectrum of COF-C12, COF-C16 and COF-C20;
FIG. 3 is a thermogravimetric analysis diagram of COF-C12, COF-C16 and COF-C20;
FIG. 4 is an SEM image of the surface of a pure PE membrane of a comparative sample;
FIG. 5 is a surface SEM image of a COF-C12 composite membrane;
FIG. 6 is a surface SEM image of a COF-C16 composite membrane;
FIG. 7 is a surface SEM image of a COF-C20 composite membrane;
FIG. 8 is a graph of ion conductivity of COF-C12, COF-C16, and COF-C20 composite membranes and a control;
FIG. 9 is a cycle diagram of a lithium-sulfur battery assembled by a COF-C12 composite separator;
FIG. 10 is a cycle diagram of a lithium-sulfur battery assembled by a COF-C16 composite separator;
FIG. 11 is a cycle diagram of a lithium-sulfur battery assembled by a COF-C20 composite separator;
FIG. 12 is a cycle chart of a lithium sulfur battery assembled with a comparative pure PE separator;
FIG. 13 is a cycle chart of a lithium-sulfur battery assembled by comparative COF-C12 powder tablets.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below by way of embodiments with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. To make various changes and modifications within the scope of the present invention.
NH according to the invention 2 NH-Cx is commercially available or can be prepared as a free-standing form as NH 2 NH-C16 is taken as an example, and the specific synthetic route is as follows:
the method comprises the following specific steps:
(1) Compound 1c: 1mmol of compound 1a,3mmol of compound 1b and 1mmol of K 2 CO 3 Adding 30mlN, N-Dimethylformamide (DMF) in N 2 The reaction is carried out for 48 hours at 65 ℃ under the protective atmosphere, after the reaction is finished, dichloromethane is used for extraction, saturated saline solution is used for washing, anhydrous sodium sulfate is used for drying, a solvent is removed by vacuum spin drying, and column chromatography is used for separation and purification to obtain a compound 1c;
(2)NH 2 NH-C16: adding the compound 1c and hydrazine hydrate into 15ml ethanol solution, reacting for 12 hours, freezing at low temperature, directly filtering, washing white solid with petroleum ether solvent for multiple times to obtain target monomer NH 2 NH-C16。
Example 1
The long alkyl chain modified covalent organic framework material (COF-C12) is composed of trihydroxy benzenetrialdehyde and NH 2 NH-C12 is reacted by Schiff baseThe organic framework structure to be formed has the following structure:
NH 2 the structure of NH-C12 is shown below:
the preparation method of COF-C12 comprises the following specific steps:
a glass ampoule (volume: about 20mL, body length: 18cm, neck length: 9 cm) was charged with trihydroxybenzenetrialdehyde (21.0 mg, 0.1mmol), NH 2 NH-C12 (84.5mg, 0.15mmol) and mesitylene/1,4-dioxane solution (3:1, v/v,4 mL). Then, the ampoule was immersed in an ultrasonic bath for 5 minutes; followed by the addition of 0.4mL of 6.0mol L -1 Acetic acid, the ampoule was immersed in the ultrasonic bath for 2 minutes. The mixture was sonicated for 2 minutes to obtain a homogeneous dispersion. The tubes were then snap frozen at 77K with a liquid nitrogen bath and degassed by three freeze pump-thaw cycles, sealed under vacuum, and heated at 120 ℃ for 3 days. Breaking the ampoule neck, centrifuging to separate yellow gel product, washing with acetone (3 × 10 mL), soaking in anhydrous acetone for 12h, and vacuum drying at 80 deg.C for 12h to obtain COF-C12 as yellow colloid powder. The reaction formula is shown as follows:
example 2
The long alkyl chain modified covalent organic framework material (COF-C16) is composed of trihydroxy benzenetrialdehyde and NH 2 The structure of the organic framework formed by reacting NH-C16 with Schiff base is as follows:
NH 2 the structure of NH-C16 is shown below:
the preparation method of COF-C16 comprises the following specific steps:
a glass ampoule (volume: about 20mL, body length: 18cm, neck length: 9 cm) was charged with trihydroxybenzenetrialdehyde (21.0 mg, 0.1mmol), NH 2 NH-C16 (101.3mg, 0.15mmol) and mesitylene/1,4-dioxane solution (3:1, v/v,4 mL). Then, the ampoule was immersed in an ultrasonic bath for 5 minutes; followed by the addition of 0.4mL of 6.0mol L -1 Acetic acid, the ampoule was immersed in the ultrasonic bath for 2 minutes. The mixture was sonicated for 2 minutes to obtain a homogeneous dispersion. The tubes were then snap frozen at 77K with a liquid nitrogen bath and degassed by three freeze pump-thaw cycles, sealed under vacuum, and heated at 120 ℃ for 3 days. Breaking the ampoule neck, centrifuging to separate yellow gel product, washing with acetone (3 × 10 mL), soaking in anhydrous acetone for 12h, and vacuum drying at 80 deg.C for 12h to obtain COF-C16 as yellow colloid powder. The reaction formula is shown as follows:
example 3
The long alkyl chain modified covalent organic framework material (COF-C20) is composed of trihydroxy benzenetrialdehyde and NH 2 The NH-C20 organic framework structure formed by Schiff base reaction has the following structure:
NH 2 the structure of NH-C20 is shown below:
the preparation method of COF-C20 comprises the following specific steps:
into a glass ampoule (volume: about 20mL, body length: 18cm, neck length: 9 cm) were charged trihydroxybenzenetrialdehyde (21.0 mg, 0.1mmol), NH 2 NH-C20 (118.1mg, 0.15mmol) and mesitylene/1,4-dioxane solution (3, 1,v/v,4 mL). Then, the ampoule was immersed in an ultrasonic bath for 5 minutes; followed by the addition of 0.4mL of 6.0mol L -1 Acetic acid, the ampoule was immersed in the ultrasonic bath for 2 minutes. The mixture was sonicated for 2 minutes to obtain a homogeneous dispersion. The tubes were then snap frozen at 77K with a liquid nitrogen bath and degassed by three freeze pump-thaw cycles, sealed under vacuum, and heated at 120 ℃ for 3 days. Breaking the ampoule neck, centrifuging to separate yellow gel product, washing with acetone (3 × 10 mL), soaking in anhydrous acetone for 12h, and vacuum drying at 80 deg.C for 12h to obtain COF-C20 as yellow colloid powder. The reaction formula is shown as follows:
example 4
Adding 100mg of COF-C12 colloidal powder into a polytetrafluoroethylene ball milling tank, then adding 15 agate ball milling beads with the diameter of 5mm, adding 20mL of N-methylpyrrolidone, carrying out ball milling at the rotating speed of 300rpm for 24h, standing after the ball milling is finished, and taking the supernatant as well-dispersed COF-C12 nanosheet solution.
Selecting a polyethylene film with the pore diameter of 100nm as a bottom film of a vacuum filtration device, then dropwise adding 20mL of well-dispersed COF-C12 nanosheet solution on the bottom film, carrying out suction filtration under the condition of 0.1MPa vacuum degree, adding 10mL of ethanol after solvent suction filtration is finished, carrying out suction filtration and cleaning, and then drying the solvent in a vacuum oven at 50 ℃ to obtain the COF-C12 composite diaphragm.
Example 5
Adding 100mg of COF-C16 colloidal powder into a polytetrafluoroethylene ball milling tank, then adding 15 agate ball milling beads with the diameter of 5mm, adding 20mL of N-methylpyrrolidone, carrying out ball milling at the rotating speed of 300rpm for 24h, standing after the ball milling is finished, and taking the supernatant as well-dispersed COF-C16 nanosheet solution.
Selecting a polyethylene film with the pore diameter of 100nm as a bottom film of a vacuum filtration device, then dropwise adding 20mL of well-dispersed COF-C16 nanosheet solution on the bottom film, carrying out suction filtration under the condition of 0.1MPa vacuum degree, adding 10mL of ethanol solvent after the solvent is completely filtered, carrying out suction filtration and cleaning, and then drying the solvent in a vacuum oven at 50 ℃ to obtain the COF-C16 composite diaphragm.
Example 6
Adding 100mg of COF-C20 colloidal powder into a polytetrafluoroethylene ball milling tank, then adding 15 agate ball milling beads with the diameter of 5mm, adding 20mL of N-methylpyrrolidone, carrying out ball milling at the rotating speed of 300rpm for 24h, standing after the ball milling is finished, and taking the supernatant as well-dispersed COF-C20 nanosheet solution.
Selecting a polyethylene film with the pore diameter of 100nm as a bottom film of a vacuum filtration device, then dropwise adding 20mL of well-dispersed COF-C20 nanosheet solution on the bottom film, carrying out suction filtration under the condition of 0.1MPa vacuum degree, adding 10mL of ethanol solvent after the solvent is completely filtered, carrying out suction filtration and cleaning, and then drying the solvent in a vacuum oven at 50 ℃ to obtain the COF-C20 composite diaphragm.
Example 7
And adding films formed by tabletting COF-C12, COF-C16 and COF-C20 composite diaphragms, a pure PE battery diaphragm and COF-C12 of a comparison sample into a stainless steel symmetrical battery as a battery diaphragm, and assembling the battery in a glove box. The specific implementation method for testing the conductivity curve of the battery is as follows: the battery was placed in an incubator, and the impedance curve of the battery was measured at 25 ℃ and 0.1 to 1MHz using a Biological system.
Example 8
The COF-C12, COF-C16 and COF-C20 composite diaphragms and films formed by tabletting pure PE diaphragms and COF-C12 serving as comparison samples are used as diaphragms of lithium-sulfur batteries, and the lithium-sulfur batteries are assembled in a glove box. The specific implementation method for testing the charge-discharge curve of the battery is as follows: and (3) placing the battery into a clean constant temperature box, and measuring a charge-discharge curve of the battery by using a blue electricity system under the condition of 0.2C charge-discharge multiplying power under the voltage of 1.7-2.8V.
FIG. 1 is XRD patterns of COF-C12, COF-C16 and COF-C20, which show that the long alkyl chain modified covalent organic framework material prepared by the invention has good crystallinity.
FIG. 2 is an IR spectrum of COF-C12, COF-C16 and COF-C20, demonstrating the formation of C-N bond.
FIG. 3 is a thermogravimetric analysis diagram of COF-C12, COF-C16 and COF-C20, which shows that the covalent organic framework material modified by long alkyl chains has excellent thermal stability and can be maintained above 400 ℃.
Fig. 4 is an SEM image of the surface of a comparative pure PE membrane, which has a much larger pore size than the COF-modified membrane surface.
Fig. 5 is a surface SEM image of a COF-C12 composite separator, illustrating that the composite separator greatly reduces the pore size of the separator.
Fig. 6 is a surface SEM image of a COF-C16 composite separator, illustrating that the composite separator greatly reduces the pore size of the separator.
Fig. 7 is a surface SEM image of a COF-C20 composite separator, illustrating that the composite separator greatly reduces the pore size of the separator.
FIG. 8 is a graph of ion conductivity of COF-C12, COF-C16, COF-C20 composite membranes and comparative samples, which illustrates that the long alkyl chain modified covalent organic framework composite membrane has more excellent lithium ion transport effect compared with pure PE battery membranes.
Fig. 9 is a cycle diagram of a lithium-sulfur battery assembled by a COF-C12 composite separator, which illustrates that the lithium-sulfur battery assembled by the COF-C12 composite separator has good cycle stability (52 cycles) and high specific capacity (650 mAh/g).
Fig. 10 is a cycle chart of a lithium-sulfur battery assembled by a COF-C16 composite separator, and illustrates that the lithium-sulfur battery assembled by the COF-C16 composite separator has good cycle stability (52 cycles) and high specific capacity (635 mAh/g).
Fig. 11 is a cycle chart of a lithium-sulfur battery assembled by a COF-C20 composite membrane, which illustrates that the lithium-sulfur battery assembled by the COF-C20 composite membrane has good cycle stability (52 cycles) and high specific capacity (630 mAh/g).
Fig. 12 is a cycle chart of a lithium-sulfur battery assembled by a pure PE separator of a comparative sample, which is unstable in cycle and has a rapid specific capacity decay.
FIG. 13 is a cycle chart of a lithium sulfur battery with a separator formed by compressing a comparative COF-C12 powder, which shows unstable cycle and rapid specific capacity decay.
Claims (10)
1. The long alkyl chain modified covalent organic framework material is characterized in that the structural formula is as follows:
2. the method of preparing a long alkyl chain modified covalent organic framework material of claim 1, comprising the steps of:
adding trihydroxy-benzenetrialdehyde and an amino compound modified by a long alkyl chain into a mesitylene/1,4-dioxane solution, adding acetic acid after ultrasonic dissolution, performing ultrasonic dissolution again to disperse the mixture into a suspension, performing liquid nitrogen freezing, vacuumizing and degassing treatment on the suspension, sealing a tube by using a flame gun under a vacuum state, reacting for 48-168 hours at 120 +/-20 ℃ to obtain a crude product, washing and filtering the crude product, performing Soxhlet extraction by using tetrahydrofuran and chloroform, and finally performing vacuum drying to obtain a long alkyl chain modified covalent organic framework material; in the mesitylene/1,4-dioxane solution, the volume ratio of mesitylene to 1,4-dioxane is 1:7 to 7:1, the structural formula of the amino compound modified by the long alkyl chain is as follows:
the structural formula of the trihydroxy mesitylene aldehyde is as follows:
3. the method of claim 2, wherein the molar ratio of trihydroxy-benzenetrialdehyde to long alkyl chain modified amine compound is 2:3, the concentration of trihydroxy-benzenetrialdehyde is 0.3-3 mol/L, and the concentration of long alkyl chain modified amine compound is 0.2-2 mol/L.
4. The method according to claim 2, wherein the number of times of freezing with liquid nitrogen, vacuuming, and degassing treatment is 3 or more; the concentration of acetic acid is 3 to 12mol/L, and the preferred concentration is 6mol/L; the reaction temperature is 120 ℃, and the reaction time is 72h; and washing the crude product with dichloromethane, ethyl acetate, methanol and acetone in sequence.
5. The preparation method of the long alkyl chain modified covalent organic framework composite membrane is characterized by comprising the following steps:
step 1, adding an organic solvent as an auxiliary agent into the long alkyl chain modified covalent organic framework material of claim 1, performing ball milling for 12-48 h, standing the mixed solution after ball milling, and taking the supernatant to obtain a long alkyl chain modified covalent organic framework nanosheet dispersion;
and 2, taking a polyethylene film as a base film, carrying out vacuum filtration on the long alkyl chain modified covalent organic framework nanosheet dispersion, adding ethanol after the filtration, carrying out filtration and cleaning, and finally carrying out vacuum drying to obtain the long alkyl chain modified covalent organic framework composite diaphragm.
6. The method according to claim 5, wherein in step 1, the organic solvent is N-methylpyrrolidone, dimethylformamide or acetonitrile; the rotating speed of the ball mill is 300-600 rpm, preferably 400rpm; the ball milling time is 6 to 48 hours, preferably 24 hours.
7. The method according to claim 5, wherein in step 2, the polyethylene film has a pore size of 50 to 200nm, preferably 100nm; in the composite membrane formed after vacuum filtration, the thickness of the covalent organic framework nanosheet layer is 2-15 μm, preferably 5 μm.
8. The preparation method according to claim 5, wherein in the step 2, the vacuum degree used in the vacuum filtration process is 0.1MPa; the vacuum drying temperature is 60-80 ℃, and the drying time is more than 10 h.
9. The covalent organic framework composite diaphragm modified by the long alkyl chain prepared by the preparation method of any one of claims 5 to 8.
10. Use of the long alkyl chain modified covalent organic framework composite separator of claim 9 in a lithium sulfur battery.
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