CN111848892A - Preparation method of carbon nanotube-loaded two-dimensional covalent organic framework electrode material - Google Patents
Preparation method of carbon nanotube-loaded two-dimensional covalent organic framework electrode material Download PDFInfo
- Publication number
- CN111848892A CN111848892A CN202010527910.0A CN202010527910A CN111848892A CN 111848892 A CN111848892 A CN 111848892A CN 202010527910 A CN202010527910 A CN 202010527910A CN 111848892 A CN111848892 A CN 111848892A
- Authority
- CN
- China
- Prior art keywords
- organic framework
- covalent organic
- carbon nanotube
- dimensional covalent
- loaded
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 79
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 58
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 58
- 239000007772 electrode material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 238000000944 Soxhlet extraction Methods 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 27
- 229910052744 lithium Inorganic materials 0.000 abstract description 26
- 238000003780 insertion Methods 0.000 abstract description 10
- 230000037431 insertion Effects 0.000 abstract description 10
- 239000011229 interlayer Substances 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 7
- 230000002441 reversible effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- -1 carbonyl compound small molecules Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000013473 2D covalent-organic framework Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002090 nanochannel Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a carbon nanotube-loaded two-dimensional covalent organic framework electrode material, which is obtained by growing a two-dimensional covalent organic framework on the surface of a carbon nanotube, and compared with a simple two-dimensional covalent organic framework with a crystal plane distance of not more than 0.35nm, the thickness of a thin two-dimensional covalent organic framework covered outside the carbon nanotube in a compound prepared by the invention is not more than 5 nm. The carbon nanotube-loaded two-dimensional covalent organic framework electrode material has a large specific surface area, can provide more lithium insertion sites, gradually expands interlayer spacing caused by repeated lithium insertion, and effectively improves the lithium ion cycle performance of the carbon nanotube-loaded two-dimensional covalent organic framework electrode material. Meanwhile, the preparation process of the composite material has short reaction time, low requirement on equipment and good prospect.
Description
Technical Field
The invention relates to a preparation method of an organic frame electrode material, in particular to a preparation method of a carbon material loaded organic frame electrode composite material, and belongs to the technical field of preparation of electrode materials of lithium ion power batteries.
Background
In the current society, rechargeable lithium batteries are the primary market for portable electronic products due to their high energy density, long cycle life, and other excellent performance characteristics. The development of Lithium Ion Batteries (LIBs) has largely relied on metal-containing electrode materials, such as transition metal oxides. However, these transition metal oxides, including cobalt, iron, nickel, manganese and other transition metal elements, are limited in scarcity in soil and may cause serious environmental problems. Exploring an environmentally friendly electrode material for LIB has been one of the hot topics in the energy field. Organic electrode materials have attracted increasing attention due to promising advantages in terms of tunable structures, many molecular designs, low cost and environmental friendliness. To date, several types of organic materials have been investigated, such as free radical or conducting polymers, organic salts and mainly conjugated carbonyl compound small molecules as electrode materials for lithium ion batteries. However, organic electrodes generally show a small reversible capacity and satisfactory cycle performance due to their poor electron conductivity and hydrophobicity in organic electrolytes. The most common strategy to address these problems to some extent is to use polymers and compositions with more conductive materials.
Covalent Organic Frameworks (COFs), which are made by covalent bonds between the light elements C, H, O, N, etc. of the rigid building blocks, typically have an extended 2D or 3D porous structure with long-range ordered frameworks and nanopores. Since COF was first reported in 2005, more COF materials with tunable structures and valuable properties have been successfully synthesized and applied to various fields such as gas storage/separation, nanochannel photovoltaics, catalysis, and semiconductors. In particular, there have been few recent reports on their use as cathode or anode materials for LIBs having higher electrochemical properties than conventional organic electrodes. The backbone structure of the functional organic unit in COF greatly hinders the dissolution of the organic electrode in the electrolyte.
It is reported that, to date, few 2D layered COF materials have 100-800mAhg when used as electrode materials for LIBs-1The reversible lithium storage capacity of (a). However, the 2D layer structure of close-packed COFs, especially the stacking manner with strong pi-pi interactions, leads to difficulties in penetration of lithium ions into the active sites inside the layers. This will inevitably lead to under-utilization of the redox active sites, thereby reducing the lithium storage capacity of the 2D COF. Therefore, the addition of the conductive carbon material and the stripping of the layered organic structure improve and optimize the performance of the electrode material, overcome the defects of poor conductivity and small reversible capacity of the covalent organic framework, and become a technical problem to be solved urgently.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art, and provides a preparation method of a carbon nanotube-loaded two-dimensional covalent organic framework electrode material, so that the performance and the conductivity of the covalent organic framework material as an electrode activation material are improved, and the reversible capacity of the covalent organic framework material is improved. The method adopts a simple one-pot method for stirring and synthesizing at room temperature, and the carbon nanotube-loaded two-dimensional covalent organic framework electrode material is obtained by growing on the surface of the carbon nanotube through a two-dimensional covalent organic framework.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of a carbon nanotube-loaded two-dimensional covalent organic framework electrode material is characterized in that a two-dimensional covalent organic framework is separated in situ by a carbon nanotube in the growth process, a thin-layer two-dimensional covalent organic framework is obtained on the surface of the carbon nanotube, and 6 lithium atoms can be stored on a conjugated benzene ring of the obtained structure.
As a preferred technical scheme of the invention, the preparation method of the carbon nanotube-loaded two-dimensional covalent organic framework electrode material comprises the following steps:
a. adopting carbon nano tubes with the average diameter of 50-80nm, 1,3, 5-benzenetricarboxylic acid and 1, 4-diaminobenzene as raw materials, adding the raw materials into 1.0-2.0mL of 1, 4-dioxane together, and performing ultrasonic dispersion for 5-10min to obtain a suspension; then adding a 3.0M acetic acid aqueous solution with the volume of 0.2-0.4mL into the suspension, and further stirring for 3-5h at the room temperature of 25-30 ℃ to obtain a green solid precipitate;
Preferably, the mass ratio of the 1,3, 5-benzenetricarboxylic acid to the carbon nanotube to the 1, 4-diaminobenzene is 1:1: 1-1: 2: 2;
the preferable reaction stirring time is 3-5 h;
b. and c, centrifuging the precipitate obtained in the step a for 3-5 times by using N, N-Dimethylformamide (DMF) and Tetrahydrofuran (THF) as solvents, performing Soxhlet extraction for 8-12h by using THF as a solvent, then performing vacuum drying for 8-12h at the temperature of 60-70 ℃, and collecting the carbon nanotube-loaded two-dimensional covalent organic framework composite material with a green final product.
As a preferred technical solution of the present invention, in the step b, the thickness of the thin two-dimensional covalent organic framework covered outside the carbon nanotube in the prepared composite of the carbon nanotube-supported two-dimensional covalent organic framework composite material is not more than 5 nm.
The invention discloses a carbon nanotube-loaded two-dimensional covalent organic framework composite material, which is prepared by the preparation method of the carbon nanotube-loaded two-dimensional covalent organic framework electrode material.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the carbon nanotube-loaded two-dimensional covalent organic framework electrode material has a large specific surface area and improved electrical conductivity, can provide more lithium insertion sites, and can store 6 lithium atoms on a conjugated benzene ring in an obtained composite structure due to gradual interlayer spacing expansion caused by repeated lithium insertion, wherein 1 lithium atom is stored in each carbon, so that the lithium ion chemical energy storage capacity and the cycle performance of the two-dimensional covalent organic framework electrode material are effectively improved;
2. The preparation process of the composite material has short reaction time, low requirement on equipment and good prospect;
3. the method is simple and easy to implement, low in cost and suitable for popularization and application.
Drawings
FIG. 1 is a comparative scanning electron micrograph of a covalent organic framework and a composite material according to a first embodiment of the present invention. Wherein, the images a and b in fig. 1 are Scanning Electron Microscope (SEM) images of the covalent organic framework and SEM images of the carbon nanotube-supported covalent organic framework composite material, respectively.
FIG. 2 shows an example of the present invention, N of the carbon nanotube-loaded covalent organic framework composite material standing for 3 days2Isothermal desorption curve (BET).
FIG. 3 is a Fourier transform infrared (FI-IR) spectrum of a carbon nanotube-loaded covalent organic framework composite in accordance with an embodiment of the present invention.
Fig. 4 is a schematic diagram of lithium storage of a carbon nanotube-loaded covalent organic framework composite according to an embodiment of the present invention.
FIG. 5 shows the small current (100mA g) of the carbon nanotube-loaded covalent organic framework lithium ion electrode material according to the embodiment of the present invention-1) And (3) a cycle performance diagram of charge and discharge.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
The first embodiment is as follows:
in this embodiment, a method for preparing a carbon nanotube-loaded two-dimensional covalent organic framework electrode material includes the following steps:
a. 1,3, 5-benzenetricarboxylic acid (16mg), CNT (16mg) and 1, 4-diaminobenzene (16mg) are added into 1.0mL of 1, 4-dioxane, and ultrasonic dispersion is carried out for 5min to obtain a suspension; a volume of 0.2mL of 3.0M aqueous acetic acid was then added to the suspension. Further stirring at 25 deg.C for 3h to obtain green solid precipitate;
b. and c, centrifuging the precipitate obtained in the step a for 3 times by using N, N-Dimethylformamide (DMF) and Tetrahydrofuran (THF) as solvents, performing Soxhlet extraction for 8h by using THF as a solvent, then drying for 8h in vacuum at 60 ℃, and collecting the carbon nanotube-supported two-dimensional covalent organic framework composite material (product A) with a green final product.
Experimental test analysis:
the carbon nanotube-loaded two-dimensional covalent organic framework composite material (product a) prepared in this example was used as a sample for experimental testing, and the procedure was as follows:
(1) selecting the composite, acetylene black and polyvinylidene fluoride (PVDF) (adhesive) to be mixed according to the mass ratio of 8:1:1, then adding N, N-dimethyl pyrrolidone (NMP) into the mixture, and performing ultrasonic dispersion to obtain colloidal black liquid; dispersing the pulp by a high-speed internal rotation type refiner for 5-7 times every time of one minute to obtain uniform black colloidal pulp;
(2) Uniformly coating the black colloidal slurry on a copper foil current collector with a loading of not more than 2mg cm-2Drying the electrode with the thickness not more than 20 μm in a vacuum oven at 50-70 deg.C for 12-24 hr; finally obtaining the carbon nano tube loaded two-dimensional covalent organic framework lithium battery electrode material.
The carbon nanotube loaded two-dimensional covalent organic framework lithium battery electrode material is adopted to carry out battery assembly and test:
testing the prepared electrode to be tested in a self-made stainless steel battery die, taking a high-purity lithium sheet as a negative electrode, taking a polypropylene porous membrane (Celgard-2400) as a diaphragm, and taking 1mol L of electrolyte-1The battery was assembled with a mixed solution of ethylene carbonate and diethyl carbonate (1: 1, w/w) and LiPF6 in a glove box filled with high-purity argon gas. In the LAND-CT2001C system, in a fixed potential range (5mV-3.0V vs. Li)+/Li) are lithiated and delithiated at different currents. The test current density was 0.1C, where 1C equals 1000mAg-1The test voltage range is 0.001-3.0V.
As shown in FIG. 1, SEM image reveals two-dimensional covalent organicThe frame is separated by the carbon nano tube in situ in the growth process, and a few thin layers of two-dimensional covalent organic frames (product A) can be obtained on the surface of the carbon nano tube. FIG. 3 is a Fourier transform infrared (FT-IR) spectrum of a carbon nanotube-loaded two-dimensional covalent organic framework composite (product A), which can be seen at 1618cm -1A strong C ═ N stretching peak can be seen, indicating the formation of imine bonds. Fig. 4 is a schematic diagram of lithium storage of a two-dimensional covalent organic framework (product a) loaded by a carbon nanotube, and it can be seen that six lithium can be stored on a conjugated benzene ring of the structure. FIG. 5 is a graph of the small current (100mA g) of a carbon nanotube supported covalent organic framework (product A) lithium ion electrode material-1) The charge-discharge cycle performance chart shows that the reversible capacity of the material is gradually increased in the cycle process before about 320 cycles, and 1021mAh g can be realized in the period of about 320-500 cycles-1Stable reversible capacity of (2). The preparation process of the electrode material has short reaction time, low requirement on equipment and good prospect. The carbon nanotube-loaded two-dimensional covalent organic framework electrode material has the advantages that the specific surface area is large, the electrical conductivity is improved, more lithium insertion sites can be provided, gradual interlayer spacing expansion caused by repeated lithium insertion is realized, 6 lithium can be stored on a conjugated benzene ring in an obtained composite structure, 1 lithium can be stored in each carbon, and the lithium ion chemical energy storage capacity and the cycle performance of the two-dimensional covalent organic framework electrode material are effectively improved.
Example two:
This embodiment is substantially the same as the first embodiment, and is characterized in that:
in this embodiment, a method for preparing a carbon nanotube-loaded two-dimensional covalent organic framework electrode material includes the following steps:
a. 1,3, 5-benzenetricarboxylic acid (16mg), CNT (32mg) and 1, 4-diaminobenzene (32mg) are added into 2.0mL of 1, 4-dioxane, and ultrasonic dispersion is carried out for 10min to obtain a suspension; a volume of 0.4mL of 3.0M aqueous acetic acid was then added to the suspension. Further stirring at room temperature of 30 ℃ for 5h to obtain a green solid precipitate;
b. and c, centrifuging the precipitate obtained in the step a for 5 times by using N, N-Dimethylformamide (DMF) and Tetrahydrofuran (THF) as solvents, performing Soxhlet extraction for 12h by using THF as a solvent, then performing vacuum drying for 12h at 70 ℃, and collecting the carbon nanotube-supported two-dimensional covalent organic framework composite material (product B) with a green final product.
The carbon nanotube-supported two-dimensional covalent organic framework composite material (product B) prepared in the embodiment is prepared into a lithium battery electrode material according to the method in the embodiment I, and the battery is assembled and tested according to the method in the embodiment I, so that 978mAh g can be realized after 500 cycles -1Stable reversible capacity of (2). The carbon nanotube-loaded two-dimensional covalent organic framework electrode material (product B) has a large specific surface area and improved electrical conductivity, can provide more lithium insertion sites, and can store 6 lithium on a conjugated benzene ring in an obtained composite structure due to gradual interlayer spacing expansion caused by repeated lithium insertion, wherein 1 lithium is stored in each carbon on average, so that the lithium ion chemical energy storage capacity and the cycle performance of the two-dimensional covalent organic framework electrode material are effectively improved.
Example three:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
the original bulk covalent organic framework was also synthesized in a similar process, but without the carbon nanotubes. Covalent organic frameworks that were allowed to stand for 3 days and carbon nanotubes-loaded two-dimensional covalent organic framework products that were allowed to stand for 3 days were obtained by the procedure of one method of the example, with an extended reaction time of 3 days. FIG. 2 is N of carbon nanotube-loaded covalent organic framework composite (product C) after standing for 3 days2Isothermal desorption curve (BET). As a result, the specific surface area of the material is determined to be as high as 108.42m2g-1。
To sum up, in the preparation method of the carbon nanotube-loaded two-dimensional covalent organic framework electrode material according to the embodiment, the two-dimensional covalent organic framework grows on the surface of the carbon nanotube, and compared with a simple two-dimensional covalent organic framework with a crystal plane distance of not more than 0.35nm, the thickness of the thin two-dimensional covalent organic framework covered outside the carbon nanotube in the composite prepared by the method is not less than 5nm, wherein the average diameter of the carbon nanotube is 50-80 nm. In the embodiment, the two-dimensional covalent organic framework is separated by the carbon nano tube in situ in the growth process, a thin-layer two-dimensional covalent organic framework can be obtained on the surface of the carbon nano tube, and six lithium can be stored on the conjugated benzene ring of the obtained structure. The carbon nanotube-loaded two-dimensional covalent organic framework electrode material has a large specific surface area, can provide more lithium insertion sites, and effectively improves the lithium ion cycle performance of the carbon nanotube-loaded two-dimensional covalent organic framework electrode material due to gradual interlayer space expansion caused by repeated lithium insertion. Meanwhile, the preparation process of the composite material has short reaction time, low requirement on equipment and good prospect.
While the embodiments of the present invention have been described with reference to the accompanying drawings, the present invention is not limited to the above embodiments, and various changes, modifications, substitutions, combinations or simplifications made according to the spirit and principles of the present invention should be equivalent substitutions, so long as the objects of the present invention are met, and the present invention is within the scope of protection of the present invention without departing from the technical principles and inventive concepts of the method for preparing the carbon nanotube-supported two-dimensional covalent organic framework electrode material of the present invention.
Claims (5)
1. A preparation method of a carbon nanotube loaded two-dimensional covalent organic framework electrode material is characterized by comprising the following steps: the two-dimensional covalent organic framework is separated by the carbon nano tube in situ in the growth process, a thin-layer two-dimensional covalent organic framework is obtained on the surface of the carbon nano tube, and 6 lithium ions can be stored on the conjugated benzene ring of the obtained structure.
2. The preparation method of the carbon nanotube-supported two-dimensional covalent organic framework electrode material according to claim 1, characterized by comprising the following steps:
a. adopting carbon nano tubes with the average diameter of 50-80nm, 1,3, 5-benzenetricarboxylic acid and 1, 4-diaminobenzene as raw materials, adding the raw materials into 1.0-2.0mL of 1, 4-dioxane together, and performing ultrasonic dispersion for 5-10min to obtain a suspension; then adding a 3.0M acetic acid aqueous solution with the volume of 0.2-0.4mL into the suspension, and further stirring for 3-5h at the room temperature of 25-30 ℃ to obtain a green solid precipitate;
b. And c, centrifuging the precipitate obtained in the step a for 3-5 times by using N, N-Dimethylformamide (DMF) and Tetrahydrofuran (THF) as solvents, performing Soxhlet extraction for 8-12h by using THF as a solvent, then performing vacuum drying for 8-12h at the temperature of 60-70 ℃, and collecting the carbon nanotube-loaded two-dimensional covalent organic framework composite material with a green final product.
3. The method for preparing the carbon nanotube-supported two-dimensional covalent organic framework composite material according to claim 2, wherein the method comprises the following steps: in the step a, the mass ratio of the 1,3, 5-benzenetricarboxylic acid to the carbon nano tube to the 1, 4-diaminobenzene is 1:1: 1-1: 2:2, and the reaction stirring time is 3-5 hours.
4. The carbon nanotube-loaded two-dimensional covalent organic framework composite material of claim 2, wherein: in the step b, the thickness of the thin two-dimensional covalent organic framework covered outside the carbon nano tube in the prepared composite of the carbon nano tube supported two-dimensional covalent organic framework composite material is not more than 5 nm.
5. A carbon nanotube-loaded two-dimensional covalent organic framework composite material is characterized in that: the carbon nanotube-supported two-dimensional covalent organic framework electrode material is prepared by the preparation method of the carbon nanotube-supported two-dimensional covalent organic framework electrode material of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010527910.0A CN111848892A (en) | 2020-06-11 | 2020-06-11 | Preparation method of carbon nanotube-loaded two-dimensional covalent organic framework electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010527910.0A CN111848892A (en) | 2020-06-11 | 2020-06-11 | Preparation method of carbon nanotube-loaded two-dimensional covalent organic framework electrode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111848892A true CN111848892A (en) | 2020-10-30 |
Family
ID=72986492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010527910.0A Pending CN111848892A (en) | 2020-06-11 | 2020-06-11 | Preparation method of carbon nanotube-loaded two-dimensional covalent organic framework electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111848892A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113903899A (en) * | 2021-09-30 | 2022-01-07 | 中原工学院 | Covalent organic framework material/carbon nano tube organic composite material and application thereof in lithium ion battery |
| CN114242927A (en) * | 2021-12-22 | 2022-03-25 | 珠海冠宇电池股份有限公司 | Positive electrode material and magnesium secondary battery containing same |
| CN114300789A (en) * | 2021-12-29 | 2022-04-08 | 吉林大学 | Preparation method of COF-based solid air positive electrode for solid lithium-air battery |
| CN114300789B (en) * | 2021-12-29 | 2024-04-30 | 吉林大学 | Preparation method of COF-based solid air positive electrode for solid lithium air battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106252634A (en) * | 2016-09-24 | 2016-12-21 | 上海大学 | Graphene aerogel load CNT and ZIF 67 electrode material of lithium battery preparation method |
| US20180272313A1 (en) * | 2014-12-19 | 2018-09-27 | Korea Institute Of Industrial Technology | Complex of carbon structure and covalent organic framework, preparation method therefor, and use thereof |
| CN109524652A (en) * | 2018-11-16 | 2019-03-26 | 华南师范大学 | A kind of covalent organic frame/graphene compositing organic material and preparation method and the application in lithium/anode material of lithium-ion battery |
| CN110164716A (en) * | 2019-05-31 | 2019-08-23 | 上海交通大学 | A kind of preparation method of the membrane electrode based on covalent organic frame material |
| CN110970233A (en) * | 2019-12-26 | 2020-04-07 | 上海交通大学 | Preparation method of micro super capacitor based on conjugated organic framework material |
| US20200123169A1 (en) * | 2017-06-02 | 2020-04-23 | Indian Institute Science Education And Research | Self-exfoliated triazole-triformyl phloroglucinol based covalent organic nanosheets for high and reversible lithium ion storage |
-
2020
- 2020-06-11 CN CN202010527910.0A patent/CN111848892A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180272313A1 (en) * | 2014-12-19 | 2018-09-27 | Korea Institute Of Industrial Technology | Complex of carbon structure and covalent organic framework, preparation method therefor, and use thereof |
| CN106252634A (en) * | 2016-09-24 | 2016-12-21 | 上海大学 | Graphene aerogel load CNT and ZIF 67 electrode material of lithium battery preparation method |
| US20200123169A1 (en) * | 2017-06-02 | 2020-04-23 | Indian Institute Science Education And Research | Self-exfoliated triazole-triformyl phloroglucinol based covalent organic nanosheets for high and reversible lithium ion storage |
| CN109524652A (en) * | 2018-11-16 | 2019-03-26 | 华南师范大学 | A kind of covalent organic frame/graphene compositing organic material and preparation method and the application in lithium/anode material of lithium-ion battery |
| CN110164716A (en) * | 2019-05-31 | 2019-08-23 | 上海交通大学 | A kind of preparation method of the membrane electrode based on covalent organic frame material |
| CN110970233A (en) * | 2019-12-26 | 2020-04-07 | 上海交通大学 | Preparation method of micro super capacitor based on conjugated organic framework material |
Non-Patent Citations (2)
| Title |
|---|
| ZHENDONG LEI ETC.: "Boosting lithium storage in covalent organic framework via activation of 14-electron redox chemistry", 《NATURE COMMUNICATIONS》 * |
| ZHENDONG LEI ETC.: "Boosting lithium storage in covalent organic framework via activation of 14-electron redox chemistry", 《NATURE COMMUNICATIONS》, vol. 9, no. 576, 8 February 2018 (2018-02-08), pages 1 - 13 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113903899A (en) * | 2021-09-30 | 2022-01-07 | 中原工学院 | Covalent organic framework material/carbon nano tube organic composite material and application thereof in lithium ion battery |
| CN114242927A (en) * | 2021-12-22 | 2022-03-25 | 珠海冠宇电池股份有限公司 | Positive electrode material and magnesium secondary battery containing same |
| CN114242927B (en) * | 2021-12-22 | 2023-07-18 | 珠海冠宇电池股份有限公司 | Positive electrode material and magnesium secondary battery containing same |
| CN114300789A (en) * | 2021-12-29 | 2022-04-08 | 吉林大学 | Preparation method of COF-based solid air positive electrode for solid lithium-air battery |
| CN114300789B (en) * | 2021-12-29 | 2024-04-30 | 吉林大学 | Preparation method of COF-based solid air positive electrode for solid lithium air battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110299516B (en) | Preparation method of carbon nanotube array loaded lithium titanate flexible electrode material | |
| CN108390033B (en) | Preparation method and application of carbon-coated antimony nanotube material as negative electrode material of sodium-ion battery | |
| CN100492721C (en) | Lithium ion battery pole piece with high multiplying power and production thereof | |
| CN108565464B (en) | Sulfur-carrying MOF @ conductive polymer material and preparation method and application thereof | |
| CN105489814B (en) | A kind of preparation method of lithium-sulfur cell modified diaphragm, modified diaphragm and the lithium-sulfur cell with the multilayer modified diaphragm | |
| CN115101741B (en) | Nitrogen-doped graphene-coated silicon-carbon composite material and preparation method and application thereof | |
| CN104103823B (en) | A kind of layering Li 4ti 5o 12the preparation method of graphene complex lithium ion battery cathode material | |
| US10727480B2 (en) | Sulfur composite cathode material and preparation method and application thereof | |
| CN111799462A (en) | Preparation method of metal manganese oxide/graphene composite electrode material | |
| CN111848892A (en) | Preparation method of carbon nanotube-loaded two-dimensional covalent organic framework electrode material | |
| Fu et al. | High reversible silicon/graphene nanocomposite anode for lithium-ion batteries | |
| CN111370656B (en) | Silicon-carbon composite material and preparation method and application thereof | |
| CN113903899A (en) | Covalent organic framework material/carbon nano tube organic composite material and application thereof in lithium ion battery | |
| CN111740080A (en) | Electrochemical sodium storage electrode made of composite nano material and preparation method thereof | |
| CN115692660A (en) | Vulcanized polyaniline composite positive electrode material, preparation method thereof and lithium-sulfur battery adopting same | |
| CN114613613B (en) | Polydopamine/graphene composite material lithium ion hybrid capacitor and preparation method thereof | |
| CN111029538B (en) | Carbon-coated silicon composite silicate material and preparation method and application thereof | |
| CN108493406B (en) | Application of high-nickel ternary cathode material as catalyst in preparation of carbon nanotube, cathode material and preparation method thereof, and lithium battery | |
| Wang et al. | Cyclodextrin polymers as effective water-soluble binder with enhanced cycling performance for Li2ZnTi3O8 anode in lithium-ion batteries | |
| CN113948699B (en) | Preparation method of MOF-5 containing six carbonyl functional groups and application of MOF-5 in high Wen Jia ion battery | |
| Jiang et al. | Preparation of straw porous carbon/graphite nanosheet composite and its electrochemical properties | |
| CN114335427B (en) | Three-dimensional V 2 O 3 Carbon nanofiber composite flexible electrode and preparation method and application thereof | |
| CN105576214A (en) | Modification method based on carbon-nitrogen conducting layer modified lithium titanate material | |
| WO2020253285A1 (en) | Porous graphene lithium cobaltate composite material, preparation method therefor, and use thereof | |
| CN108091495B (en) | Application of microcrystalline graphite material as negative electrode material of lithium ion capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201030 |
|
| RJ01 | Rejection of invention patent application after publication |