CN115260423B - Covalent organic framework material modified by long alkyl chain, preparation method and application - Google Patents
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Abstract
The invention discloses a covalent organic framework material modified by a long alkyl chain, 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 trihydroxybenzene trioxymethylene and two amide groups of an amino compound modified by the long alkyl chain to form a-C=C-NH-NH-covalent bond. And after ball milling and stripping the covalent organic framework material modified by the long alkyl chain to form a nano sheet, compounding the covalent organic framework nano sheet on a polyethylene film by adopting a vacuum-assisted self-assembly method to prepare the composite membrane. The long alkyl chain modified covalent organic framework composite membrane has excellent electrolyte wettability and polysulfide shuttle 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 covalent organic framework material modified by a long alkyl chain, 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, practical use of lithium sulfur batteries has been plagued by capacity fade and low coulombic efficiency, which is mainly caused by the severe shuttle effect of lithium polysulfide. Many studies have been made on the battery in order to improve the efficiency and the cycle stability of the battery. Among them, a battery separator having an effective lithium polysulfide shuttle inhibition has received great attention. Since conventional polymer separator pore sizes do not reach the size that inhibits lithium polysulfide shuttling, it is urgent to develop a nanoscale pore size battery separator with that inhibits lithium polysulfide shuttling. However, it is still a challenge to reduce the pore size while ensuring a reduction in the overall thickness thereof, thereby increasing 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.), typically solid powders, and therefore difficult to process into thin films. Chinese patent application 2021107755394 discloses a covalent organic framework film modified with alkyl chains, a method for preparing the same and application thereof, wherein the covalent organic framework film is prepared by an interfacial method, and the thickness of the covalent organic framework film is still too thick, more than 50 microns, although the covalent organic framework film is improved compared with solid powder. The literature (Nano Lett. 2021,21,7,2997-3006) reports a lithium sulfur battery separator using lithium sulfonate COFs as a modification layer, which has a thickness exceeding 25 μm, and a specific capacity reduced to 400mAh/g after 100 cycles, and which is in a continuous decrease trend, and which is inferior in stability.
Disclosure of Invention
The invention aims to provide a covalent organic framework material modified by a long alkyl chain, a preparation method and application of the covalent organic framework material as a battery diaphragm in a lithium-sulfur battery.
The technical scheme for realizing the purpose of the invention is as follows:
the covalent organic framework material modified by long alkyl chain is amino compound (NH) modified by three aldehydes and long alkyl chain in trihydroxy trimellitic aldehyde 2 NH-Cx, (x=12, 16, 20)) to form a hexagonal topology synthesized by-c=c-NH-covalent bond, the structural formula is as follows:
the structural formula of the amino compound modified by the long alkyl chain is as follows:
the structural formula of the trihydroxy benzene tricarboxaldehyde is as follows:
the preparation method of the covalent organic framework material modified by the long alkyl chain comprises the following steps:
adding trihydroxy trimellitic aldehyde 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 into a suspension, performing liquid nitrogen freezing, vacuumizing and degassing treatment on the suspension, sealing a tube by using a flame gun in a vacuum state, then reacting 48-168 h at 120+/-20 ℃ to obtain a crude product, washing the crude product, performing suction filtration, performing Soxhlet extraction by tetrahydrofuran and chloroform, and finally performing vacuum drying to obtain the covalent organic framework material modified by the long alkyl chain, wherein the volume ratio of the mesitylene to the 1, 4-dioxane solution is 1: 7-7: 1.
preferably, the molar ratio of the trihydroxybenzene trialdehyde to the long alkyl chain modified amine compound is 2:3.
Preferably, the number of freezing, vacuuming and degassing treatments of liquid nitrogen is 3 or more.
Preferably, the concentration of the trihydroxy trimellitic aldehyde is 0.3-3 mol/L, and the concentration of the long alkyl chain modified amino compound 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 72 hours.
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 membrane based on the long alkyl chain modified covalent organic framework material, which comprises the following steps:
step 1, adding an organic solvent serving as an auxiliary agent into a covalent organic framework material modified by a long alkyl chain, ball-milling for 12-48 hours, standing the ball-milled mixed solution, and taking supernatant to obtain a covalent organic framework nano-sheet dispersion liquid modified by the long alkyl chain;
and 2, vacuum filtering the long alkyl chain modified covalent organic framework nano sheet dispersion liquid by taking a polyethylene film as a base film, adding ethanol after the vacuum filtering is finished, performing vacuum filtering and washing, and finally vacuum drying to obtain the long alkyl chain modified covalent organic framework composite membrane.
Preferably, in step 1, the organic solvent is N-methylpyrrolidone, dimethylformamide or acetonitrile, more preferably N-methylpyrrolidone.
Preferably, in step 1, the ball milling speed is 300 to 600rpm, more preferably 400rpm; the ball milling time is 6 to 48 and h, more preferably 24 hours.
Preferably, in step 2, the pore size of the polyethylene film is 50 to 200nm, more preferably 100nm.
Preferably, in step 2, the thickness of the covalent organic framework nanoplatelets in the composite film formed after vacuum filtration is 2-15 μm, 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 hours.
Further, the invention provides application of the long alkyl chain modified covalent organic framework composite membrane in lithium-sulfur batteries.
Compared with the prior art, the invention has the following advantages:
(1) The invention uses the COFs modified by long alkyl chains to regulate the state and the interlayer spacing, thereby improving the ball milling stripping efficiency. The adoption of the nano-sheet composite structure can greatly reduce the thickness of the diaphragm to 9-15 mu m, compared with a covalent organic framework material diaphragm and a pure PE polymer film which are directly pressed into powder, the long alkyl chain reduces the aperture of the covalent organic framework, so that the shuttling of lithium polysulfide can be inhibited, and meanwhile, the alkyl chain has excellent electrolyte wettability, and the passing of the lithium polysulfide is blocked through physical repulsion and chemical adsorption.
(2) The lithium-sulfur battery formed by taking the long alkyl chain modified covalent organic framework composite membrane as the membrane has high specific capacity of 600mAh/g, excellent cycling stability, capacity attenuation inhibition, and high specific capacity stability after cycling for 100 circles, wherein the specific capacity is more than 550 mAh/g.
Drawings
FIG. 1 is an XRD pattern for COF-C12, COF-C16 and COF-C20;
FIG. 2 is an infrared spectrum of COF-C12, COF-C16 and COF-C20;
FIG. 3 is a thermogravimetric analysis of COF-C12, COF-C16 and COF-C20;
FIG. 4 is a SEM image of the surface of a comparative pure PE separator;
FIG. 5 is a surface SEM image of a COF-C12 composite separator;
FIG. 6 is a surface SEM image of a COF-C16 composite separator;
FIG. 7 is a surface SEM image of a COF-C20 composite separator;
FIG. 8 is an ion conductivity graph of COF-C12, COF-C16 and COF-C20 composite separators and comparative samples;
FIG. 9 is a cycle chart of a lithium sulfur battery assembled from a COF-C12 composite separator;
FIG. 10 is a cycle chart of a lithium sulfur battery assembled from a COF-C16 composite separator;
FIG. 11 is a cycle chart of a lithium sulfur battery assembled from a COF-C20 composite separator;
FIG. 12 is a cycle chart of a lithium sulfur battery assembled from a comparative pure PE separator;
fig. 13 is a cycle chart of a lithium sulfur battery assembled by comparative COF-C12 powder tabletting.
Detailed Description
The present invention will be further described in detail below with reference to examples, which are provided to illustrate the objects, technical solutions and advantages of the present invention. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. To make several variants and improvements, all falling within the scope of protection of the present invention.
NH according to the invention 2 NH-Cx is commercially availableCan also be prepared by self, by NH 2 NH-C16 is exemplified by the following synthetic route:
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 30ml of N, N-Dimethylformamide (DMF) in N 2 After the reaction is finished, extracting with dichloromethane, washing with saturated saline, drying with anhydrous sodium sulfate, removing solvent by vacuum spin drying, and separating and purifying by column chromatography to obtain a compound 1c;
(2)NH 2 NH-C16: adding the compound 1c and hydrazine hydrate into 15ml of 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 covalent organic framework material (COF-C12) modified by long alkyl chain is prepared from trihydroxy trimellitic aldehyde and NH 2 The organic framework structure formed by the schiff base reaction of NH-C12 is shown as follows:
NH 2 the structure of NH-C12 is shown below:
the preparation method of the COF-C12 comprises the following specific steps:
a glass ampoule (volume: 20mL, length of 18cm, neck length of 9 cm) was filled with trihydroxybenzene trialdehyde (21.0 mg,0.1 mmol), NH 2 NH-C12 (84.5 mg,0.15 mmol) and mesitylene/1, 4-dioxane solution (3:1, v/v,4 mL). Then, the ampoule is 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 an ultrasonic bath for 2 minutes. The mixture was sonicated for 2 minutes to obtain a uniform dispersion. The tube was then flash 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 ampoule bottle neck, centrifuging to separate yellow gel product, washing with acetone (3×10mL), soaking in anhydrous acetone for 12h, and vacuum drying at 80deg.C for 12h to obtain COF-C12 as yellow colloid powder. The reaction formula is as follows:
example 2
The long alkyl chain modified covalent organic framework material (COF-C16) is prepared from trihydroxy trimellitic aldehyde and NH 2 The organic framework structure formed by the schiff base reaction of NH-C16 is shown as follows:
NH 2 the structure of NH-C16 is shown below:
the preparation method of the COF-C16 comprises the following specific steps:
a glass ampoule (volume: 20mL, length of 18cm, neck length of 9 cm) was filled with trihydroxybenzene trialdehyde (21.0 mg,0.1 mmol), NH 2 NH-C16 (101.3 mg,0.15 mmol) and mesitylene/1, 4-dioxane solution (3:1, v/v,4 mL). Then, the ampoule is immersed in an ultrasonic bath for 5 minutes; then 0.4mL of 6.0mol L was added -1 Acetic acid, the ampoule was immersed in an ultrasonic bath for 2 minutes. The mixture was sonicated for 2 minutes to obtain a uniform dispersion. The tube was then flash 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 ampoule bottle neck, centrifuging to separate yellow gelThe product was washed with acetone (3X 10 mL), soaked in anhydrous acetone for 12h, and vacuum dried at 80℃for 12h to give COF-C16 as yellow colloidal powder. The reaction formula is as follows:
example 3
The covalent organic framework material (COF-C20) modified by long alkyl chain is prepared from trihydroxy trimellitic aldehyde and NH 2 The organic framework structure formed by the schiff base reaction of NH-C20 is shown as follows:
NH 2 the structure of NH-C20 is shown below:
the preparation method of the COF-C20 comprises the following specific steps:
a glass ampoule (volume: 20mL, length of 18cm, neck length of 9 cm) was filled with trihydroxybenzene trialdehyde (21.0 mg,0.1 mmol), NH 2 NH-C20 (118.1 mg,0.15 mmol) and mesitylene/1, 4-dioxane solution (3:1, v/v,4 mL). Then, the ampoule is immersed in an ultrasonic bath for 5 minutes; then 0.4mL of 6.0mol L was added -1 Acetic acid, the ampoule was immersed in an ultrasonic bath for 2 minutes. The mixture was sonicated for 2 minutes to obtain a uniform dispersion. The tube was then flash 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 ampoule bottle neck, centrifuging to separate yellow gel product, washing with acetone (3×10ml), soaking in anhydrous acetone for 12h, and vacuum drying at 80deg.C for 12h to obtain COF-C20 as yellow colloid powder. The reaction formula is as follows:
example 4
100mg of COF-C12 colloid powder is added into a ball milling tank of polytetrafluoroethylene, 15 agate ball milling beads with the diameter of 5mm are added, 20mL of N-methyl pyrrolidone is added, ball milling is carried out for 24 hours at the rotating speed of 300rpm, standing is carried out after ball milling is finished, and the supernatant is taken as a well-dispersed COF-C12 nanosheet solution.
Selecting a polyethylene film with the aperture of 100nm as a bottom film of a vacuum suction filtration device, then dripping 20mL of a well-dispersed COF-C12 nanosheet solution on the bottom film, performing suction filtration under the condition of 0.1MPa vacuum degree, waiting for the solvent to be completely filtered, adding 10mL of ethanol, performing suction filtration and washing, and then drying the solvent in a vacuum oven at 50 ℃ to obtain the COF-C12 composite membrane.
Example 5
100mg of COF-C16 colloid powder is added into a ball milling tank of polytetrafluoroethylene, 15 agate ball milling beads with the diameter of 5mm are added, 20mL of N-methyl pyrrolidone is added, ball milling is carried out for 24 hours at the rotating speed of 300rpm, standing is carried out after ball milling is finished, and the supernatant is taken as a well-dispersed COF-C16 nanosheet solution.
Selecting a polyethylene film with the aperture of 100nm as a bottom film of a vacuum suction filtration device, then dripping 20mL of a well-dispersed COF-C16 nanosheet solution on the bottom film, performing suction filtration under the condition of 0.1MPa vacuum degree, waiting for the completion of the suction filtration of a solvent, adding 10mL of ethanol solvent for suction filtration and washing, and then drying the solvent in a vacuum oven at 50 ℃ to obtain the COF-C16 composite membrane.
Example 6
100mg of COF-C20 colloid powder is added into a ball milling tank of polytetrafluoroethylene, 15 agate ball milling beads with the diameter of 5mm are added, 20mL of N-methyl pyrrolidone is added, ball milling is carried out for 24 hours at the rotating speed of 300rpm, standing is carried out after ball milling is finished, and the supernatant is taken as a well-dispersed COF-C20 nanosheet solution.
Selecting a polyethylene film with the aperture of 100nm as a bottom film of a vacuum suction filtration device, then dripping 20mL of a well-dispersed COF-C20 nanosheet solution on the bottom film, performing suction filtration under the condition of 0.1MPa vacuum degree, waiting for the completion of the suction filtration of a solvent, adding 10mL of ethanol solvent for suction filtration and washing, and then drying the solvent in a vacuum oven at 50 ℃ to obtain the COF-C20 composite membrane.
Example 7
The films formed by tabletting the COF-C12, the COF-C16, the COF-C20 composite diaphragm, the comparative pure PE battery diaphragm and the COF-C12 are respectively added into a stainless steel symmetrical battery as battery diaphragms, and the battery is assembled in a glove box. The specific implementation method of the conductivity curve of the test battery is as follows: the impedance profile of the cell was measured using a Biological system at 25℃and 0.1-1 MHz in an incubator.
Example 8
The films obtained by tabletting the COF-C12, COF-C16 and COF-C20 composite films and the pure PE film and the COF-C12 film as comparison samples were used as films of lithium-sulfur batteries, and the lithium-sulfur batteries were assembled in a glove box. The battery charge-discharge curve is tested, and the specific implementation method is as follows: and (3) placing the battery in a clean incubator, and measuring the charge-discharge curve of the battery by a blue electric system under the condition of 0.2C charge-discharge multiplying power under the voltage of 1.7-2.8V.
FIG. 1 is an XRD pattern of COF-C12, COF-C16 and COF-C20 illustrating that the long alkyl chain modified covalent organic framework material prepared according to the present invention has good crystallinity.
FIG. 2 is an infrared spectrum of COF-C12, COF-C16 and COF-C20 demonstrating the formation of C-N bonds.
FIG. 3 is a thermogravimetric analysis of COF-C12, COF-C16 and COF-C20 illustrating that the long alkyl chain modified covalent organic framework material 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 with a pore size much larger than the COF modified membrane surface.
Fig. 5 is a SEM image of the surface of the 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 an ion conductivity graph of COF-C12, COF-C16, COF-C20 composite separator and comparative sample, demonstrating that the long alkyl chain modified covalent organic framework composite separator has more excellent lithium ion transport effect compared to the pure PE battery separator.
Fig. 9 is a cycle chart of a lithium sulfur battery assembled from COF-C12 composite separator, illustrating that the lithium sulfur battery assembled from COF-C12 composite separator has good cycle stability (cycle 52) and high specific capacity (650 mAh/g).
Fig. 10 is a cycle chart of a lithium sulfur battery assembled from COF-C16 composite separator, illustrating that the lithium sulfur battery assembled from COF-C16 composite separator has good cycle stability (cycle 52) and high specific capacity (635 mAh/g).
Fig. 11 is a cycle chart of a lithium sulfur battery assembled from COF-C20 composite separator, illustrating that the lithium sulfur battery assembled from COF-C20 composite separator has good cycle stability (cycle 52) and high specific capacity (630 mAh/g).
Fig. 12 is a cycle chart of a lithium sulfur battery assembled from a comparative pure PE separator, which is not stable in cycle and decays rapidly in specific capacity.
Fig. 13 is a cycle chart of a lithium sulfur battery of a separator formed by tabletting COF-C12 powder as a comparative sample, which is unstable in cycle and fast in specific capacity decay.
Claims (13)
1. A long alkyl chain modified covalent organic framework material characterized by the structural formula:
，
or (b)
。
2. The method for preparing a long alkyl chain modified covalent organic framework material according to claim 1, comprising the steps of:
adding trihydroxy benzene trialdehyde 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 into a suspension, performing liquid nitrogen freezing, vacuumizing and degassing treatment on the suspension, sealing a pipe by using a flame gun in a vacuum state, then reacting for 48-168 hours at 120+/-20 ℃ to obtain a crude product, washing the crude product, performing suction filtration, performing Soxhlet extraction by tetrahydrofuran and chloroform, and finally performing vacuum drying to obtain a covalent organic framework material modified by the long alkyl chain; in the mesitylene/1, 4-dioxane solution, the volume ratio of the mesitylene to the 1, 4-dioxane is 1:7~7:1, wherein the structural formula of the long alkyl chain modified amino compound is as follows:
，/>or->；
The structural formula of the trihydroxy benzene trialdehyde is as follows:
。
3. the method of claim 2, wherein the molar ratio of the trihydroxybenzene trialdehyde to the long alkyl chain modified amine compound is 2:3.
4. The preparation method according to claim 2, wherein the number of times of freezing, vacuuming and degassing treatment with liquid nitrogen is 3 or more; the concentration of acetic acid is 3-12 mol/L; the reaction temperature is 120 ℃ and the reaction time is 72 h; the crude product was washed successively with dichloromethane, ethyl acetate, methanol, acetone.
5. The method according to claim 2, wherein the acetic acid concentration is 6mol/L.
6. The preparation method of the long alkyl chain modified covalent organic framework composite membrane is characterized by comprising the following steps of:
step 1, adding an organic solvent as an auxiliary agent into the covalent organic framework material modified by long alkyl chain in the step 1, ball-milling for 12-48 hours, standing the ball-milled mixed solution, and taking supernatant to obtain a dispersion liquid of the covalent organic framework nano-sheets modified by long alkyl chain;
and 2, vacuum filtering the long alkyl chain modified covalent organic framework nano sheet dispersion liquid by taking a polyethylene film as a base film, adding ethanol after the vacuum filtering is finished, performing vacuum filtering and washing, and finally vacuum drying to obtain the long alkyl chain modified covalent organic framework composite membrane.
7. The method according to claim 6, wherein in step 1, the organic solvent is N-methylpyrrolidone, dimethylformamide or acetonitrile; the ball milling rotating speed is 300-600 rpm; the ball milling time is 6-48 h.
8. The method according to claim 6, wherein in the step 1, the ball milling speed is 400rpm and the ball milling time is 24h.
9. The method according to claim 6, wherein in the step 2, the pore diameter of the polyethylene film is 50 to 200 nm; in the composite membrane formed after vacuum filtration, the thickness of the covalent organic framework nano sheet layer is 2-15 mu m.
10. The method according to claim 6, wherein in the step 2, the pore diameter of the polyethylene film is 100 nm; in the composite membrane formed after vacuum filtration, the thickness of the covalent organic framework nano sheet layer is 5 mu m.
11. The method according to claim 6, wherein in the step 2, the vacuum degree is 0.1MPa; the vacuum drying temperature is 60-80 ℃, and the drying time is more than 10 hours.
12. The long alkyl chain modified covalent organic framework composite membrane prepared by the preparation method according to any one of claims 6 to 11.
13. Use of the long alkyl chain modified covalent organic framework composite separator according to claim 12 in lithium sulfur batteries.
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