CN113881064B - Ethylenediamine tetraacetic dianhydride-based polyimide COF material, and preparation method and application thereof - Google Patents

Ethylenediamine tetraacetic dianhydride-based polyimide COF material, and preparation method and application thereof Download PDF

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CN113881064B
CN113881064B CN202111381957.1A CN202111381957A CN113881064B CN 113881064 B CN113881064 B CN 113881064B CN 202111381957 A CN202111381957 A CN 202111381957A CN 113881064 B CN113881064 B CN 113881064B
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lithium ion
cof
negative electrode
dianhydride
ethylenediamine tetraacetic
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CN113881064A (en
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熊维伟
钱悦
张志倩
宋海鑫
刘周佳
柏亿轩
尹瑞泽
张禹杰
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Jiangsu University of Science and Technology
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses an ethylene diamine tetraacetic dianhydride-based polyimide COF material, and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Dissolving 5,10,15, 20-tetra (4-aminophenyl) porphyrin (TAPP) and ethylenediamine tetraacetic dianhydride in an organic solution, and ultrasonically mixing; (2) Adding a catalyst into the mixture, then freezing by liquid nitrogen, vacuumizing, freezing for several cycles, and then putting the mixture into a thermostat for heat preservation for several days to obtain a suspension; (3) And after the suspension is cooled to room temperature, centrifugally collecting precipitates, and drying to obtain the COF material. The COF material with the Tetraaminophenylporphyrin (TAPP) as the structural unit, which is prepared by the invention, is used as the lithium ion negative electrode material, has good stability, large specific surface area and uniform pore channel structure, can effectively promote the transfer of electrons, and obtains excellent electrochemical energy storage performance.

Description

Ethylenediamine tetraacetic dianhydride-based polyimide COF material, and preparation method and application thereof
Technical Field
The invention relates to the field of lithium ion battery negative electrode materials, in particular to an ethylene diamine tetraacetic dianhydride-based polyimide COF material, a preparation method thereof and application thereof in a lithium ion battery negative electrode material.
Background
In recent years, rapid development in the field of new energy power generation puts new requirements on matched energy storage systems. In the updating and upgrading of energy storage batteries, lithium ion batteries have become a key research field due to various advantages of the lithium ion batteries, and have been practically applied to a large number of energy storage projects, so that certain effect is achieved. However, due to environmental problems such as heavy metal pollution, water pollution, and soil pollution, LIBs are worried about their future application prospects. Therefore, the development and preparation of high-performance, sustainable and green electrode materials are of great importance for the application of lithium ion batteries.
Covalent organic framework Compounds (COFs) are an emerging class of porous crystalline materials, have a periodic two-dimensional or three-dimensional network structure, and are crystalline porous materials formed by connecting organic structural units with dynamic covalent bonds. Since the first example of COFs reported by Yaghi in 2005, many new COFs have emerged. Because COFs materials have ordered and controllable pore structures, permanent porosity, large specific surface area, post-modified active groups, high thermal stability, high chemical stability and other unique properties, the COFs materials have wide application prospects in multiple fields of gas adsorption and storage, separation, catalysis, sensing, drug delivery, energy storage, photoelectric devices and the like. To date, COFs have also been widely reported as electrode materials because of their large number of redox active centers, higher stability, long-range ordered open channels, and low solubility, which contribute to the diffusion path of ions/electrons through nanoporous channels. However, COFs materials also suffer from the following disadvantages: (1) Compared with an inorganic molecular sieve, the material synthesized by the method of boric acid self-polymerization and boric acid ester formation is easy to decompose when meeting water, has poor stability and is not beneficial to the wide application of the material; (2) The challenges of finding a new rigid framework, developing a new connection mode and designing and synthesizing COFs materials with novel structural properties are also faced at present; (3) Most COFs materials are synthesized under solvothermal conditions, so that the operation difficulty is high, the requirements on reaction conditions are strict, the large-scale synthesis of the COFs materials is limited, and the industrial application of the COFs materials is further hindered. At present, the method which is simple and easy to operate and can synthesize a large amount of COFs materials is urgent; (4) Designing and synthesizing functional COFs materials and realizing application research of the materials in different fields are also a challenge. The COF negative electrode material for the lithium ion battery in the existing scheme has the problem of poor stability, so that the use performance of the COF negative electrode material is influenced, the existing modification process is more complicated, more equipment is involved, the process is more complicated, and the control on the production of products is not favorable, so that the COF negative electrode material has very important practical significance for improving the simplification of COFs materials and processes.
Disclosure of Invention
The invention aims to: aiming at the problems in the prior art, the invention provides a preparation method of an ethylene diamine tetraacetic dianhydride-based polyimide COF material.
The invention also provides the ethylenediamine tetraacetic dianhydride-based polyimide COF material and an application of the ethylenediamine tetraacetic dianhydride-based polyimide COF material as a lithium ion negative electrode material.
The technical scheme is as follows: in order to achieve the purpose, the preparation method of the polyimide COF lithium ion negative electrode material based on the ethylenediamine tetraacetic dianhydride comprises the following steps:
(1) Dissolving 5,10,15, 20-tetra (4-aminophenyl) porphyrin (TAPP) and ethylenediamine tetraacetic dianhydride in an organic solution, and performing ultrasonic treatment on the mixture;
(2) Adding a catalyst into the mixture obtained in the step (1), quickly freezing, vacuumizing, thawing again, and carrying out heat preservation reaction on the reaction mixture to obtain a suspension;
(3) After cooling to room temperature, the resulting violet black suspension was centrifuged, the precipitate was collected, dried in a vacuum oven for a period of time and the solvent was removed to give a violet black powdered product COF material.
Wherein the molar ratio of the 5,10,15, 20-tetra (4-aminophenyl) porphyrin (TAPP) to the ethylenediamine tetraacetic dianhydride is 1:1-1:2.
preferably, the molar ratio of 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin (TAPP) to ethylenediaminetetraacetic dianhydride is 1:2.
Wherein, the organic solvent can be N-methyl pyrrolidone, N-dimethylformamide, 1,3,5-trimethylbenzene or dichloromethane.
Wherein, the catalyst can be acetic acid or isoquinoline.
Wherein the dosage of the catalyst is 0.1-0.4mL.
Wherein, in the step (2), the mixture is quickly frozen by liquid nitrogen and then vacuumized until the internal pressure is 0.15-0.2mmHg, and the liquid nitrogen freezing-vacuumizing-unfreezing is adopted as a cycle, and the heat preservation reaction is repeated for 2-3 times. The purpose of freezing, vacuumizing and unfreezing the liquid nitrogen is to remove oxygen in the reaction solution, so that the experimental effect is better.
Wherein the temperature of the heat preservation reaction is 120-150 ℃, and the reaction time is 3-7 days.
Preferably, the incubation reaction is carried out at 120 ℃ for 3 days.
Wherein, the centrifugal separation can use DMF, ethanol, tetrahydrofuran or methanol for washing for a plurality of times.
Wherein the temperature of the vacuum drying is 60-120 ℃.
The polyimide COF material based on the ethylenediamine tetraacetic dianhydride prepared by the preparation method provided by the invention.
The invention relates to an application of a polyimide COF material based on ethylenediamine tetraacetic dianhydride in the field of lithium ion battery negative electrode materials.
The invention provides a preparation method of a lithium ion negative electrode material of an ethylene diamine tetraacetic acid dianhydride-based polyimide COF material, which can effectively solve the problem that the COF negative electrode material for a lithium ion battery has poor stability so as to influence the use performance of the COF negative electrode material, and the existing modification process is more complicated, involves more equipment, has more complex process, is unfavorable for controlling the production of products and the like. The ethylenediamine tetraacetic dianhydride used in the present invention contains an acid anhydride bond, which can form an imide bond with an amino group on tetraaminophenylporphyrin, thereby forming a polyimide polymer, and has good thermal stability and high chemical stability compared with other high molecular materials.
The selected ethylenediaminetetraacetic dianhydride has high nitrogen content and a good lithium storage function, does not have a benzene ring, and can form a long intermediate chain, so that the ethylenediaminetetraacetic dianhydride has an excellent steric hindrance effect. Polyimide based on ethylenediamine tetraacetic dianhydrideThe synthesis of COF-like materials is shown below. For tetraaminophenylporphyrins, the structure is due to-NH 2 The electron donating effect and the lone pair electrons on the N atom increase the electron cloud density on the porphyrin ring, enlarge the conjugated system of the porphyrin ring and improve the electron delocalization, and the ethylenediamine tetraacetic dianhydride has no benzene ring, forms a long intermediate chain, has a good steric hindrance effect, makes the material more stable, avoids excessive lithiation, and the dianhydride containing the benzene ring has no steric hindrance effect. The N atom has the highest binding energy in the-CO-N-CO-unit because the N atom is connected with two strongly electron-withdrawing carbonyl groups, and the carbonyl groups store lithium, so that the energy storage performance is better.
Figure BDA0003363478640000031
The invention is characterized in that a COF material prepared by reacting specific ethylenediamine tetraacetic dianhydride with TAPP is used as a battery cathode, so that the battery has good energy storage performance, the effect of the invention cannot be obtained by reacting the existing other dianhydrides with TAPP, mainly because the ethylenediamine tetraacetic dianhydride has no benzene ring, the formed intermediate chain has long length and good steric hindrance effect, the content of nitrogen is high, nitrogen and C = O (carbonyl) can play a role in storing lithium, and other dianhydrides have no characteristics.
The polyimide COF material formed by reacting the specific ethylenediamine tetraacetic dianhydride with the TAPP is an organic crystal form porous material combined by covalent bonds, has a regular structure and uniform pore channels, and has high thermal stability and chemical stability; the material has more applications in the aspects of gas adsorption, photoelectricity, catalysis and the like, but is applied to the field of lithium ion negative electrode materials for the first time.
Has the advantages that: compared with the prior art, the invention has the following advantages:
the invention provides a preparation method of a COF material with Tetraaminophenylporphyrin (TAPP) as a structural unit, the prepared COF material can be used as a lithium ion negative electrode material, the COF material obtained by a solvent method can be used as the lithium ion negative electrode material, the operation process is relatively simple and easy to control, and the volatilization of toxic substances can be effectively prevented in a closed system.
The polyimide material prepared by the invention has excellent thermal stability and chemical stability, regular structure, uniform pore channel and larger specific surface area, can effectively promote the transfer of electrons, and has excellent performance. The polyimide material prepared by the invention can be applied to the field of lithium ion battery cathode materials, and has stable cycle performance and excellent electrochemical energy storage performance, thereby expanding the application of the material in the field of lithium ion cathode materials.
Drawings
FIG. 1 is an SEM image of an EDTA dianhydride-based polyimide-based COF material prepared according to the present invention;
FIG. 2 is a Fourier transform infrared (FT-IR) diagram of an ethylenediamine tetraacetic dianhydride-based polyimide COF material prepared according to the present invention;
FIG. 3 shows that the prepared polyimide COF material based on the ethylenediamine tetraacetic dianhydride is 200mA g -1 Current density of 200 cycles of the performance plot;
FIG. 4 shows that the prepared polyimide COF material based on ethylenediamine tetraacetic dianhydride is 500mA g -1 Cycling the performance graph 500 times at current density;
FIG. 5 shows that the prepared EDTA-based polyimide COF material is at 1000mA g -1 Cycling 800 performance plots at current density;
FIG. 6 shows the rate capability of the EDTA-based polyimide COF material at different current densities.
FIG. 7 shows that the polyimide COF material based on ethylenediamine tetraacetic dianhydride prepared by the invention is at 0.01-3.00V, and the sweep rate is 0.2mV s -1 Cyclic voltammogram of (a).
Detailed Description
The invention will be further described with reference to specific embodiments and the accompanying drawings.
The experimental methods described in the examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Wherein, the conductive agent (Super-P), the polyvinylidene fluoride (with the average molecular weight of 40-50 ten thousand), the N-methylpyrrolidone, the isoquinoline, the 5,10,15, 20-Tetraaminophenylporphyrin (TAPP) and the ethylenediamine tetraacetic dianhydride are all purchased from the alatine.
Example 1
The specific preparation steps of the polyimide COF material based on the ethylenediamine tetraacetic dianhydride are as follows:
5,10,15,20-Tetraaminophenylporphyrin (TAPP) (0.15mmol, 0.1184g) and ethylenediaminetetraacetic dianhydride (0.15mmol, 0.0384g) were dissolved in a mixed solution of N-methylpyrrolidone (1 mL) and 1,3,5-trimethylbenzene (1 mL), sufficiently dissolved by sonication, and then 0.1mL of isoquinoline was added thereto, rapidly frozen with liquid nitrogen (the solution did not flow), then evacuated to an internal pressure of 0.15mmHg, and thawed. Liquid nitrogen freezing, vacuumizing and unfreezing are repeated for 3 times. The reaction mixture was incubated at 120 ℃ for 3 days in a thermostat to obtain a suspension. And after the reaction is finished, centrifuging to remove supernatant to obtain purple black precipitate, centrifuging and washing the purple black precipitate for multiple times by using tetrahydrofuran and acetone, and finally drying in vacuum drying at 60 ℃ to remove the solvent to obtain a purple black powdery product, namely the ethylene diamine tetraacetic acid dianhydride-based polyimide COF material. Fig. 1 is an SEM image of the final COF material prepared by the solvothermal synthesis method; FIG. 2 is a FT-IR diagram of a COF material prepared by the present invention, and it can be seen from FIG. 2 that the COF material is 1402cm -1 The band at (A) well demonstrates the formation of a C-N-C new bond, and 1675cm -1 Characteristic peak of acid anhydride in the vicinity of 3329cm -1 、1673cm -1 The characteristic bands of the adjacent TAPP monomers do not appear, which fully shows that the two monomers form new substances through imide bonds, and proves the successful synthesis of COF materials.
Example 2
Example 2 was prepared identically to example 1, except that: 5,10,15,20 tetra (4 aminophenyl) porphyrin (TAPP) and ethylenediaminetetraacetic dianhydride in a molar ratio of 1:2, the organic solution can be replaced with N, N-dimethylformamide; the catalyst adopts acetic acid; the reaction was maintained at 150 ℃ for 7 days.
Example 3
The COF material prepared by the invention is used for testing the electrochemical performance of the lithium ion negative electrode material.
The testing steps are as follows: weighing the following components in a mass ratio of 7:2:1 (COF material, prepared in example 1), conductive agent (Super-P) and polymer binder (polyvinylidene fluoride, PVDF), adding an appropriate amount of NMP (N-methylpyrrolidone) as a solvent to prepare a slurry, wherein the NMP is added in an amount sufficient to prepare the slurry in a non-dense and non-dilute state; coating the slurry on the rough surface of copper foil to a thickness of about 150nm, placing in a vacuum oven at 80 deg.C for 24 hr, cutting the copper foil coated with active material into electrode sheets with a diameter of 12mm by a slicer, wherein the active material (COF) on each copper foil is about 1.0mg/cm 2 The charge/discharge capacity was calculated based on the weight of the active material in the electrode. For assembling the lithium ion battery, celgard2600 and lithium sheet were used as battery separator and counter electrode, respectively, with 1mol L of electrolyte -1 LiPF6 solution (ethylene carbonate/dimethyl carbonate/diethyl carbonate V: V = 1; the cell was packed in a glove box at ambient temperature 25 c and the oxygen and moisture content was below 1ppm. The LAND CT 2001A blue light system is used for constant current charging and discharging test, and the CHI660E electrochemical workstation is used for testing cyclic voltammetry (the voltage range is 0.01-3.0V, and the scanning rate is 0.2mV s) -1 ) And impedance (frequency range 0.01 Hz-100 kHz). FIG. 3 shows that the COF material prepared by the invention is used as a lithium ion negative electrode material at a voltage of 0.01-3V,200mA g -1 The current density of (2) was measured and the performance chart was repeated 200 times, and as can be seen from FIG. 3, the reversible specific capacity was 791mAh g -1 . FIG. 4 shows that the COF material prepared by the invention is used as a lithium ion negative electrode material at 500mA g -1 The current density of (1) is cycled for 500 times, and as can be seen from FIG. 4, the reversible specific capacity is 613mAh g -1 。
FIG. 5 shows that the COF material prepared by the present invention is used as a lithium ion negative electrode material at 1000mA g -1 The current density of (1) is cycled for 800 times, and as can be seen from FIG. 5, the reversible specific capacity is 400mAh g -1 . The material prepared by the invention circulates for hundreds of times under different current densitiesThe remaining capacity after the cycle is still very high, and fig. 3-5 prove that the cycle performance and the energy storage performance are good, and meanwhile, the remaining capacity after the cycle is performed for hundreds of times is higher, which shows that the stability is very good. FIG. 6 shows the rate capability of the COF material prepared by the present invention as the lithium ion negative electrode material under different current densities, and it can be seen from FIG. 6 that the current densities are 100, 200, 500, 1000 and 2000mA g -1 The capacity of the COF electrode is 871, 720, 520, 353 and 188mAh g respectively -1 And the excellent rate capability is proved. FIG. 7 shows that the COF material prepared by the present invention has a sweep rate of 0.2mV s at 0.01-3.00V -1 As can be seen from fig. 7, in the first cathodic reduction reaction, there are significant reduction peaks near 0.21 and 0.67V, which disappear in the subsequent scan due to the formation of a Solid Electrolyte Interface (SEI). For the first anodic scan, one large anodic peak (0.61V) and one small anodic peak (1.29V) were attributed to the oxidation process of the discharge products. In the next second and third scans, the redox trends were essentially the same, indicating that the material had good reversibility. The reduction peaks after the second cycle are all shifted towards higher voltages compared to the first cycle, indicating a significant improvement in the electrochemical kinetics of the electrode material.

Claims (8)

1. A preparation method of an ethylene diamine tetraacetic dianhydride-based polyimide COF material for a lithium ion negative electrode material is characterized by comprising the following steps:
(1) Dissolving 5,10,15, 20-tetra (4-aminophenyl) porphyrin TAPP and ethylenediamine tetraacetic dianhydride in an organic solution, and ultrasonically mixing;
(2) Adding a catalyst into the mixture obtained in the step (1), quickly freezing, vacuumizing, thawing again, and carrying out heat preservation reaction on the reaction mixture to obtain a suspension;
(3) After the suspension is cooled to room temperature, centrifugally collecting precipitates, and drying to obtain a COF material;
the molar ratio of the 5,10,15, 20-tetra (4-aminophenyl) porphyrin TAPP to the ethylenediamine tetraacetic dianhydride in the step (1) is 1:1-1:2;
the temperature of the heat preservation in the step (2) is 120-150 ℃; the reaction time is 3-7 days.
2. The method for preparing an ethylenediamine tetraacetic dianhydride-based polyimide-based COF material for a lithium ion negative electrode material according to claim 1, wherein the organic solution in the step (1) is one or more of N-methylpyrrolidone, N-dimethylformamide, 1,3,5-trimethylbenzene or dichloromethane.
3. The method for preparing an ethylenediamine tetraacetic dianhydride-based polyimide-based COF material for a lithium ion negative electrode material according to claim 1, wherein the catalyst in the step (2) is acetic acid or isoquinoline, and the amount of the catalyst is 0.1-0.4mL.
4. The method for preparing the ethylenediamine tetraacetic dianhydride-based polyimide COF material for the lithium ion negative electrode material according to claim 1, wherein in the step (2), liquid nitrogen is used for quick freezing and vacuuming until the internal pressure is 0.15-0.2mmHg, and the liquid nitrogen freezing-vacuuming-unfreezing is used as a cycle, and the heat preservation reaction is repeated for 2-3 times.
5. The method for preparing an ethylenediaminetetraacetic dianhydride-based polyimide-based COF material for a lithium ion negative electrode material according to claim 1, wherein the centrifugation in the step (3) is performed by washing with DMF, ethanol, tetrahydrofuran, or methanol for a plurality of times.
6. The method for preparing an ethylenediaminetetraacetic dianhydride-based polyimide-based COF material for a lithium ion negative electrode material according to claim 1, wherein the drying in step (3) is vacuum drying at a temperature of 60 ℃ to 120 ℃.
7. An ethylene diamine tetraacetic dianhydride-based polyimide COF material for a lithium ion negative electrode material prepared by the preparation method of claim 1.
8. The application of the ethylenediamine tetraacetic dianhydride-based polyimide COF material for the lithium ion negative electrode material in the field of lithium ion battery negative electrode materials in claim 7.
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