CN116082591A - Preparation method and application of three-dimensional covalent organic framework 3D COF material based on 8-communicated cubic ligand - Google Patents

Preparation method and application of three-dimensional covalent organic framework 3D COF material based on 8-communicated cubic ligand Download PDF

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CN116082591A
CN116082591A CN202310228926.5A CN202310228926A CN116082591A CN 116082591 A CN116082591 A CN 116082591A CN 202310228926 A CN202310228926 A CN 202310228926A CN 116082591 A CN116082591 A CN 116082591A
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cof material
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郑芬芬
王欢
尹瑞泽
晏宇畅
雒腾飞
甘媛
廖垚垚
郑佳进
熊维伟
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Jiangsu University of Science and Technology
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Abstract

The invention discloses a preparation method and application of a three-dimensional covalent organic framework 3D COF material based on 8-communication cubic ligands, wherein the preparation method comprises the following steps: dissolving 3, 5-dibromobenzaldehyde and pyrrole in an acid solvent, heating and reacting to generate a product A, reacting with p-acyl phenyl boric acid to generate a product B, dissolving the product B and TAPP in an organic solvent, adding a catalyst, then circulating liquid nitrogen, freezing, vacuumizing and thawing, preserving heat at constant temperature, cooling, centrifuging, collecting precipitate, and drying to obtain the product [8+4] type 3D COF material. The 3D [8+4] COF material prepared by condensing the 8-connected cubic ligand TTEP and the 4-connected square plane construction unit can promote charge transfer by a 3D porous structure and uniform active sites when being used as a lithium ion battery anode material, is beneficial to intercalation and deintercalation of lithium ions, inhibits volume expansion and obtains excellent practical electrochemical energy storage performance.

Description

Preparation method and application of three-dimensional covalent organic framework 3D COF material based on 8-communicated cubic ligand
Technical Field
The invention relates to the field of lithium ion battery cathode materials, in particular to a preparation method and application of a three-dimensional covalent organic framework 3D COF material based on 8-connected cubic ligands.
Background
With the continuous development of the industrial age, the worldwide productivity is continuously improved, and the power in the production is mainly provided by non-renewable fossil energy sources. Along with the continuous reduction of energy reserves and the continuous rising of emerging industries, green and renewable energy sources are required to be developed, wherein new energy sources such as solar energy, wind energy, water conservancy and tidal energy are mainly used, in order to solve the intermittent problem of the energy sources, requirements are put forward on the development of energy storage equipment, lithium batteries are rapidly developed and practically applied according to the high capacity, the practicability and the stability of the lithium batteries, and meanwhile, the development and preparation of electrode materials with high specific capacity, high volume density and safety are of great significance to the development of the lithium batteries and the practical application of the equipment such as power, 3C and the like.
Covalent organic framework Compounds (COFs) are an emerging crystalline organic polymer with inherent porosity, structural periodicity and light element components, and a covalently-connected two-dimensional or three-dimensional expansion framework with periodicity is constructed through organic units, so that the COFs material is widely researched and applied in a plurality of fields such as gas adsorption, luminescence, electrocatalysis, energy storage, semiconductors and the like. In the field of electrochemical energy storage, the current anode material is the most widely applied carbon material, has the advantages of abundant reserves, wide sources, low cost, stable electrochemical properties and the like, but also has the defects of low coulomb efficiency, low specific capacity, poor multiplying power performance and the like for the first time, cannot meet the requirements of high-performance batteries, cannot meet the requirements of high volume density, high specific capacity and the like of the current energy storage equipment, and therefore, needs to develop a novel anode material. The COFs materials realize rapid development due to the characteristics of various structures, high porosity, high chemical stability and high theoretical capacity, but most of traditional COFs material researches are concentrated on 2DCOFs, and the layered structure, rich active sites, high porosity and clear channels are favorable for the transmission and intercalation and deintercalation of charges and lithium ions, but in practical application, the practical specific capacity of the 2D COFs materials is not ideal, and the dense packing of the layer structure leads to the unidirectional one-dimensional (1D) pore channels with minimum transmissibility and a large number of buried active sites, so that the electrochemical performance of the unidirectional one-dimensional (1D) pore channels is limited to a certain extent. In contrast, in 3D COFs materials, the framework structure can avoid pi-plane stacking phenomena, which results in higher surface area, more uniform active sites, and better stability than 2D COFs, resulting in maximum utilization of ion diffusion multipass and active sites. However, conjugated 3D COFs are still very rare due to the lack of sufficient conjugated 3D building blocks compared to the abundant variety of 2D COFs materials, so that the development of multi-connected organic ligand building blocks and the exploration of high quality synthetic methods are necessary for the development of conjugated three-dimensional COFs, especially for the application of COFs materials in the field of lithium ion battery anode materials.
Disclosure of Invention
The invention aims to: aiming at the problems existing in the prior art, the invention provides a preparation method of a three-dimensional covalent organic framework 3D COF material based on an 8-communication cubic ligand, and the 3D COF material prepared by the preparation method has rich active sites which are uniformly distributed and better structural stability, can be used as an electrochemical active center, can inhibit the dissolution and stacking phenomena and the volume expansion problem of a 2D COF material in an organic electrolyte, can be used as a cathode material of a novel high-performance lithium ion battery, can solve the problems of poor stacking and conductivity and volume expansion existing in the conventional electrode material, and has better stability, capacity and safety.
The invention also provides the three-dimensional covalent organic framework 3D COF material based on the 8-communication cubic ligand and application thereof as a lithium ion anode material.
The technical scheme is as follows: in order to achieve the above purpose, the preparation method of the three-dimensional covalent organic framework 3D COF material based on 8-connected cubic ligands comprises the following steps:
(1) Dissolving 3, 5-dibromobenzaldehyde and pyrrole in an acidic solvent, and heating to react to generate an intermediate product A;
(2) The product A and p-acyl phenyl boric acid are subjected to Suzuli coupling reaction to generate a product B;
(3) Dissolving the product B and 5,10,15, 20-tetra (4-aminophenyl) porphyrin (TAPP) in an organic solvent, and fully dispersing and dissolving by ultrasonic waves;
(4) Adding a catalyst into the mixture obtained in the step (3), and then, carrying out circulating liquid nitrogen freezing, vacuumizing and thawing, and then, carrying out constant-temperature heat preservation to obtain a suspension;
(5) And cooling the suspension to room temperature, centrifuging, collecting the precipitate, and drying to obtain the product [8+4] type 3D COF material.
Wherein the molar ratio of the 3, 5-dibromobenzaldehyde to the pyrrole in the step (1) is 1:1-1:1.2; the acid solution is acetic acid or propionic acid; the heating temperature is 130-150 ℃; the reaction time is 2-4 hours.
Preferably, 3, 5-dibromobenzaldehyde and pyrrole are heated to perform condensation cyclization to synthesize 5,10,15, 20-tetra (3, 5-dibromophenyl) porphyrin (TDBrEP).
Preferably, the molar mass ratio of 3, 5-dibromobenzaldehyde to pyrrole is 1:1.1, and the solvent selects propionic acid; the heating temperature is 140 ℃; the reaction time was 3 hours; 3, 5-dibromobenzaldehyde and pyrrole are subjected to condensation cyclization reaction under heating, and the intermediate product A is obtained by suction filtration, washing and drying.
Wherein the molar ratio of the intermediate product A to the p-acyl phenyl boric acid in the step (2) is 1:8-1:10; the heating temperature condition of the Suzuli coupling reaction is 80-120 ℃, and the reaction time is 1-3 days; the solvent for the Suzuli coupling reaction is dioxane, tetrahydrofuran and water or dioxane and water.
Wherein, the alkaline is added in the Suzuli coupling reaction in the step (2)Metal salts and catalysts; the alkaline metal salt is Na 2 CO 3 、K 2 CO 3 Or CsCO 3 The method comprises the steps of carrying out a first treatment on the surface of the The catalyst is tetra (triphenylphosphine) palladium (0) and AsPh 3 、n-Bu 3 P or Ph 2 P(CH 2 ) 2 PPh 2 (dppe)。
Preferably, the product A and the p-acyl phenylboronic acid are subjected to Suzuli coupling reaction to generate a 5,10,15, 20-tetra (([ 1,1':3',1 '-triphenyl ] -4, 4' -dicarboxaldehyde)) (TTEP) ligand, and the product is obtained through extraction and spin-drying.
More preferably, the molar ratio of product a to p-acyl phenylboronic acid is 1:10; the solvent is tetrahydrofuran and water; the alkaline metal being K 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the The catalyst is tetra (triphenylphosphine) palladium (0); under the protection of argon, the reaction temperature is 100 ℃; the reaction time is 2 days; the extract liquid is dichloromethane, chloroform, ethyl acetate and the like.
Wherein the intermediate product B of step (3) is a 5,10,15, 20-tetrakis (([ 1,1':3',1 '-triphenyl ] -4, 4' -dicarboxaldehyde))) (TTEP) ligand; the molar ratio of TTEP to TAPP is 1:2-1:3; the organic solvent is one or more of dioxane, N-methyl pyrrolidone, N-dimethylformamide and 1,3, 5-trimethylbenzene.
Preferably, the molar ratio of TTEP to 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin (TAPP) is 1:2; the organic solvents were N-methylpyrrolidone (NMP) and 1,3, 5-trimethylbenzene.
Wherein, the catalyst in the step (4) can be 6M acetic acid.
Wherein, in the step (4), liquid nitrogen is rapidly frozen and then vacuumized until the internal pressure is 0.15-0.2mmHg, and the liquid nitrogen freezing, vacuumization and thawing are used as a cycle, and the heat preservation reaction is repeated for 2-3 times. The purpose of liquid nitrogen freezing-vacuumizing-thawing is to remove oxygen in the reaction solution, so that the experimental effect is better.
Wherein the temperature of the heat preservation in the step (4) is 100-140 ℃, and the reaction time is 3-7 days.
Preferably, the incubation is carried out at 120℃for a period of 5 days.
Wherein, DMF, dichloromethane or tetrahydrofuran and methanol can be used for washing for a plurality of times during the centrifugal separation in the step (5).
Wherein the drying in the steps is vacuum drying, and the temperature of the vacuum drying is 60-120 ℃.
The three-dimensional covalent organic framework 3D COF material based on the 8-communicated cubic ligand, which is prepared by the preparation method, is prepared.
The invention relates to an application of a three-dimensional covalent organic framework 3D COF material based on an 8-communication cubic ligand in the field of lithium ion battery cathode materials.
The invention provides a preparation method of a lithium ion anode material of a three-dimensional covalent organic framework 3D COF material based on an 8-connected cubic ligand, which can effectively solve the problems that a one-way one-dimensional (1D) pore channel has smaller transmissibility and a large number of buried active sites due to the dense accumulation of layer structures of a 2D COFs anode material for a lithium ion battery, so that the electrochemical performance of the lithium ion battery in actual use is affected. The 8-communicated aldehyde porphyrin ligand (TTEP) used in the invention has a porphine ring at the center, four substituents on the porphine ring cannot be coplanar due to the steric hindrance effect, the TTEP has a symmetrical three-dimensional cubic structure in space, the synthetic COF material is guaranteed to have a 3D structure, the stacking problem of 2D COFs materials is avoided, active sites are uniformly distributed and fully exposed to be fully utilized, and simultaneously, a multidimensional ion movement path can be provided, so that the multi-dimensional COF material has high connectivity and good stability.
The 8-communication cubic porphyrin ligand and the tetra-amino phenyl porphyrin (TAPP) two construction units selected by the invention are provided with central conjugated large pi-electron delocalization rings, and polyimide 3D COF materials formed by the two construction units are provided with strong conductivity in the parallel and vertical directions, so that the charge transmission is facilitated, the stability of a three-position framework can be maintained, and the large plane of the tetra-amino phenyl porphyrin (TAPP) plays a supporting role in the gradual synthesis process, so that the construction of a three-dimensional framework structure is facilitated. The synthesis of the 3D COF materials prepared according to the present invention is shown in fig. 10. The two construction units have more nitrogen content and benzene rings, and a large number of imine bonds are uniformly distributed in the 3D structure, so that the problem that the internal active sites cannot be fully utilized due to the stacking problem can be avoided, the problem of volume change in the process of lithium ion insertion and extraction is relieved, and meanwhile, abundant lithium storage sites can be provided and fully utilized, meanwhile, the lithium storage sites have good stability, and excellent lithium storage performance is obtained.
The invention synthesizes the [8+4] type 3D COF, and the [8+4] type 3D COF is firstly applied to the lithium battery anode material and has excellent electrochemical performance. From the structure of raw materials and COF and the synthetic steps and geometric expansion structure shown in FIG. 10, it can be seen that the [8+4] 3D COF material synthesized in the invention has the number of functional groups represented by 8 and 4, and the two unit functional groups are condensed to form [8+4] type, and the 3D [8+4] COF material prepared by condensing 8-connected cubic ligand TTEP and 4-connected square plane construction units has the 3D topological structure capable of avoiding pi-pi lamination phenomenon of 2D COFs material, and has symmetrical cubic nodes, high connectivity, permanent porosity and high specific surface area; the benzene rings and the like exist on the general planar 2D COF, so that pi-pi action is generated between layers, layers are closely stacked, the interlayer spacing is too small to be beneficial to movement and combination of lithium ions, and the pore size, the specific surface area and the like are also influenced.
Meanwhile, as can be seen from the frame structure of the 3D COF prepared by the invention, the interlayer has structural support with multidimensional pore channels (as shown in fig. 10), so that active sites can be uniformly distributed, the 3D porous structure and the uniform active sites can promote charge transfer when the frame structure is used as a negative electrode material of a lithium ion battery, the intercalation and deintercalation of lithium ions are facilitated, the volume expansion is inhibited, and excellent practical electrochemical energy storage performance is obtained, and the serious interlayer accumulation of the planar 2D COF can also accumulate active sites (functional groups or c=n bonds and the like), the interlayer is unfavorable for ion movement, and only pore channels in a one-dimensional movement direction can be accumulated.
The invention mainly uses the synthesized 3D COF material prepared by the reaction of the 8-connected cubic porphyrin ligand and the 4-connected rectangular TAPP ligand as the anode active material of the lithium ion battery, and explores a high-quality 3D COF synthesis method through a high-connectivity cubic building block, thereby promoting the development of synthesizing the COF material with a novel topological structure by using the high-connectivity building block and greatly enriching the types of 3D COFs. The 3D COF has a stable three-dimensional framework structure, and can effectively solve the problem that the active sites are gathered and a single ion channel causes that the actual application cannot obtain good electrochemical performance due to severe pi-pi stacking between 2D COF layers synthesized by the traditional triangle and quadrilateral building units. Meanwhile, porphyrin center electron-rich delocalization rings are arranged in the horizontal direction and the vertical direction of the material frame, so that the conductivity of the material can be improved. The [8+4] type high-connectivity 3D COF is applied to the field of lithium ion battery cathode materials for the first time, and excellent electrochemical performance is obtained.
Conventional COF materials have problems such as poor conductivity and poor physical electrochemical properties due to stacking problems, and a large amount of conductive agent is generally required to increase the conductivity of the electrode, but this reduces the energy density (the capacity of the carbon-based conductive agent is low). The stacking problem is conventionally solved by stripping, including mechanical ball milling and other modes, but the particle size and stacking can be reduced to a certain extent, and the stacking problem cannot be fundamentally solved. On the other hand, chemical stripping is usually carried out by adding other structures of branches on a two-dimensional material and other molecules between layers to spatially relieve the accumulation, but the steric hindrance may be increased, the synthesis process is more complicated, the conjugation of a COFs framework may be influenced, the structural stability is further influenced, and the method is less and has general effect. By combining the problems, the invention adopts a specific method to firstly utilize TTEP and TAPP two monomers to form [8+4] type 3D COF, the material is a 3D frame material, the structure of the material fundamentally solves the stacking problem, is more stable relative to the structure of a 2D material, and can avoid the interlayer spacing increase caused by interlayer lithium ion insertion, so that the problems of poor stability, poor cycle life, safety and the like caused by electrode volume change are solved. On the other hand, the problem of conductivity is solved, the large pi-electron delocalization ring of the material structure in the horizontal and vertical directions can improve the conductivity of the material, further improve parameters such as electron conductivity and the like, avoid the problem of reducing the capacity density due to the doping of a large amount of conductive agents, and have good electrochemical performance and very high capacity relative to other materials.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
the invention provides a preparation method of a lithium ion anode material based on a three-dimensional covalent organic framework 3D COF material with 8 communicated cubic ligands, which is characterized in that the 3D high-connectivity building block is communicated with 8, and then the 3D COF material with interpenetrating three-dimensional topological structure and high-connectivity permanent gaps is synthesized by a solvothermal method, so that the 3D COF material can be used as the lithium ion anode material, and the enrichment of the 3D COF material and the application in various fields are possible.
The 3D COF lithium ion battery cathode material prepared by the invention is different from the current situations that the existing graphite material has low energy density and the COFs electrode material has high theoretical capacity, but the actual specific capacity, low conductivity and poor stability, the 3D COF material synthesized by the unique cubic ligand of the material enables rich active sites to be uniformly distributed, the conjugated space frame structure has excellent thermal stability and chemical stability, the structure fundamentally solves the stacking problem of the 2D COF material, is more stable than the 2D material structure, can avoid the increase of interlayer spacing caused by inserting lithium ions between layers, and further solves the problems of poor battery stability, poor cycle life, safety and the like caused by the change of the electrode volume. On the other hand, the material has a central conjugated large pi-electron delocalization ring on the parallel and vertical planes, provides good charge transmission performance, obtains high conductivity, stable cycle performance and excellent electrochemical energy storage performance, and the [8+4] type high-connectivity 3D COF prepared by the invention is firstly applied to the field of lithium ion battery cathode materials, and obtains excellent electrochemical performance.
Drawings
FIG. 1 shows a construction unit TTEP of a 3D COF material of a three-dimensional covalent organic framework based on 8-linked cubic ligands prepared according to the invention 1 H NMR chart;
FIG. 2 is an SEM image of a three-dimensional covalent organic framework 3D COF material based on 8-linked cubic ligands prepared according to the present invention;
FIG. 3 is a Fourier transform infrared (FT-IR) diagram of a three-dimensional covalent organic framework 3D COF material based on 8-way cubic ligands prepared according to the invention;
FIG. 4 is a polycrystalline X-ray diffraction (PXRD) diagram of a 3D COF material of a three-dimensional covalent organic framework based on 8-linked cubic ligands prepared according to the present invention;
FIG. 5 is a nitrogen adsorption-desorption (BET) diagram of a three-dimensional covalent organic framework 3D COF material based on 8-linked cubic ligands prepared according to the present invention;
FIG. 6 shows that the three-dimensional covalent organic framework 3D COF material based on 8-connected cubic ligands prepared by the invention is in 200mA g -1 250 cycles of the current density of (c) performance map;
FIG. 7 shows that the three-dimensional covalent organic framework 3D COF material based on 8-connected cubic ligands prepared by the invention is at 1000mA g -1 A 1000 cycle performance plot at current density of (c);
FIG. 8 shows the rate capability of a 3D COF material based on an 8-connected cubic ligand with a three-dimensional covalent organic framework prepared by the invention under different current densities;
FIG. 9 shows that the 3D COF material of the three-dimensional covalent organic framework based on 8-connected cubic ligands prepared by the invention has the sweeping speed of 0.2mV s at 0.01-3.00V -1 Cyclic voltammograms of (2);
FIG. 10 shows the steps and framework structure of a three-dimensional covalent organic framework 3D COF material based on 8-way cubic ligands prepared according to the present invention.
Detailed Description
The invention is further described below with reference to specific embodiments and figures.
The experimental methods described in the examples, unless otherwise specified, are all conventional; the reagents and materials, unless otherwise specified, are commercially available.
Wherein 3, 5-dibromobenzaldehyde, pyrrole, methanol, p-acyl phenyl boric acid, tetrahydrofuran (THF), anhydrous potassium carbonate, propionic acid and Dichloromethane (DCM) are all purchased from the Tatany technology exploration platform. Ketjen black, polyvinylidene fluoride (average molecular weight 40-50 ten thousand), N-methylpyrrolidone (NMP), mesitylene, glacial acetic acid, 5,10,15, 20-tetraaminophenyl porphyrin (TAPP), tetra (triphenylphosphine) palladium (0) are all purchased from an Aba Ding Huaxue reagent network.
Example 1
The preparation method of the three-dimensional covalent organic framework 3D COF material based on the 8-linked cubic ligand comprises the following steps:
(1) 3, 5-dibromobenzaldehyde (3.96 g,15 mmol) and 200ml propionic acid were added to a 500ml double port round bottom bottle, N 2 Stirring and dissolving under protection, when the reaction is heated to reflux, dropwise adding 1.1ml of pyrrole diluted by 10ml of propionic acid into a reaction system, heating the reaction system to 140 ℃ for continuous reflux reaction for 3 hours, cooling after the reaction is finished, carrying out suction filtration, washing the solid with a large amount of methanol, and transferring to a vacuum drying oven for 12 hours at 80 ℃ to obtain a purple product A.
(2) Product A compound (1 g,0.8 mmol), p-acylphenylboronic acid (1670 mg,8.0 mmol), tetrakis (triphenylphosphine) palladium (0) (240 mg,0.2 mmol) and anhydrous potassium carbonate (2.67 g,19.2 mmol) were weighed into a 250ml double neck round bottom bottle, the mixture was degassed three times under argon atmosphere and THF (70 ml) and H were added to the reaction system 2 O (20 ml), the reaction was heated to 100deg.C and stirred for 48 hours. 50ml of DCM was added to the mixture to dissolve and extract three times, anhydrous sodium sulfate was added to the extract to remove water, the mixture was filtered to collect the filtrate and spin-dried, and recrystallized multiple times from methylene chloride and methanol to give 5,10,15, 20-tetra (tetrakis (([ 1,1':3',1 "-triphenylamine)]-4,4 "-dicarboxaldehyde)), and (TTEP).
(3) TTEP (0.0724 g,0.05 mmol) and 5,10,15, 20-tetraaminophenyl porphyrin (TAPP) (0.675 g,0.1 mmol) were dissolved in a mixture of NMP (2 mL) and 1,3, 5-trimethylbenzene (2 mL), and the mixture was well dissolved by sonication;
(4) Adding 0.4mL of 6M AcOH into the mixture in the step (3), transferring the mixed solution into a Pyrex tube, quickly freezing the mixed solution by liquid nitrogen (the solution does not flow), vacuumizing to the internal pressure of 0.15mmHg, thawing, and repeating the steps for 3 times by taking the liquid nitrogen freezing-vacuumizing-thawing as a cycle. The reaction mixture was incubated at 120℃for 3 days in an incubator.
(5) And (3) centrifuging the suspension obtained in the step (4) to remove the supernatant to obtain a dark brown precipitate, then centrifuging and Soxhlet extracting the product for multiple times by using THF (20 ml multiplied by 3 times) and acetone (20 ml multiplied by 3 times), and finally drying the solid under vacuum at 80 ℃ for 12 hours to obtain a dark brown solid product which is the three-dimensional covalent organic framework 3D COF material based on 8-communicated cubic ligands.
FIG. 1 is a block diagram of a cube construction element TTEP according to the invention 1 An H-NMR chart of the sample, 1 H NMR(400MHz,Chloroform-d)δ10.15–10.05(m,2H),9.06(s,2H),8.60(s,2H),8.35(s,1H),8.13–7.99(m,8H)。
fig. 2 is an SEM image of a 3D COF material prepared according to the present invention, and as can be seen from fig. 2, the 3D COF material has a flower-like morphology composed of sheets, which is different from an irregular stacking morphology of sheets of most of the existing 2D COFs. FIG. 3 is a FT-IR chart of a 3D COF material prepared according to the invention, and it can be seen from FIG. 3 that the 3D COF material is in 1620cm -1 The band at this point is sufficient to demonstrate the formation of new bonds of c=n, whereas 1696cm -1 C=o characteristic peak and 3340cm for the nearby TTEP monomer -1 No N-H characteristic bands of the nearby TAPP monomers are present, which is a sufficient indication that both monomers form new species via imine linkages. Fig. 4 is a PXRD pattern of the 3D COF material prepared in the present invention, and as can be seen from fig. 4, the 3D COF material shows diffraction peaks at 2.74 °, 6.42 ° and 10.42 °, which indicates the formation of a framework network structure, and proves that the synthesis of the 3D COF material with high crystallinity is successful. FIG. 5 is a BET diagram of a 3D COF material prepared according to the present invention, as can be seen from FIG. 5, using N at 77K 2 Adsorption isotherm analysis investigated the specific surface area of 3D COF materials. In the low pressure range (P/P0<0.05)，N 2 The rapid uptake of (a) indicates a typical type I isotherm, revealing its microporous nature, its framework structure with high specific surface area and micropore filling.
Example 2
The 3D COF material prepared by the invention is used for electrochemical performance test of lithium ion anode materials.
The testing steps are as follows: the 3D COF material prepared in example 1 was used as an active material, and about 35mg of the active material was weighed according to the active material: conductive agent (ketjen black): the polymeric binder (polyvinylidene fluoride, PVDF) was 7:2:1, grinding in a mortar, and adding about 350 μlNMP (N-methyl pyrrolidone) is used as a solvent to fully dissolve the adhesive, and is stirred for 12 hours to be uniformly mixed, so that slurry with flowing trend is obtained; coating the slurry on the rough surface of the copper foil through a film drawing device, selecting 150 mu m surface by a four-side film drawing device, keeping the coated film in a vacuum drying oven at 80 ℃ for more than 10 hours to fully volatilize the solvent, cutting the copper foil coated with the active material into electrode plates with the diameter of 12mm by using a slicing machine, and controlling the mass of the active material on each electrode plate to be about 1.0 mg. For assembling lithium ion batteries, celgard2600 and lithium sheets were used as battery separator and counter electrode, respectively, with an electrolyte of 1mol L -1 LiPF of (a) 6 Solution (ethylene carbonate/dimethyl carbonate/diethyl carbonate V: v=1:1:1); the cell was assembled in a glove box at an ambient temperature of 25 ℃ with both oxygen and moisture levels below 1ppm. The LAND CT 2001A blue electric system is used for constant current charge and discharge test, and the CHI660E electrochemical workstation is used for testing cyclic voltammetry (voltage range 0.01-3.0V, scanning rate 0.2mV s -1 ) And impedance (frequency range 0.01 Hz-100 kHz). FIG. 6 shows that the 3D COF material prepared by the method is used as a lithium ion anode material at the voltage of 0.01-3V and 200mA g -1 As can be seen from FIG. 6, the current density of (C) is 250 times, and the reversible specific capacity after stabilization is 1190mAh g -1 . FIG. 7 shows the COF material prepared by the method of the present invention as a lithium ion negative electrode material at 1000mAg -1 As can be seen from FIG. 7, the reversible specific capacity is 736mAh g -1 。
The ultra-high specific capacity and excellent stability in the small-current short-cycle and large-current long-cycle tests prove that the structure characteristics of the material bring about excellent energy storage performance and cycle performance when the active sites are fully utilized, and as shown in FIG. 8, the 3D COF material prepared by the invention is taken as the lithium ion anode material, and the multiplying power performance of the lithium ion anode material under different current densities is shown in FIG. 8, when the current densities are 200, 500, 1000, 2000, 4000 and 200mAg -1 At this time, the capacities of the 3D COF electrodes were 889, 517, 442, 298, 222 and 1199mAh g, respectively -1 It was confirmed that it has excellent rate performance and structural stability. FIG. 9 shows that the COF material prepared according to the present invention has a sweep rate of 0.2mV s at 0.01-3.00V -1 As can be seen from fig. 9, in the first cathodic reduction, there are significant reduction peaks around 0.30 and 0.73V, which disappear in the subsequent scan due to the formation of a Solid Electrolyte Interface (SEI). For the first anodic scan, there are two low potential anodic peaks at 0.53V and 1.24V. The tendency to redox is substantially the same in the next second and third scans, indicating that the material has good reversibility. The reduction of the redox potential difference after the second turn compared to the first turn indicates that the polarization of the electrode material is reduced and the electrochemical powertrain is significantly improved.
Example 3
Example 3 was prepared in the same manner as in example 1, except that: the molar ratio of the 3, 5-dibromobenzaldehyde to the pyrrole in the step (1) is 1:1, the acidic solution is acetic acid, and the heating temperature is 130 ℃; the reaction time was 4 hours.
The molar ratio of the product A to the p-acyl phenyl boric acid in the step (2) is 1:8, the heating temperature condition for the reaction is 80 ℃, and the reaction time is 3 days; the solvent condition of the reaction is dioxane, and the alkaline metal salt condition of the reaction is K 2 CO 3 The catalyst condition is AsPh 3 。
The molar ratio of TTEP to TAPP in the step (3) is 1:2, and the organic solution is dioxane (2 ml) and mesitylene (2 ml).
And (3) rapidly freezing the liquid nitrogen used in the step (4), vacuumizing to the internal pressure of 0.2mmHg, repeating the steps of freezing, vacuumizing and thawing the liquid nitrogen into a cycle, and carrying out heat preservation reaction for 2 times, wherein the heat preservation temperature is 100 ℃, and the reaction time is 7 days.
Example 4
Example 4 was prepared in the same manner as example 1, except that: the molar ratio of the 3, 5-dibromobenzaldehyde to the pyrrole in the step (1) is 1:1.2, the acidic solution is pyridine, and the heating temperature is 150 ℃; the reaction time was 2 hours.
The molar ratio of the product A to the p-acyl phenyl boric acid in the step (2) is 1:10, the heating temperature condition of the reaction is 120 ℃, and the reaction time is 1 day; the solvent conditions of the reaction are dioxane and water, and the alkali of the reactionSexual metal salt condition CsCO 3 The catalyst condition is n-Bu 3 P。
The molar ratio of TTEP to TAPP in the step (3) is 1:3, and the organic solution is N-methylpyrrolidone.
The temperature of the heat preservation in the step (4) is 140 ℃, and the reaction time is 3 days.

Claims (10)

1. The preparation method of the three-dimensional covalent organic framework 3D COF material based on the 8-communicated cubic ligand is characterized by comprising the following steps of:
(1) Dissolving 3, 5-dibromobenzaldehyde and pyrrole in an acid solvent, and heating to react to generate a product A;
(2) The product A and p-acyl phenyl boric acid are subjected to Suzuli coupling reaction to generate a product B;
(3) Dissolving the product B and 5,10,15, 20-tetra (4-aminophenyl) porphyrin (TAPP) in an organic solvent, and fully dispersing and dissolving by ultrasonic waves;
(4) Adding a catalyst into the mixture obtained in the step (3), and then, carrying out circulating liquid nitrogen freezing, vacuumizing and thawing, and then, carrying out constant-temperature heat preservation to obtain a suspension;
(5) And cooling the suspension to room temperature, centrifuging, collecting the precipitate, and drying to obtain the product [8+4] type 3D COF material.
2. The method for preparing a three-dimensional covalent organic framework 3D COF material based on 8-linked cubic ligands according to claim 1, characterized in that the molar ratio of 3, 5-dibromobenzaldehyde to pyrrole in step (1) is 1:1-1:1.2; the acid solution is acetic acid or propionic acid; the heating temperature is 130-150 ℃; the reaction time is 2-4 hours.
3. The method for preparing a three-dimensional covalent organic framework 3D COF material based on 8-linked cubic ligands according to claim 1, characterized in that the molar ratio of the intermediate product a to p-acyl phenyl boronic acid in step (2) is 1:8-1:10; the heating temperature condition of the Suzuli coupling reaction is 80-120 ℃, and the reaction time is 1-3 days; the solvent for the Suzuli coupling reaction is dioxane, tetrahydrofuran and water or dioxane and water.
4. The method for preparing a three-dimensional covalent organic framework 3D COF material based on 8-linked cubic ligands according to claim 1, wherein a basic metal salt and a catalyst are added in the Suzuli coupling reaction in step (2); the alkaline metal salt is Na 2 CO 3 、K 2 CO 3 Or CsCO 3 The method comprises the steps of carrying out a first treatment on the surface of the The catalyst is tetra (triphenylphosphine) palladium (0) and AsPh 3 、n-Bu 3 P or Ph 2 P(CH 2 ) 2 PPh 2 (dppe)。
5. The method of preparing a three-dimensional covalent organic framework 3D COF material based on 8-linked cubic ligands according to claim 1, characterized in that the intermediate product B of step (3) is a 5,10,15, 20-tetrakis (([ 1,1':3',1 "-triphenyl ] -4,4" -dicarboxaldehyde))) (TTEP) ligand; the molar ratio of TTEP to TAPP is 1:2-1:3; the organic compound is one or more of dioxane, N-methyl pyrrolidone, N-dimethylformamide and 1,3, 5-trimethylbenzene.
6. The method for preparing a three-dimensional covalent organic framework 3D COF material based on 8-linked cubic ligands according to claim 1, wherein the catalyst in step (4) is preferably acetic acid.
7. The method for preparing the 3D COF material based on the three-dimensional covalent organic frameworks with 8-communication cubic ligands according to claim 1, wherein in the step (4), liquid nitrogen is rapidly frozen and vacuumized until the internal pressure is 0.15-0.2mmHg, and the liquid nitrogen freezing-vacuumizing-thawing is used as a cycle, and the heat preservation reaction is repeated for 2-3 times.
8. The method for preparing the three-dimensional covalent organic framework 3D COF material based on 8-linked cubic ligands according to claim 1, wherein the temperature of the heat preservation in the step (4) is 100-140 ℃ and the reaction time is 3-7 days.
9. The three-dimensional covalent organic framework 3D COF material based on 8-linked cubic ligands prepared by the preparation method of claim 1.
10. Use of the three-dimensional covalent organic framework 3D COF material based on 8-linked cubic ligands according to claim 9 in the field of lithium ion battery negative electrode materials.
CN202310228926.5A 2023-03-10 2023-03-10 Preparation method and application of three-dimensional covalent organic framework 3D COF material based on 8-communicated cubic ligand Pending CN116082591A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117343256A (en) * 2023-12-06 2024-01-05 四川大学 Functionalized covalent organic framework material and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117343256A (en) * 2023-12-06 2024-01-05 四川大学 Functionalized covalent organic framework material and preparation method and application thereof
CN117343256B (en) * 2023-12-06 2024-02-13 四川大学 Functionalized covalent organic framework material and preparation method and application thereof

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