CN111446414B - Covalent organic framework material, preparation method and application thereof - Google Patents

Covalent organic framework material, preparation method and application thereof Download PDF

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CN111446414B
CN111446414B CN202010264724.2A CN202010264724A CN111446414B CN 111446414 B CN111446414 B CN 111446414B CN 202010264724 A CN202010264724 A CN 202010264724A CN 111446414 B CN111446414 B CN 111446414B
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organic framework
covalent organic
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cof
framework material
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CN111446414A (en
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夏书标
刘建军
成飞翔
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Qujing Normal University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a covalent organic framework material, a preparation method and application thereof, wherein the preparation method comprises the steps of refluxing cyclohexadecanone octahydrate and diaminomaleonitrile, filtering out a black suspension while the black suspension is hot, washing the black suspension with hot AcOH to obtain a black solid, and suspending the black solid in 30 wt% of HNO3Heating to obtain dark brown suspension, pouring the hot dark brown suspension into ice water, filtering the suspension to obtain black solid HAT-CN, and carbonizing the black solid HAT-CN under the protection of nitrogen or inert gas to prepare the covalent organic framework material COF-CN. The first discharge specific capacity of the electrode material prepared by the invention reaches 1695mAh/g under the current density of 0.01V-3V and 100 mA/g; the discharge capacity after 50 cycles was 708 mAh/g.

Description

Covalent organic framework material, preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a covalent organic framework material, a preparation method and application thereof.
Background
The traditional fossil energy faces the problems of resource shortage and environmental pollution, and the development of new energy and new energy technology is urgent. Lithium ion batteries are the most mature energy storage technology developed in the last decade, but there is still a need to find more excellent electrode materials to obtain larger storage capacity, higher energy density and longer cycle life. Carbon nanomaterials with sp 2-hybridized backbones have many attractive properties, such as high electrical conductivity and abundant availability. These materials find wide application in the fields of absorption, catalysis, energy storage and conversion, etc. Carbon has the smallest voxel size in chemical constitution and its properties can be tuned by tuning its atomic framework structure. In addition to the variability in geometry, carbon-based materials can also achieve a wide range of specific properties in terms of electron and surface atomic structure through heteroatom doping. The incorporation of nitrogen into the carbon skeleton has been extensively studied, and the doping of heteroatoms makes the structure more polar and provides specific binding sites, both of which result in a greatly increased enthalpy of interaction between the adsorbent and the guest compared to conventional activated carbon.
Although sp2The carbon material of the hybrid skeleton hasBut the materials reported at present have some defects, such as few redox active sites, small specific capacitance, easy dissolution in electrolyte, poor cycle stability, etc. In order to overcome the above disadvantages, many recent researchers have found that a covalent organic framework material (COF) has not only the advantages of the above carbon materials but also a novel structure and excellent stability, which is skillfully constructed by a strong covalent bond with an organic building block. However, covalent organic polymer materials have poor conductivity and large molecular weight, so that the covalent organic framework electrode materials with large capacity, high rate performance and high cycle stability are still difficult to obtain. According to the invention, a COF electrode material monomer is prepared by a condensation reaction of cyclohexadecanone octahydrate and diaminomaleonitrile under the condition of taking acetic acid as a solvent, and then the COF electrode material monomer is carbonized under the protection of nitrogen or inert gas to prepare a covalent organic framework material COF-CN. The covalent organic framework material is used as a lithium ion battery cathode material, and shows higher specific capacity and cycling stability. In the current research on covalent organic framework electrode materials, the method has the advantages of simple synthesis method, high capacity and high cycle stability, and the research on the electrode materials which can be directly used is rare, so the research of the patent has good application prospect. Many researchers recently discovered that covalent organic framework materials (COFs), which are cleverly constructed by strong covalent bonds with organic building blocks, have excellent structural novelty and stability.
Disclosure of Invention
In view of the problems mentioned in the background art, the invention aims to provide an electrode material of a lithium ion battery with high specific discharge capacity and stable cycle performance.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of a covalent organic framework material, which comprises the following steps:
(1) refluxing cyclohexanone octahydrate and diaminomaleonitrile in a solvent, filtering out a black suspension while the suspension is hot, and washing the black suspension by hot AcOH (acetic acid) to obtain a black solid;
(2) suspending the black solid in 30wt％HNO3Heating to obtain dark brown suspension;
(3) pouring the hot dark brown suspension into ice water and filtering the suspension to obtain hexaazatriphenylhexacyanogen (HAT-CN) as a black solid;
(4) and carbonizing HAT-CN under the protection of nitrogen or inert gas at different temperatures to prepare the covalent organic framework material COF-CN.
Further, the molar ratio of the cyclohexadecanone octahydrate to the diaminomaleonitrile in the step (1) is 1: 8.
Further, the solvent in the step (1) is AcOH.
Further, the heating temperature in the step (2) is 80-120 ℃.
Further, the carbonization temperature in the step (4) is from room temperature to 80 ℃, and then from 80 ℃ to 1000 ℃, and the carbonization temperature is heated by a ramp heating technology.
Further, the heating ramp was 2 ℃ min from room temperature to 80 ℃-1The heating ramp is 4 ℃ min from 80 ℃ to 1000 DEG C-1。
The invention also provides a covalent organic framework material COF-CN prepared by the preparation method of the covalent organic framework material.
The invention also provides application of the covalent organic framework material in preparation of an electrode material of a lithium ion battery.
Further, the preparation method of the electrode material of the lithium ion battery comprises the following steps: preparing a mixture of HAT-CN, PVDF (polyvinylidene fluoride) and conductive graphite KS6 according to a mass ratio of 70:10:20, adding NMP (N-methylpyrrolidone) as a solvent, stirring to prepare lithium ion battery electrode slurry, coating the electrode slurry on a copper foil with the thickness of 12 mu m, coating the copper foil with the thickness of 50 mu m, and drying at 100 ℃ for 12 hours to obtain the lithium ion battery electrode.
The invention discloses the following technical effects:
the covalent organic framework material COF-CN prepared by the method is used as an electrode material of a lithium ion battery, and the first discharge specific capacity reaches 1695mAh/g under the current density of 0.01V-3V and 100 mA/g; the discharge capacity after 50 cycles was 708 mAh/g. The invention has low requirements on synthesis equipment, and the synthesized covalent organic framework (COF-CN) material has novel and stable structure and is a novel lithium ion battery electrode material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a schematic diagram of the synthesis of the electrode material of COF-CN lithium ion battery of the invention;
FIG. 2 is a schematic structural diagram of a COF-CN electrode material of the present invention;
FIG. 3 is an XRD pattern of the COF-CN electrode material prepared in example 1;
FIG. 4 is a SEM and EDX elemental distribution diagram for a COF-CN700 electrode material;
FIG. 5 is a TEM image of the COF-CN700 electrode material;
FIG. 6 is a COF-CN700 electrode material adsorption curve;
FIG. 7 is a first charge-discharge curve of COF-CN700 electrode material;
FIG. 8 is a 50 cycle curve for COF-CN700 electrode material;
FIG. 9 is a rate curve of COF-CN700 electrode material;
FIG. 10 is an SEM image of the electrode material of COF-CN 900;
FIG. 11 is a TEM image of the COF-CN900 electrode material;
FIG. 12 is a first charge-discharge curve of COF-CN900 electrode material;
FIG. 13 is a 50 cycle plot of the COF-CN900 electrode material;
FIG. 14 is a rate curve for COF-CN900 electrode material.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
Cyclohexanone octahydrate (4g, 12.6mmol) and diaminomaleonitrile (10.88g, 100.8mmol) were refluxed in AcOH (150mL) for 2h, the black suspension was filtered off hot and washed with hot AcOH (3X 25mL) to give a black solid, which was suspended in 30% HNO3(60mL) and heated at 100 ℃ for 3h to give a hot dark brown colorThe suspension, hot dark brown suspension poured into ice water (200mL) and cooled overnight, the suspension filtered and the solid refluxed in MeCN (400mL) for 2 hours and filtered. The filtrate was evaporated in vacuo to give hexaazatriphenylhexacyanobenzonitrile (HAT-CN) as an orange solid (2.4g, 50% yield). Preparation of COF-CN by carbonizing HAT-CN (500mg) in a horizontal tube furnace under a nitrogen stream at various temperatures ranging from room temperature to 80 ℃ and heating ramps set at 2 ℃ min-1From 80 ℃ to 700 ℃ at 4 ℃ to min-1And preparing COF-CN which is marked as COF-CN 700.
Preparing a mixture of COF-CN700, PVDF and KS6 according to the mass ratio of 70:10:20, adding NMP as a solvent, and stirring for 2 hours to prepare the lithium ion battery electrode slurry. And (3) coating the electrode viscous slurry on a copper foil with the thickness of 12 microns, wherein the coating thickness is 50 microns, and drying at 100 ℃ for 12 hours to obtain the lithium ion battery electrode. The lithium ion battery negative pole piece is cut into a circular pole piece with the diameter of 14mm, and the lithium ion battery counter electrode adopts a metal lithium piece with the diameter of 15 mm. The electrolyte is as follows: 1mol/L LiPF6The button cell was assembled in a 2032 type glove box filled with argon gas, dissolved in a solvent of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) (molar ratio EC: DMC 1: 1).
The structure of the synthesized COF-CN700 material is characterized, and as can be seen from FIGS. 2 and 3, the COF-CN700 obtained in the example is similar to the theoretically simulated structure, which indicates that the target product is obtained. The COF-CN700 material particles synthesized by SEM topography analysis and EDX spectrum analysis are hexagonal sheet-shaped, and contain elements of C and N. TEM results show that the COF-CN700 material has a lattice fringe spacing of about 0.250 nm. The BET nitrogen adsorption result shows that the COF-CN700 material has larger adsorption capacity, which indicates that the material has better mesopores. The electrochemical test results shown in FIGS. 7 and 8 show that the first discharge specific capacity reaches 1700mAhg at a current density of 100mA/g-1And the specific discharge capacity after 50 cycles is 610mAhg-1. The capacity retention rate after 50 cycles was 83.6% calculated from the second discharge capacity, and good rate capability was exhibited.
Example 2
Mixing the six ingredients of cyclohexaneKetone octahydrate (4g, 12.6mmol) and diaminomaleonitrile (10.88g, 100.8mmol) were refluxed in AcOH (150mL) for 2h, the black suspension was filtered off while hot and washed with hot AcOH (3X 25mL) to give a black solid, which was suspended in 30 wt% HNO3(60mL) and heated at 100 ℃ for 3h to give a hot dark brown suspension, which was poured into ice water (200mL) and cooled overnight. The suspension was filtered and the solid was refluxed in MeCN (400mL) for 2 hours and filtered, and the filtrate was evaporated in vacuo to give hexaazatriphenylhexacyano (HAT-CN) as an orange solid (2.4g, 50% yield). COF-CN was prepared by carbonizing HAT-CN (500mg) in a horizontal tube furnace under a nitrogen stream at various temperatures for 1 hour. The different temperatures are from room temperature to 80 ℃, and the heating slopes are respectively set to be 2 ℃ and min-1From 80 ℃ to 900 ℃ at 4 ℃ and min, respectively-1And preparing a covalent organic framework material COF-CN which is marked as COF-CN 900.
Preparing a mixture of COF-CN900, PVDF and KS6 according to the mass ratio of 70:10:20, adding NMP as a solvent, and stirring for 2 hours to prepare the lithium ion battery electrode slurry. And (3) coating the electrode viscous slurry on a copper foil with the thickness of 12 microns, wherein the coating thickness is 50 microns, and drying at 100 ℃ for 12 hours to obtain the lithium ion battery electrode. The lithium ion battery negative pole piece is cut into a circular pole piece with the diameter of 14mm, and the lithium ion battery counter electrode adopts a metal lithium piece with the diameter of 15 mm. The electrolyte is 1mol/L LiPF6The button cell was assembled in a 2032 type glove box filled with argon gas, dissolved in a solvent of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) (molar ratio EC: DMC 1: 1).
The morphology analysis of the synthesized COF-CN900 material shows that the synthesized COF-CN900 material particles still have a hexagonal sheet-like morphology in FIG. 10. TEM results show that the COF-CN900 material has a lattice fringe spacing of about 0.266nm, which is larger than the COF-CN 700. The electrochemical test result is shown in figure 12, under the current density of 100mA/g, the first discharge specific capacity reaches 1695mAhg-1And the discharge specific capacity after 50 cycles is 708mAhg-1. The capacity retention rate after 50 cycles is 85.2%, the cycle performance is excellent, and the rate performance is better calculated from the second discharge capacity.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (8)

1. A method of preparing a covalent organic framework material, comprising the steps of:
(1) refluxing cyclohexanone octahydrate and diaminomaleonitrile in a solvent, filtering out a black suspension while the suspension is hot, and washing the black suspension by using hot AcOH to obtain a black solid, wherein the molar ratio of the cyclohexanone octahydrate to the diaminomaleonitrile is 1: 8;
(2) suspending the black solid in 30 wt% HNO3Heating to obtain dark brown suspension;
(3) pouring the hot dark brown suspension into ice water, and filtering the suspension to obtain solid hexaazatriphenylene hexacyano-HAT-CN;
(4) and carbonizing HAT-CN under the protection of nitrogen or inert gas at different temperatures to prepare the covalent organic framework material COF-CN.
2. The method of claim 1, wherein the solvent of step (1) is AcOH.
3. The method of claim 1, wherein the heating temperature in step (2) is 80-120 ℃.
4. The method of claim 1, wherein the carbonization temperature in step (4) is from room temperature to 80 ℃ and further from 80 ℃ to 1000 ℃, and the covalent organic framework material is heated by a ramp-up technique.
5. The method of preparing a covalent organic framework material according to claim 4,it is characterized in that the heating slope from room temperature to 80 ℃ is 2 ℃ min-1The heating ramp is 4 ℃ min from 80 ℃ to 1000 DEG C-1。
6. A covalent organic framework material COF-CN prepared according to the method of preparation of a covalent organic framework material according to any one of claims 1 to 5.
7. Use of the covalent organic framework material COF-CN according to claim 6 for the preparation of an electrode material for lithium ion batteries.
8. The use according to claim 7, wherein the preparation method of the electrode material of the lithium ion battery comprises the following steps: preparing a mixture of COF-CN, PVDF and conductive graphite according to a mass ratio of 70:10:20, adding NMP as a solvent, stirring to prepare lithium ion battery electrode slurry, coating the lithium ion battery electrode slurry on a copper foil with the thickness of 12 mu m, and drying at 100 ℃ for 12 hours to obtain the lithium ion battery electrode.
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