CN112466670A - Porous CTF nano sheet and preparation method and application thereof - Google Patents
Porous CTF nano sheet and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- C01B32/00—Carbon; Compounds thereof
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- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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Abstract
The invention discloses a porous CTF nano-sheet and a preparation method thereof, firstly, modifying silicon dioxide by adopting an aminosilane coupling agent to prepare an amino-functionalized silicon dioxide nano-sphere; thirdly, cyanuric chloride is grafted to the modified silicon dioxide nanospheres through a substitution reaction, and then 4- (4-aminophenoxy) benzonitrile is grafted through the substitution reaction; and then carrying out high-temperature polymerization and pyrolysis by adopting a zinc chloride ionothermal method, and finally etching the silicon dioxide template to obtain the porous CTF nano material with the sheet structure. The porous CTF nanosheet prepared by the method disclosed by the invention is high in O and N content and large in specific surface area, and when the porous CTF nanosheet is used as a supercapacitor electrode material, the specific capacitance is high, the rate capability is good, and the cycle life is long. The method has the advantages of simple operation, easily obtained raw materials, economy and high efficiency.
Description
Technical Field
The invention relates to a Covalent Triazine Framework (CTF) polymer, in particular to a CTF material with rich pore-size structure and ultrathin nanosheet morphology, a preparation method of a porous CTF nanosheet and application of the porous CTF nanosheet to a supercapacitor electrode material, and belongs to the technical field of materials.
Background
Super Capacitor (SC) is the key core product of green energy saving and emission reduction, and has attracted attention in recent years. Compared with an alkali metal battery, the SC has the advantages of simple structure, high power density, wide working temperature range, high charging speed, long service life and the like, and has important commercial prospects in the fields of 3C consumer electronics, military industry, urban public transportation, rail transit, petroleum machinery, wind power generation, road lighting and the like. The electrode material is the core component of the SC, and the type and the performance of the electrode material greatly determine the commercialization, scale development and application of the SC.
The covalent triazine-based framework (CTFs) is a covalent organic porous polymer containing triazine ring, and has the characteristics of light skeleton, large specific surface area, adjustable structure and the like. The electrode material has adjustable three-dimensional pore structure, homogeneously distributed heteroatoms such as N, O and the like, and has extremely high physical and chemical stability, so that the electrode material is widely concerned in the research of the electrode material of the super capacitor at present. CTFs form a spatial network polymer mainly by the self-polymerization of nitrile monomers under ionothermal reaction. Therefore, the controllable regulation of the pore channel structure and the content and distribution of the heteroatom of the CTFs can be realized by designing nitrile monomers containing the heteroatom with different structures. However, the morphology is also one of the important factors affecting the capacitive properties of the electrode material. For example, the unique two-dimensional nanosheet structure can increase the exposure rate of active sites on the surface of the material, increase the penetration capacity of the material to an electrolyte and shorten an ion transmission path, so that the material has high specific capacitance, excellent rate capability and cycle life when used as an electrode material of a supercapacitor.
At present, the controllable preparation of the CTFs electrode material mainly focuses on two aspects of pore size distribution and doping form, and a research report on morphology regulation of the CTFs electrode material is not discovered at all. In order to further realize the controllable preparation of the pore size distribution, the doping form and the morphology structure of the CTFs electrode material, the invention designs a novel O/N triazine-containing building unit modified by a silicon dioxide template, and obtains a novel triazine polymer by an ionothermal method. The triazine polymer has the advantages of high specific surface area, abundant pore structures, relatively uniform nanosheet structures and the like, and has excellent electrochemical performance when being used as an electrode material in 6MKOH electrolyte.
Disclosure of Invention
Aiming at the advantages of heteroatom-doped Covalent Triazine Framework (CTF) nanosheets in application of electrode materials, the invention provides a porous CTF nanosheet and a preparation method thereof, and also provides application of the porous CTF nanosheet in the field of electrode materials. The porous CTF nanosheet prepared by the method is high in O and N content and large in specific surface area. When the material is used as an electrode material, particularly as an electrode material of a super capacitor, the material has high capacitance performance, good rate performance and long cycle life. The method has the advantages of simple operation, easily obtained raw materials, economy and high efficiency.
According to a first embodiment provided by the present invention, there is provided a porous CTF nanoplatelet.
A porous CTF nanoplatelet prepared by a process comprising: the preparation method comprises the steps of modifying silicon dioxide by using an aminosilane coupling agent, grafting cyanuric chloride onto the modified silicon dioxide through a substitution reaction, grafting 4- (4-aminophenoxy) benzonitrile through the substitution reaction, performing high-temperature ionic thermal polymerization reaction on the benzonitrile and zinc chloride, and finally performing pyrolysis to obtain the porous CTF nanosheet.
In the present invention, the porous CTF nanoplatelets have 200m2·g-1To 700m2·g-1Preferably 300m2·g-1To 600m2·g-1More preferably 400m2·g-1To 500m2·g-1The BET specific surface area of (2) is more preferably 420m2·g-1To 480m2·g-1BET specific surface area of (2).
In the present invention, the porous CTF nanoplatelets have an average thickness of 1-30nm, preferably 5-25nm, more preferably 10-20nm, and even more preferably the porous CTF nanoplatelets have an average thickness of 12-18 nm.
In the present invention, the porous CTF nanoplatelets have an O content (at%) of 2.0% to 5.0%, preferably an O content (at%) of 2.6% to 4.5%, more preferably an O content (at%) of 3.0% to 4.0%.
In the present invention, the porous CTF nanoplatelets have an N content (at%) of 4.0% to 7.0%, preferably an N content (at%) of 4.5% to 5.5%, more preferably an N content (at%) of 4.6% to 6.0%.
In the present invention, when the porous CTF nanosheet is used as an electrode material for a capacitor, it is at 0.5A-g-1Has a specific capacitance of more than 150F g at a current density of (1)-1Preferably, the specific capacitance is greater than 180 F.g-1More preferably, the specific capacitance is more than 200 Fg-1。
According to a second embodiment provided by the present invention, there is provided a method of making porous CTF nanoplates.
A method of producing a porous CTF nanoplate or a method of producing a porous CTF nanoplate as described in the first embodiment, the method comprising the steps of:
(1) preparation of the silicon dioxide nanospheres: mixing ethanol and water, adding ammonia water into the mixed solution, uniformly stirring, adding tetraethyl orthosilicate, stirring, and separating to obtain monodisperse silicon dioxide nanospheres, which are recorded as: SiO 22；
(2) Preparation of amino modified silica nanospheres: SiO obtained by the step (1)2Dispersing in a solvent I, adding an aminosilane coupling agent under the protection of nitrogen or inert gas, reacting, and separating after the reaction is stopped to obtain amino modified silicon dioxide nanospheres, which are recorded as: SiO 22-NH2；
(3) Preparation of cyanuric chloride grafted silica nanospheres: SiO obtained by the step (2)2-NH2Dispersing in a solvent II, adding cyanuric chloride, reacting under the protection of nitrogen or inert gas, separating and collecting solid powder after the reaction is stopped to obtain light yellow powder, and recording as: SiO 22-TCT；
(4)4Preparation of silica nanospheres grafted with (4-aminophenoxy) benzonitrile: SiO obtained by the step (3)2-TCT is dispersed in a solvent III, 4- (4-aminophenoxy) benzonitrile is added, the reaction is carried out under the protection of nitrogen or inert gas, and after the reaction is stopped, solid powder is separated and collected to obtain yellow powder which is recorded as: SiO 22-CN；
(5) Preparation of the polymer: SiO obtained by the step (4)2-CN and ZnCl2Adding the mixture into a mortar, grinding the mixture until the mixture is uniformly mixed, adding the uniformly mixed mixture into a sealed tube, vacuumizing the sealed tube, sealing the tube after the mixture is completely dried, and heating the sealed tube to perform polymerization reaction; a polymer was obtained, noted: SiO 22-CTFN；
(6) Preparation of porous CTF nanosheets: SiO obtained by the step (5)2-CTFNAnd carrying out pyrolysis and carbonization reactions under the protection of nitrogen or inert gas to obtain the porous CTF nanosheet.
Preferably, the step (1) is specifically: mixing absolute ethyl alcohol and deionized water, adding 18-40 wt% of ammonia water (preferably 20-32 wt% of ammonia water, and more preferably 25-28 wt% of ammonia water) into the mixed solution of the absolute ethyl alcohol and the deionized water, uniformly stirring, adding tetraethyl orthosilicate, stirring at room temperature for 1-12h (preferably 2-10h, and more preferably 4-8h), centrifugally separating, ultrasonically washing with the deionized water and the absolute ethyl alcohol, and drying in vacuum to obtain monodisperse silicon dioxide nanospheres, which are recorded as: SiO 22。
Preferably, the step (2) is specifically: SiO obtained by the step (1)2Dispersing in a solvent I (preferably anhydrous toluene), carrying out ultrasonic treatment for 5-120min (preferably 10-90min, more preferably 20-60min), then dropwise adding an aminosilane coupling agent under the protection of nitrogen or helium or argon, and continuing to react for 2-48h (preferably 6-24h, more preferably 8-18 h); after the reaction is stopped, centrifugally separating, ultrasonically washing with toluene and absolute ethyl alcohol respectively, and drying in vacuum to obtain the amino modified silicon dioxide nanospheres which are recorded as follows: SiO 22-NH2。
Preferably, the step (3) is specifically: SiO obtained by the step (2)2-NH2Dispersing in solvent II (preferably anhydrous tetrahydrofuran), adding cyanuric chloride and alkali solution (preferably N, N-diisopropylethylamine or triethylamine or diethylamine) into the dispersion, and reacting under the protection of nitrogen or helium or argon (preferably at 1-30 deg.C for 1-48h, more preferably at 2-20 deg.C for 2-24 h); after the reaction is stopped, collecting solid powder by using a reduced pressure suction filtration device, washing the solid powder by using tetrahydrofuran and ethanol respectively, and drying the solid powder in vacuum to obtain light yellow powder which is recorded as: SiO 22-TCT。
Preferably, the step (4) is specifically: SiO obtained by the step (3)2Dispersing TCT in a solvent III (preferably anhydrous N, N-dimethylformamide), adding 4- (4-aminophenoxy) benzonitrile, and an alkali solution (preferably N, N-diisopropylethylamine or triethylamine or diethylamine) to the dispersion, and carrying out reflux reaction for 2-48h (preferably 6-24h) under the protection of nitrogen, helium or argon; after the reaction was stopped, the solid powder was collected using a vacuum filtration apparatus and washed with N, N-dimethylformamide and ethanol, respectively, and dried under vacuum to give a yellow powder, which was recorded as: SiO 22-CN。
Preferably, the step (5) is specifically: SiO obtained by the step (4)2-CN and ZnCl2Adding into mortar, grinding under infrared lamp until mixing, adding into sealed tube, placing the sealed tube in oil pan of 90-300 deg.C (preferably 100-; a polymer was obtained, noted: SiO 22-CTFN。
Preferably, the step (6) is specifically: SiO prepared in step (5)2-CTFNAfter the polymerization is completed, taking out the polymer, placing the polymer in a pyrolysis furnace (preferably a high-temperature tubular furnace), and raising the temperature to a pyrolysis temperature (the pyrolysis temperature is preferably 650-; putting the carbonized material into a container, adding deionized water, and adding the deionized water to the container at a temperature of between 45 and 10 DEG CStirring in an oil bath pan at 0 deg.C (preferably 60-90 deg.C), and vacuum filtering; adding dilute hydrochloric acid (preferably 0.5-2M hydrochloric acid), stirring for 1-24h (preferably 2-18h), vacuum filtering, and washing with deionized water to neutrality; adding HF or ammonium fluoride (preferably 5-20% by mass), stirring for 1-24h (preferably 2-18h), adjusting the pH to be neutral by using alkali liquor (preferably 0.5-3M NaOH), washing with deionized water, and finally drying the product to constant weight to obtain the porous CTF nanosheet.
In the present invention, the volume ratio of ethanol and water mixed in step (1) is 1:0.1 to 10, preferably 1:0.5 to 8, more preferably 1:1 to 5.
In the present invention, the amount of ammonia added in step (1) is 1 to 20% by volume, preferably 2 to 15% by volume, more preferably 3 to 10% by volume of ethanol.
In the present invention, the volume ratio of tetraethyl orthosilicate to ethanol in step (1) is 1:2 to 20, preferably 1:5 to 15, and more preferably 1:8 to 12.
In the present invention, the particle size of the amino-modified silica nanospheres prepared in step (1) is 50-600nm, preferably 100-500nm, and more preferably 150-400 nm.
In the invention, the aminosilane coupling agent in the step (2) is 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane.
In the present invention, SiO in step (2)2And the aminosilane coupling agent is added in a mass ratio of 1:0.1-5, preferably 1:0.2-4, more preferably 1: 0.3-2.
In the present invention, SiO in step (3)2-NH2And cyanuric chloride in a mass ratio of 1:0.2 to 3, preferably 1:0.3 to 2, more preferably 1:0.5 to 1.5.
In the present invention, SiO in step (4)2The mass ratio of (E) -TCT to 4- (4-aminophenoxy) benzonitrile is from 1:0.5 to 10, preferably from 1:1 to 8, more preferably from 1:1.5 to 5.
In the present invention, SiO in step (5)2-CN and ZnCl2Is added in a molar ratio of 1:0.1-10, preferably 1:0.2-8, more preferably 1: 0.3-6.
According to a third embodiment provided by the present invention, there is provided a use of porous CTF nanoplatelets.
According to the use of the porous CTF nanoplatelets of the first embodiment or the porous CTF nanoplatelets prepared by the method of the second embodiment, the porous CTF nanoplatelets are used as an electrode material.
Preferably, the porous CTF nanosheets are used as an organic electrode material.
Preferably, the porous CTF nanosheets are used as an electrode material for a capacitor or supercapacitor.
Firstly, modifying silicon dioxide (preferably silicon dioxide nanospheres) by adopting an aminosilane coupling agent to prepare amino-functionalized silicon dioxide nanospheres; thirdly, cyanuric chloride is grafted to the modified silicon dioxide nanospheres through a substitution reaction, and then 4- (4-aminophenoxy) benzonitrile is grafted through the substitution reaction; and then carrying out high-temperature polymerization and pyrolysis by adopting a zinc chloride ionothermal method, and finally etching the silicon dioxide template to obtain the porous CTF nano material with the sheet structure. The porous CTF nanosheet prepared by the method disclosed by the invention is high in O and N content and large in specific surface area, and when the porous CTF nanosheet is used as a supercapacitor electrode material, the specific capacitance is high, the rate capability is good, and the cycle life is long. The method has the advantages of simple operation, easily obtained raw materials, economy and high efficiency.
In the present invention, silica is first modified by an aminosilane coupling agent (e.g., 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane) to obtain a silica with "-NH groups2"modified silica spheres of groups, followed by grafting cyanuric chloride onto the modified silica, in particular onto a silica bearing" -NH groups2"modified silica spheres of groups" -NH2"on the radical; adding 4- (4-aminophenoxy) benzonitrile into the reaction, reacting the 4- (4-aminophenoxy) benzonitrile with the silica sphere after the two-step modification grafting, reacting the 4- (4-aminophenoxy) benzonitrile with a "chlorocyan" group on the modified silica sphere, and substituting the 4- (4-aminophenoxy) benzonitrile for a "Cl" atom on the modified silica sphere so as to graft the modified silica sphere; carrying out high-temperature ionothermal polymerization on the silicon dioxide spheres subjected to dispersion modification and zinc chlorideAnd (4) reacting, and finally performing pyrolysis to obtain the porous CTF nano sheet.
In the invention, the function of adding alkali liquor in the step (3) is as follows: the HCl generated by the substitution reaction is neutralized with an alkali solution, providing reaction speed and yield. Preferably, the alkali liquor is N, N-diisopropylethylamine or triethylamine or diethylamine.
In the invention, the function of adding alkali liquor in the step (4) is as follows: the HCl generated by the substitution reaction is neutralized with an alkali solution, providing reaction speed and yield. Preferably, the alkali liquor is N, N-diisopropylethylamine or triethylamine or diethylamine.
In the present invention, in the step (5), deionized water is added after the carbonization in order to remove residual zinc chloride.
In the present invention, in step (5), the dilute hydrochloric acid is added after the carbonization in order to remove residual impurities.
In the present invention, in step (5), HF or ammonium fluoride is added after the carbonization for the purpose of removing silicon dioxide.
The raw materials, reagents and equipment used in the present invention are as follows:
tetraethyl orthosilicate: michelin chemical reagent, Inc., AR
Anhydrous ethanol: michelin chemical reagent, Inc., AR
Ammonia water: michelin chemical reagent, Inc., AR
3-aminopropyltrimethoxysilane: michelin chemical reagent, Inc., AR
Anhydrous toluene: michelin chemical reagent, Inc., AR
Anhydrous tetrahydrofuran: michelin chemical reagent, Inc., AR
Dimethyl acetamide: michelin chemical reagent, Inc., AR
Cyanuric chloride: michelin chemical reagent, Inc., AR
N, N-diisopropylethylamine: michelin chemical reagent, Inc., AR
4- (4-aminophenoxy) benzonitrile: annagig chemical company, AR.
HCl: tianjin, Fuyu Fine chemical Co., Ltd, AR.
Polytetrafluoroethylene: aladdin Chemicals Inc., 60 wt%.
N2: hong Yuan gas Co., Ltd, Hunan Zhong Tai.
Foamed nickel: changshaoyuan new materials, Limited liability company.
Transmission Electron Microscope (TEM): FEI Tecnai F20
X-ray photoelectron spectroscopy (XPS): K-Alpha 1063, Seimer Feishell science, England.
Specific surface area and pore size analyzer: micromeritics, Inc., Tristar II 3020, USA.
An electrochemical workstation: shanghai Chenghua instruments Inc., CHI 760D.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. the method is simple, the used raw materials are easy to obtain, and the polymer monomer is synthesized with ZnCl2The polymerization to form triazine ring under high temperature condition is the first time.
2. The method realizes the regulation and control of the heteroatom content, the lamella thickness and the pore diameter structure of the CTF nanosheet organic electrode material by changing the raw material ratio and controlling the preparation conditions.
3. The CTF nanosheet organic electrode material prepared by the method has the advantages of large specific surface area, uniform pore size distribution and high O and N contents, and has excellent electrochemical performance when being used as an electrode material of a super capacitor.
Drawings
Fig. 1 is a process flow diagram for preparing the porous CTF nanosheet according to the present invention.
Fig. 2 is a transmission electron micrograph of porous CTF nanoplates prepared according to example 1 of the invention.
Fig. 3 is a N2 adsorption-desorption curve of porous CTF nanoplates prepared according to example 1 of the present invention.
Fig. 4 is a pore size distribution curve of porous CTF nanoplates prepared in example 1 of the present invention.
Fig. 5 is an XPS spectrum of porous CTF nanoplates prepared according to example 1 of the present invention.
Fig. 6 is a cyclic voltammetry test chart of the porous CTF nanosheet prepared in example 1 of the present invention when applied to a supercapacitor.
Fig. 7 is a constant current charge and discharge test chart when the porous CTF nanosheet prepared in example 1 of the present invention is applied to a supercapacitor.
Detailed Description
The technical solution of the present invention is illustrated below, and the claimed scope of the present invention includes, but is not limited to, the following examples.
According to a first embodiment provided by the present invention, there is provided a porous CTF nanoplatelet.
A porous CTF nanoplatelet prepared by a process comprising: the preparation method comprises the steps of modifying silicon dioxide by using an aminosilane coupling agent, grafting cyanuric chloride onto the modified silicon dioxide through a substitution reaction, grafting 4- (4-aminophenoxy) benzonitrile through the substitution reaction, performing high-temperature ionic thermal polymerization reaction on the benzonitrile and zinc chloride, and finally performing pyrolysis to obtain the porous CTF nanosheet.
In the present invention, the porous CTF nanoplatelets have 200m2·g-1To 700m2·g-1Preferably 300m2·g-1To 600m2·g-1More preferably 400m2·g-1To 500m2·g-1The BET specific surface area of (2) is more preferably 420m2·g-1To 480m2·g-1BET specific surface area of (2).
In the present invention, the porous CTF nanoplatelets have an average thickness of 1-30nm, preferably 5-25nm, more preferably 10-20nm, and even more preferably the porous CTF nanoplatelets have an average thickness of 12-18 nm.
In the present invention, the porous CTF nanoplatelets have an O content (at%) of 2.0% to 5.0%, preferably an O content (at%) of 2.6% to 4.5%, more preferably an O content (at%) of 3.0% to 4.0%.
In the present invention, the porous CTF nanoplatelets have an N content (at%) of 4.0% to 7.0%, preferably an N content (at%) of 4.5% to 5.5%, more preferably an N content (at%) of 4.6% to 6.0%.
In the present invention, when the porous CTF nanosheet is used as an electrode material for a capacitor, it is at 0.5A-g-1Has a specific capacitance of more than 150F g at a current density of (1)-1Preferably, the specific capacitance is greater than 180 F.g-1More preferably, the specific capacitance is more than 200 Fg-1。
According to a second embodiment provided by the present invention, there is provided a use of porous CTF nanoplatelets.
Using the porous CTF nanosheets as an electrode material.
Preferably, the porous CTF nanosheets are used as an organic electrode material.
Preferably, the porous CTF nanosheets are used as an electrode material for a capacitor or supercapacitor.
Structural characterization of biochar in the following examples is by N2Adsorption (Micromeritics TriStar II 3020) test. The specific surface area is calculated according to the Brunauer-Emmett-Teller (BET) theory, and the Pore Size Distribution (PSD) is calculated by using the adsorption branch of the adsorption isotherm and by using the Barrett-Joyner-Halenda (BJH) model.
The preparation method of the electrode when the CTF nanosheet is used as the electrode material of the supercapacitor in the following example is as follows:
the prepared CTF nano sheet is used as an active substance, conductive carbon black is used as a conductive agent, polytetrafluoroethylene emulsion (PTFE,60 wt%) is used as a binder, and foamed nickel is used as a current collector. Dispersing the three substances in ethanol according to the ratio of 8:1:1, stirring and ultrasonically treating until the three substances are uniformly mixed, grinding the mixture in a mortar, and uniformly coating the mixture on a foamed nickel sheet when the ethanol is volatilized and the mixture is in a slurry state. After the electrode prepared by the method is slightly dried, the electrode is kept for 5min to be compacted under the pressure of 10MPa, and then the electrode is placed into a 120 ℃ oven to be dried for 12h for standby. The loading amount of the active substances of the organic electrode materials is respectively 3mg cm-2Left and right.
The electrochemical test method of the CTF organic material as the electrode material of the super capacitor in the following examples is as follows:
the capacitance performance of the single electrode was tested using a CHI760D electrochemical workstation three-electrode system, in which the counter electrode was a platinum wire electrode, Hg/HgO was a reference electrode, and 6M KOH solution was an electrolyte. In the example, the electrochemical performance test is mainly carried out by adopting methods such as Cyclic Voltammetry (CV), constant current charging and discharging (GC), Electrochemical Impedance Spectroscopy (EIS) and the like. The range of the cyclic voltammetry test voltage of a single electrode is set to be-1-0V. The current density of the charge and discharge test is set to 0.5-20A g-1And the voltage range is-1 to 0V. The cyclic charge and discharge test was performed by a three-electrode system with a current density set at 1A g-1Wherein the counter electrode and the reference electrode are the same electrode, and the working voltage range is set to be 0-1V.
The specific capacitance of the organic electrode material is calculated by a discharge curve of constant current charge and discharge according to the following formula: cgI/(mdV/dt). Where I is a constant current, m is a mass of the active material, and dV/dt is a slope calculated from a discharge curve excluding a voltage drop portion.
Example 1
A method of making porous CTF nanoplates, the method comprising the steps of:
(1) after 90ml of absolute ethyl alcohol and 10ml of deionized water were mixed, 6ml of ammonia (26 wt%) was added to the above solution, after stirring well, 9ml of tetraethyl orthosilicate was added, stirred at room temperature for 6 hours, centrifuged, and washed with deionized water and absolute ethyl alcohol with ultrasound. Vacuum drying yielded monodisperse silica nanospheres, noted: SiO 22；
(2) 1g of SiO2Dispersing in 100ml of anhydrous toluene, carrying out ultrasonic treatment for 30 minutes, slowly dropwise adding 0.5ml of 3-aminopropyltrimethoxysilane into the dispersion under the protection of nitrogen, and continuing the reaction for 12 hours. After the reaction is stopped, performing centrifugal separation, performing ultrasonic washing by using toluene and absolute ethyl alcohol respectively, and performing vacuum drying to obtain the amino modified silicon dioxide nanospheres, which are recorded as follows: SiO 22-NH2；
(3) 1g of SiO2-NH2Dispersed in 50ml of anhydrous tetrahydrofuran, and 1g of cyanuric chloride and 2ml of N, N-diisopropylethylamine were added to the above dispersion to react at 5 ℃ for 12 hours under nitrogen protection. After the reaction is stopped, collecting solid powder by using a decompression suction filtration device, washing the solid powder by using tetrahydrofuran and ethanol respectively, drying the solid powder in vacuum to obtain light yellow powder,is recorded as: SiO 22-TCT；
(4) 1g of SiO2-TCT was dispersed in 50ml of anhydrous N, N-dimethylformamide, and 2g of 4- (4-aminophenoxy) benzonitrile and 2ml of N, N-diisopropylethylamine were added to the above dispersion, followed by reflux reaction under a nitrogen atmosphere for 12 hours. After the reaction was stopped, the solid powder was collected using a vacuum filtration apparatus and washed with N, N-dimethylformamide and ethanol, respectively, and dried under vacuum to give a yellow powder, which was recorded as: SiO 22-CN；
(5) 1g of SiO2-CN monomer and 500mg ZnCl2Adding into mortar, and grinding under infrared lamp until mixing. Then, adding the uniformly mixed medicine into a sealed tube, placing the sealed tube in an oil pan at 150 ℃, vacuumizing for 4 hours, sealing the tube after the mixture is completely dried, placing the sealed tube in a muffle furnace, and polymerizing for 40 hours at 600 ℃;
(6) after polymerization was complete, the polymer was removed, the bulk polymer was crushed and placed in a high temperature tube furnace under N2Heating to 800 ℃ at the speed of 5 ℃/min under the protection of (1), carrying out 2h, putting the carbonized organic electrode material into a 1000mL round-bottom flask, adding a large amount of water, stirring overnight in a 90 ℃ oil bath, carrying out suction filtration, adding 500mL of 1M dilute hydrochloric acid, stirring for 12 hours, carrying out suction filtration, washing with water for several times until the solution is neutral, adding 10% HF, stirring for 12 hours, adjusting the pH to be neutral by using 1M NaOH, washing for several times by using deionization, and finally drying the product to constant weight to obtain 80mg porous CTF nanosheets.
The porous CTF nanosheet prepared in this example was tested:
the prepared porous CTF nano sheet has a graphene-like nano sheet structure as shown in figure 2, and the average thickness of the nano sheet is 16 nm. As shown in FIG. 3, the BET specific surface area is as high as 415m2·g-1Total pore volume of 0.2cm3·g-1. As shown in fig. 4, the pore diameter of the material is mostly microporous, a part is mesoporous, a small part is macroporous, and the material has ideal pore diameter distribution. As shown in FIG. 5, the O content was 3.75 at%, and the N content was 5.92 at%. When used as an electrode material of a super capacitor. As shown in FIG. 6, at 0.5A · g-1At a current density of (A), the CTF nanosheet is organicThe specific capacitance of the electrode material was 225F g-1。
Example 2
A method of making porous CTF nanoplates, the method comprising the steps of:
(1) after 90ml of absolute ethyl alcohol and 10ml of deionized water are mixed, 6ml of ammonia water (25-28 wt%) is added into the solution, after the mixture is uniformly stirred, 9ml of tetraethyl orthosilicate is added, the mixture is stirred for 6 hours at room temperature, and the mixture is centrifugally separated and washed by deionized water and absolute ethyl alcohol by ultrasound. Vacuum drying yielded monodisperse silica nanospheres, noted: SiO 22；
(2) 1g of SiO2Dispersing in 100ml of anhydrous toluene, carrying out ultrasonic treatment for 30 minutes, slowly dropwise adding 0.5ml of 3-aminopropyltrimethoxysilane into the dispersion under the protection of nitrogen, and continuing the reaction for 12 hours. After the reaction is stopped, performing centrifugal separation, performing ultrasonic washing by using toluene and absolute ethyl alcohol respectively, and performing vacuum drying to obtain the amino modified silicon dioxide nanospheres, which are recorded as follows: SiO 22-NH2；
(3) 1g of SiO2-NH2Dispersed in 50ml of anhydrous tetrahydrofuran, and 1g of cyanuric chloride and 2ml of N, N-diisopropylethylamine were added to the above dispersion to react at 5 ℃ for 12 hours under nitrogen protection. After the reaction is stopped, collecting solid powder by using a reduced pressure suction filtration device, washing the solid powder by using tetrahydrofuran and ethanol respectively, and drying the solid powder in vacuum to obtain light yellow powder which is recorded as: SiO 22-TCT；
(4) 1g of SiO2-TCT was dispersed in 50ml of anhydrous N, N-dimethylformamide, and 2g of 4- (4-aminophenoxy) benzonitrile and 2ml of N, N-diisopropylethylamine were added to the above dispersion, followed by reflux reaction under a nitrogen atmosphere for 12 hours. After the reaction was stopped, the solid powder was collected using a vacuum filtration apparatus and washed with N, N-dimethylformamide and ethanol, respectively, and dried under vacuum to give a yellow powder, which was recorded as: SiO 22-CN；
(5) 1g of SiO2-CN monomer and 500mg ZnCl2Adding into mortar, and grinding under infrared lamp until mixing. Then, the evenly mixed medicine is added into a sealed tube, and the sealed tube is placed in an oil pan with the temperature of 150 ℃ for vacuumizing for 4 hoursAfter the mixture is completely dried, sealing the tube, placing the sealed tube in a muffle furnace, and polymerizing for 40 hours at 600 ℃;
(6) after polymerization was complete, the polymer was removed, the chunks were ground down and placed in a high temperature tube furnace under N2Heating to 700 ℃ at the speed of 5 ℃/min under the protection of (1), heating for 2h, putting the carbonized organic electrode material into a 1000mL round-bottom flask, adding a large amount of water, stirring overnight in a 90 ℃ oil bath, performing suction filtration, adding 500mL of 1M dilute hydrochloric acid, stirring for 12 hours, performing suction filtration, washing with water for several times to be neutral, adding 10% HF, stirring for 12 hours, adjusting the pH to be neutral by using 1M NaOH, washing for several times by using deionization, and finally drying the product to constant weight to obtain 85mg of porous CTF nanosheets.
Example 2 porous CTF nanoplates prepared have BET specific surface areas of up to 400m2·g-1Total pore volume of 0.22cm3·g-1The O content was 3.55 at%, and the N content was 4.73 at%. When used as an electrode material of a supercapacitor, the amount of the organic acid is 0.5A · g-1The specific capacitance of the organic electrode material of the CTF nanosheet is 200 Fg at the current density of (2)-1。
Example 3
A method of making porous CTF nanoplates, the method comprising the steps of:
(1) after 90ml of absolute ethyl alcohol and 10ml of deionized water are mixed, 6ml of ammonia water (25-28 wt%) is added into the solution, after the mixture is uniformly stirred, 8ml of tetraethyl orthosilicate is added, the mixture is stirred for 6 hours at room temperature, and the mixture is centrifugally separated and is respectively washed by deionized water and absolute ethyl alcohol by ultrasound. Vacuum drying yielded monodisperse silica nanospheres, noted: SiO 22；
(2) 1g of SiO2Dispersing in 100ml of anhydrous toluene, carrying out ultrasonic treatment for 30 minutes, slowly dropwise adding 0.45ml of 3-aminopropyltriethoxysilane into the dispersion under the protection of nitrogen, and continuing to react for 12 hours. After the reaction is stopped, performing centrifugal separation, performing ultrasonic washing by using toluene and absolute ethyl alcohol respectively, and performing vacuum drying to obtain the amino modified silicon dioxide nanospheres, which are recorded as follows: SiO 22-NH2；
(3) 1g of SiO2-NH2Dispersed in 50ml of anhydrous tetrahydrofuran, and 2g of cyanuric chloride and 2ml of N, N-diisopropylethylamine were added to the above dispersion to react at 5 ℃ for 12 hours under nitrogen protection. After the reaction is stopped, collecting solid powder by using a reduced pressure suction filtration device, washing the solid powder by using tetrahydrofuran and ethanol respectively, and drying the solid powder in vacuum to obtain light yellow powder which is recorded as: SiO 22-TCT；
(4) 1g of SiO2-TCT was dispersed in 50ml of anhydrous N, N-dimethylformamide, and 2g of 4- (4-aminophenoxy) benzonitrile and 2ml of N, N-diisopropylethylamine were added to the above dispersion, followed by reflux reaction under a nitrogen atmosphere for 12 hours. After the reaction was stopped, the solid powder was collected using a vacuum filtration apparatus and washed with N, N-dimethylformamide and ethanol, respectively, and dried under vacuum to give a yellow powder, which was recorded as: SiO 22-CN；
(5) 1g of SiO2-CN monomer and 500mg ZnCl2Adding into mortar, and grinding under infrared lamp until mixing. Then, adding the uniformly mixed medicine into a sealed tube, placing the sealed tube in an oil pan at 150 ℃, vacuumizing for 4 hours, sealing the tube after the mixture is completely dried, placing the sealed tube in a muffle furnace, and polymerizing for 40 hours at 600 ℃;
(6) after polymerization was complete, the polymer was removed, the chunks were ground down and placed in a high temperature tube furnace under N2Heating to 900 ℃ at the speed of 5 ℃/min under the protection of (1), heating for 2 hours, putting the carbonized organic electrode material into a 1000mL round-bottom flask, adding a large amount of water, stirring overnight in a 90 ℃ oil bath, performing suction filtration, adding 500mL of 1M dilute hydrochloric acid, stirring for 12 hours, performing suction filtration, washing with water for several times until the mixture is neutral, adding 10% HF, stirring for 12 hours, adjusting the pH to be neutral by using 1M NaOH, washing for several times by using deionization, and finally drying the product to constant weight to obtain 75mg of porous CTF nanosheets.
Example 3 porous CTF nanoplates prepared have BET specific surface areas up to 405m2·g-1Total pore volume of 0.25cm3·g-1The O content was 3.46 at%, and the N content was 4.80 at%. When the O/N doped CTF nano-sheet is used as an electrode material of a super capacitor, the concentration is 0.5 A.g-1At a current density of 203 F.g in specific capacitance-1。
Example 4
Example 1 was repeated except that 20 wt% aqueous ammonia was used in step (1).
Example 5
Example 1 was repeated except that argon was used as the protective gas.
Example 6
Example 1 was repeated except that triethylamine was used in place of N, N-diisopropylethylamine in step (3) and step (4).
Example 7
Example 2 was repeated except that diethylamine was used in place of N, N-diisopropylethylamine in step (3) and step (4).
Example 8
Example 1 was repeated except that 16% ammonium fluoride was used instead of HF in step (5).
Claims (10)
1. A porous CTF nanoplate characterized by: the porous CTF nanosheet is prepared by the following method: the preparation method comprises the steps of modifying silicon dioxide by using an aminosilane coupling agent, grafting cyanuric chloride onto the modified silicon dioxide through a substitution reaction, grafting 4- (4-aminophenoxy) benzonitrile through the substitution reaction, performing high-temperature ionic thermal polymerization reaction on the benzonitrile and zinc chloride, and finally performing pyrolysis to obtain the porous CTF nanosheet.
2. Porous CTF nanoplatelets according to claim 1 characterized in that: the porous CTF nanosheet has a thickness of 200m2·g-1To 700m2·g-1Preferably 300m2·g-1To 600m2·g-1More preferably 400m2·g-1To 500m2·g-1BET specific surface area of (a); and/or
The porous CTF nanoplatelets have an average thickness of 1-30nm, preferably 5-25nm, more preferably 10-20 nm.
3. Porous CTF nanoplatelets according to claim 1 or 2 characterized in that: the porous CTF nanoplatelets have an O content (at%) of 2.0% to 5.0%, preferably an O content (at%) of 2.6% to 4.5%, more preferably an O content (at%) of 3.0% to 4.0%; and/or
The porous CTF nanoplatelets have an N content (at%) of 4.0% to 7.0%, preferably an N content (at%) of 4.5% to 5.5%, more preferably an N content (at%) of 4.6% to 6.0%.
4. Porous CTF nanoplatelets according to any of claims 1-3 characterized in that: when the porous CTF nanosheet is used as an electrode material for a capacitor, the concentration is 0.5A-g-1Has a specific capacitance of more than 150F g at a current density of (1)-1Preferably, the specific capacitance is greater than 180 F.g-1More preferably, the specific capacitance is more than 200 Fg-1。
5. A method of making porous CTF nanoplatelets or a method of making porous CTF nanoplatelets according to any of claims 1-4, comprising the steps of:
(1) preparation of the silicon dioxide nanospheres: mixing ethanol and water, adding ammonia water into the mixed solution, uniformly stirring, adding tetraethyl orthosilicate, stirring, and separating to obtain monodisperse silicon dioxide nanospheres, which are recorded as: SiO 22；
(2) Preparation of amino modified silica nanospheres: SiO obtained by the step (1)2Dispersing in a solvent I, adding an aminosilane coupling agent under the protection of nitrogen or inert gas, reacting, and separating after the reaction is stopped to obtain amino modified silicon dioxide nanospheres, which are recorded as: SiO 22-NH2；
(3) Preparation of cyanuric chloride grafted silica nanospheres: SiO obtained by the step (2)2-NH2Dispersing in a solvent II, adding cyanuric chloride, reacting under the protection of nitrogen or inert gas, separating and collecting solid powder after the reaction is stopped to obtain light yellow powder, and recording as: SiO 22-TCT；
(4) Preparation of 4- (4-aminophenoxy) benzonitrile grafted silica nanospheres: will be described in detail(3) Preparation of the obtained SiO2-TCT is dispersed in a solvent III, 4- (4-aminophenoxy) benzonitrile is added, the reaction is carried out under the protection of nitrogen or inert gas, and after the reaction is stopped, solid powder is separated and collected to obtain yellow powder which is recorded as: SiO 22-CN；
(5) Preparation of the polymer: SiO obtained by the step (4)2-CN and ZnCl2Adding the mixture into a mortar, grinding the mixture until the mixture is uniformly mixed, adding the uniformly mixed mixture into a sealed tube, vacuumizing the sealed tube, sealing the tube after the mixture is completely dried, and heating the sealed tube to perform polymerization reaction; a polymer was obtained, noted: SiO 22-CTFN；
(6) Preparation of porous CTF nanosheets: SiO obtained by the step (5)2-CTFNAnd carrying out pyrolysis and carbonization reactions under the protection of nitrogen or inert gas to obtain the porous CTF nanosheet.
6. The method of claim 5, wherein: the step (1) is specifically as follows: mixing absolute ethyl alcohol and deionized water, adding 18-40 wt% of ammonia water (preferably 20-32 wt% of ammonia water, and more preferably 25-28 wt% of ammonia water) into the mixed solution of the absolute ethyl alcohol and the deionized water, uniformly stirring, adding tetraethyl orthosilicate, stirring at room temperature for 1-12h (preferably 2-10h, and more preferably 4-8h), centrifugally separating, ultrasonically washing with the deionized water and the absolute ethyl alcohol, and drying in vacuum to obtain monodisperse silicon dioxide nanospheres, which are recorded as: SiO 22(ii) a And/or
The step (2) is specifically as follows: SiO obtained by the step (1)2Dispersing in a solvent I (preferably anhydrous toluene), carrying out ultrasonic treatment for 5-120min (preferably 10-90min, more preferably 20-60min), then dropwise adding an aminosilane coupling agent under the protection of nitrogen or helium or argon, and continuing to react for 2-48h (preferably 6-24h, more preferably 8-18 h); after the reaction is stopped, centrifugally separating, ultrasonically washing with toluene and absolute ethyl alcohol respectively, and drying in vacuum to obtain the amino modified silicon dioxide nanospheres which are recorded as follows: SiO 22-NH2。
7. The method of claim 5The method is characterized in that: the step (3) is specifically as follows: SiO obtained by the step (2)2-NH2Dispersing in solvent II (preferably anhydrous tetrahydrofuran), adding cyanuric chloride and alkali solution (preferably N, N-diisopropylethylamine or triethylamine or diethylamine) into the dispersion, and reacting under the protection of nitrogen or helium or argon (preferably at 1-30 deg.C for 1-48h, more preferably at 2-20 deg.C for 2-24 h); after the reaction is stopped, collecting solid powder by using a reduced pressure suction filtration device, washing the solid powder by using tetrahydrofuran and ethanol respectively, and drying the solid powder in vacuum to obtain light yellow powder which is recorded as: SiO 22-TCT; and/or
The step (4) is specifically as follows: SiO obtained by the step (3)2Dispersing TCT in a solvent III (preferably anhydrous N, N-dimethylformamide), adding 4- (4-aminophenoxy) benzonitrile, and an alkali solution (preferably N, N-diisopropylethylamine or triethylamine or diethylamine) to the dispersion, and carrying out reflux reaction for 2-48h (preferably 6-24h) under the protection of nitrogen, helium or argon; after the reaction was stopped, the solid powder was collected using a vacuum filtration apparatus and washed with N, N-dimethylformamide and ethanol, respectively, and dried under vacuum to give a yellow powder, which was recorded as: SiO 22-CN。
8. The method of claim 5, wherein: the step (5) is specifically as follows: SiO obtained by the step (4)2-CN and ZnCl2Adding into mortar, grinding under infrared lamp until mixing, adding into sealed tube, placing the sealed tube in oil pan of 90-300 deg.C (preferably 100-; a polymer was obtained, noted: SiO 22-CTFN(ii) a And/or
The step (6) is specifically as follows: SiO prepared in step (5)2-CTFNAfter the polymerization is completed, the polymer is taken out, placed in a pyrolysis furnace (preferably a high-temperature tubular furnace), and heated to the pyrolysis temperature (the pyrolysis temperature is preferably 650-1000 ℃, more preferably 700-950 ℃) under the protection of nitrogen or helium or argonMore preferably 720-900 ℃), carrying out pyrolysis and carbonization reactions (the pyrolysis time is 1-5h, preferably 1.5-3 h); putting the carbonized material into a container, adding deionized water, stirring in an oil bath pan at 45-100 ℃ (preferably 60-90 ℃), and performing suction filtration; adding dilute hydrochloric acid (preferably 0.5-2M hydrochloric acid), stirring for 1-24h (preferably 2-18h), vacuum filtering, and washing with deionized water to neutrality; adding HF or ammonium fluoride (preferably 5-20% by mass), stirring for 1-24h (preferably 2-18h), adjusting the pH to be neutral by using alkali liquor (preferably 0.5-3M NaOH), washing with deionized water, and finally drying the product to constant weight to obtain the porous CTF nanosheet.
9. The method according to any one of claims 5-8, wherein: the volume ratio of the ethanol and the water mixed in the step (1) is 1:0.1-10, preferably 1:0.5-8, and more preferably 1: 1-5; the volume addition amount of the ammonia water is 1-20% of that of the ethanol, preferably 2-15%, and more preferably 3-10%; the volume ratio of tetraethyl orthosilicate to ethanol is 1:2-20, preferably 1:5-15, more preferably 1: 8-12; the particle size of the prepared amino modified silicon dioxide nanosphere is 50-600nm, preferably 100-500nm, and more preferably 150-400 nm; and/or
The amino silane coupling agent in the step (2) is 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane; SiO 22And aminosilane coupling agent with the addition mass ratio of 1:0.1-5, preferably 1:0.2-4, more preferably 1: 0.3-2; and/or
SiO in step (3)2-NH2And cyanuric chloride in a mass ratio of 1:0.2-3, preferably 1:0.3-2, more preferably 1: 0.5-1.5; and/or
SiO in step (4)2-TCT and 4- (4-aminophenoxy) benzonitrile in a mass ratio of 1:0.5 to 10, preferably 1:1 to 8, more preferably 1:1.5 to 5; and/or
SiO in step (5)2-CN and ZnCl2The addition mass ratio of (A) to (B) is 1:0.1-10, preferably 1:0.2-8, more preferably 1: 0.3-6.
10. Use of porous CTF nanoplatelets according to any of claims 1-4 or prepared by the method of any of claims 5-9, characterized in that: the porous CTF nanosheets are used as an electrode material, preferably, the porous CTF nanosheets are used as an electrode material for a capacitor or supercapacitor.
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