CN110483799A - A kind of controllable method for preparing and its stored energy application based on covalent organic frame - Google Patents
A kind of controllable method for preparing and its stored energy application based on covalent organic frame Download PDFInfo
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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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- 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 present invention provides a kind of controllable method for preparing and its stored energy application based on covalent organic frame, withβBased on the covalent organic framework COFs material of -one amide connection, by the selection of design and polymerized monomer pre-polymerization environment to its topological structure, the effective control of energy storage component in COFs material being successfully introduced into microscopic appearance is realized.Anthraquinone molecular can make COFs material show apparent electrochemical energy storage activity as energy storage component, pass through mechanical lapping and double inducing actions of differential responses solvent during organic frame unit molecule pre-polymerization simultaneously, COFs material is realized in the oriented growth of different dimensions, the final microscopic appearance that obtains is the covalent organic crystal material G-S-COFs energy storage material of stick tufted；Solvent method polymerization is directlyed adopt, the covalent organic crystal material C-S-COFs of flower-shape being made of nanometer sheet is finally obtained.The invention has the advantages that on the basis of guaranteeing that the energy storage of COFs material is active, effectively improve that COFs material pattern under the conditions of solvent heat is unformed and the uncontrollable disadvantage of growth course.
Description
Technical field
The invention belongs to technical field of function materials, and in particular to one kind is based on the controllable of covalent organic framework (COFs)
Preparation Method and its stored energy application as electrode material for super capacitor.
Background technique
COFs is a kind of all by having of being formed of dynamic covalent chemical polymerization reaction by light element (hydrogen, boron, carbon, nitrogen etc.)
The porous polymer material of phase property crystalline network frame structure.Since Yaghi professor seminar in 2005 successfully synthesizes for the first time
Since COFs material, due to the great potential that it shows on structure feature and performance development, it is strong academia has been caused
Research interest, be widely used in gas storage with separate, photoelectric material, the fields such as catalysis and energy storage.
Have benefited from ordered arrangement of the structural unit on molecular scale, COFs and other unordered porous organic polymer (examples
Such as: conjugation microporous polymer, super cross-linked polymer, intrinsic microporous polymer and porous fragrant frame compound etc.) compare, table
The stacked arrangement skeleton of more regular one-dimensional tunnel structure and high-sequential is revealed, this is not only expected to realize its high-ratio surface
Product making full use of in thermal energy storage process, and solid structure base has been established for the accurate functionalization of such material microstructure
Plinth.With the metal-organic framework material equally synthesized by " netted chemistry " (Reticular chemistry) design principle
(MOFs) it compares, since by high forces (covalent bond) connection structure unit, COFs can show more outstanding chemistry
Stability.Excellent architectural characteristic, finally creates COFs and the perfection of electrode material for super capacitor design demand agrees with.
Solvent-thermal method is the main method of current synthesis COFs material.Due to lack to during solvent thermal polymerization it is each because
Effective control of element can not often be precisely controlled the pattern and size of COFs material in actual fabrication process, it is micro- to ultimately cause its
Seeing structural advantage can not give full play in thermal energy storage process.
Summary of the invention
The present invention is with one kindβCovalent organic framework (COFs) material of -one amide connection is research object, by opening up to it
Flutter the design of structure and the selection of polymerized monomer pre-polymerization environment, realize energy storage component in COFs material be successfully introduced into it is microcosmic
Effective control of pattern.
The technical solution adopted by the invention is as follows:
A kind of controllable method for preparing based on covalent organic frame, withβ-one amide connection covalent organic framework COFs material be
It is main, COFs material is introduced using anthraquinone molecular as energy storage component, by mechanical lapping and reaction dissolvent in organic frame unit point
Double inducing actions during sub- pre-polymerization or by directlying adopt solvent method polymerization, realize COFs material in the orientation of different dimensions
Growth obtains the novel C OFs energy storage material with diverse microcosmic appearance.
A kind of controllable method for preparing based on covalent organic frame, using trihydroxy benzene trioxin and diamino-anthraquinone as
COFs structural molecule carries out external force mechanical intervention to monomer material first, then cooperation is anti-using pre- poly- solvent heat two-step method
The inductive effect of solvent is answered, to change the growth pattern of oligomer, guides COFs crystal in different dimensional under the conditions of high temperature polymerization
Oriented growth is spent, the covalent organic crystal material G-S-COFs that microscopic appearance is stick tufted is obtained, specifically includes the following steps:
Step (1) passes through external force mechanical intervention and reaction dissolvent polarity using trihydroxy benzene trioxin and diamino-anthraquinone as raw material
Adjusting, obtain oligomer G-COFs during monomer molecule pre-polymerization；
Under the conditions of 90-120 DEG C of solvent heat, reversible schiff base reaction occurs step (2) for oligomer G-COFs, passes through self assembly
Process is changed into the covalent organic crystal material G-S-COFs of high-sequential, stick cluster pattern of uniform size.
The external force mechanical intervention is mechanical lapping.
In step (1), trihydroxy benzene trioxin and diamino-anthraquinone molecule monomer are according to mass ratio 0.4-4.2: 0.6-
Mesitylene/dioxanes mixed solvent (2-6 μ L) and catalyst is slowly added dropwise in process of lapping in 5.0(g) mixed grinding
(0.1-1 μL)。
In step (2), specific position are as follows: mix step (1) oligomer G-COFs, 3-12 mL mesitylene and dioxanes
Solvent and 0.6-1.2 mL catalyst are placed in ampoule bottle (about 25 mL of volume, pipe shaft long 20 cm) for system liquid nitrogen frozen,
It is evacuated to vacuum again, subsequent flame sealing is put into 24-120 h in 90-120 DEG C of baking oven and (guarantees when system is warmed to room temperature
Without any interference, glass tube is carefully knocked open to the end of reacting), solid is collected to centrifuge tube, uses tetrahydrofuran, dichloromethane respectively
Alkane, acetone, dehydrated alcohol and deionized water washing, drying, obtain the covalent organic crystal material G-S-COFs of the stick cluster pattern.
A kind of controllable method for preparing based on covalent organic frame is with trihydroxy benzene trioxin and diamino-anthraquinone molecule
Raw material directlys adopt solvent method polymerization, finally obtains the covalent organic crystal for the emulation flower-shape that microscopic appearance is nanometer sheet composition
Material C-S-COFs, specifically: the trihydroxy benzene trioxin 0.4-4.2 g and diamino-anthraquinone monomer 0.6-5.0 g are direct
3-12 mL mesitylene, dioxanes mixed solvent and 0.6-1.2 mL catalyst is added, mixture ultrasonic disperse is uniform, with
After be transferred to static 0.5 h in ampoule bottle (about 25 mL of volume, pipe shaft long 20 cm), by system liquid nitrogen frozen, then vacuumize,
Subsequent flame sealing, when system is warmed to room temperature, be put into 24-120 h in 90-120 DEG C of baking oven (guarantee without any interference, to
Reaction terminates carefully to knock glass tube open), solid is collected to centrifuge tube, uses tetrahydrofuran, methylene chloride, acetone, anhydrous second respectively
Pure and mild deionized water washing, drying, finally obtain the covalent organic crystal material of emulation flower-shape that microscopic appearance is nanometer sheet composition
C-S-COFs。
Diamino-anthraquinone monomer of the present invention is selected from:
1,5- diamino-anthraquinone
2,6- diamino-anthraquinone
The volume ratio of the mixed solvent mesitylene and dioxanes is 1:1-9；The catalyst is acetic acid, deionized water, third
Acid, any one in 2- crassitude.
Application of two kinds of C-S-COFs, G-S-COFs materials prepared by the present invention as electrode material for super capacitor, such as
Under: weigh the electrode material of 16 mg and with acetylene black mixed grinding, be subsequently dispersed in 0.4 mL Nafion solution, take 5 μ
L drop is on glass-carbon electrode, drying at room temperature, and the energy storage situation of such electrode material is tested by electrochemical workstation.
Compared with prior art, the beneficial effects of the present invention are:
1. the present invention by withβThe covalent organic framework COFs material of -one amide connection is research object, by tying to its topology
The selection of the design of structure and polymerized monomer pre-polymerization environment, realize energy storage component in COFs material be successfully introduced into and microscopic appearance
Effective control；Anthraquinone molecular can make COFs material show apparent electrochemical energy storage activity as energy storage component, simultaneously
By the double inducing actions of mechanical lapping and reaction dissolvent during organic frame unit molecule pre-polymerization, COFs material is realized
It is final to obtain the novel C OFs energy storage material with diverse microcosmic appearance in the oriented growth of different dimensions.
2. the present invention using trihydroxy benzene trioxin and has the active diamino-anthraquinone of electrochemical energy storage as COFs first
Structural molecule, the present invention use pre- poly- solvent heat two-step method,
External mechanical effect is introduced during COFs pre-polymerization first, mechanical lapping mixing is carried out to monomer material, then cooperation is adjusted
The inductive effect of opposed polarity reaction dissolvent in pre-polymerization environment is controlled, to change the growth pattern (life of extending in molecule face of oligomer
Long or molecule interlayer π-π is stacked), it finally guides COFs crystal in different dimensions oriented growth under the conditions of high temperature polymerization, obtains
Functionalization COFs electrode material with single-size and specific morphology, the present invention are guaranteeing the active basis of COFs material energy storage
On, effectively improve that COFs material pattern under the conditions of solvent heat is unformed and the uncontrollable disadvantage of growth course.
3. the present invention by differential responses factor (external mechanical act on and polymerize environment) for COFs Material growth mistake
The influence of journey realizes effective control of the microcosmic crystal morphology of COFs material.Although different growth mechanisms results in different
Pattern, but two kinds of products (G-S-COFs and C-S-COFs) that synthesis obtains are made of identical structural unit.Due to its knot
Containing having the active diamino-anthraquinone of electrochemical energy storage (DAAQ) structure in structure unit, this material is in ultracapacitor energy storage
In show quick oxidation-reduction process, its 2D layered structure and the contribution of its electroactive monomer can be attributed to.
In addition to this, the change of pattern is so that product of the present invention helps to develop as electrode material for super capacitor applicability difference
Novel functional material.
Detailed description of the invention
The infrared spectrogram of Fig. 1 2,6- diamino-anthraquinone (DAAQ), G-S-COFs, C-S-COFs；
G-S-COFs scanning electron microscope (SEM) photograph under 10,000 times of amplification factors of Fig. 2；
C-S-COFs scanning electron microscope (SEM) photograph under 10,000 times of amplification factors of Fig. 3；
G-S-COFs scanning electron microscope (SEM) photograph under 20,000 times of amplification factors of Fig. 4；
C-S-COFs scanning electron microscope (SEM) photograph under 20,000 times of amplification factors of Fig. 5；
The scanning electron microscope (SEM) photograph of the M-COFs only reacted under mesitylene solvent under 20,000 times of amplification factors of Fig. 6；
The scanning electron microscope (SEM) photograph of the D-COFs only reacted under dioxanes solvent under 20,000 times of amplification factors of Fig. 7；
The scanning electron microscope (SEM) photograph of the A-COFs reacted under acetonitrile solvent under 20,000 times of amplification factors of Fig. 8；
The nitrogen adsorption desorption curve of Fig. 9 G-S-COFs, C-S-COFs；
The X-ray diffraction analysis figure of Figure 10 G-S-COFs, C-S-COFs；
The thermogravimetric test chart of Figure 11 G-S-COFs, C-S-COFs；
The molecular structure and its optimization structure of single six Fang great Huan of Figure 12；
The ordered stacks of six Fang great Huan of Figure 13 structure optimization；
Figure 14 G-S-COFs, C-S-COFs are as electrode material in 5 mV s-1Under cyclic voltammetry curve comparison diagram；
The cyclic voltammetry curve of Figure 15 G-S-COFs electrode material；
The cyclic voltammetry curve of Figure 16 C-S-COFs electrode material；
The stable circulation test chart of Figure 17 G-S-COFs electrode material；
The stable circulation test chart of Figure 18 C-S-COFs electrode material；
Figure 19 .M-COFs electrode material is in 5 mV s-1CV curve；
Figure 20 .D-COFs electrode material is in 5 mV s-1CV curve；
Figure 21 .A-COFs electrode material is in 5 mV s-1CV curve.
Specific embodiment
The present invention is described in further detail below with reference to embodiment；
Embodiment 1
A kind of controllable method for preparing based on covalent organic frame, by the trihydroxy benzene trioxin of 0.42 g(0.2mmol) and
0.65 g(0.3mmol) 2,6- diamino-anthraquinone be added agate mortar, while grinding while 6 μ L mesitylene and dioxanes is added dropwise
The 6 mol/L acetic acid of (1:1) mixed solvent and 0.1 μ L are as catalyst until powder becomes orange red.Gained is orange red
The ampoule bottle (about 25 mL of volume, long 20 cm of pipe shaft) equipped with 12 mL mesitylene and dioxanes (1:1) solution is added in powder
In, mixture ultrasonic disperse is uniform, and the 6 mol/L acetums of 0.6mL are added dropwise.It is then that system liquid nitrogen is cold
Freeze, tube sealing is evacuated to after vacuum 96 h in the baking oven for be put into 120 DEG C with flame gun sealing and guarantees without any interference.It is cold to baking oven
But it to taking out ampoule bottle after room temperature, obtains product and uses tetrahydrofuran respectively, methylene chloride washs repeatedly, is put into 85 DEG C of vacuum and dries
Dry 12 h of case obtain stick tufted G-S-COFs material.
1 products therefrom of embodiment is tested for the property and is characterized:
1, G-S-COFs electrode material infrared spectroscopy
It will be seen from figure 1 that DAAQ monomer is in 3420 and 3314 cm-1The peak that place occurs is-NH2Stretching vibration absworption peak, and gather
Object G-S-COF is closed in 3100-3300 cm-1- the NH at place2Stretching vibration disappears, in 3440cm-1There is wide absorption peak, explanation in place
Consumption of raw materials is sufficient.In addition, in 1235-1250 cm-1Occur the stretching vibration absworption peak of C-N in range, further demonstrates that
The formation of G-S-COFs.
, G-S-COFs electrode material scanning electron microscope
Fig. 2 and Fig. 4 is scanning electron microscope (SEM) photograph of the G-S-COFs under different amplification.It can be seen from the figure that pre- by grinding
It prepares us and has obtained the covalent organic framework polymer material of stick tufted that size is consistent and is evenly distributed.
, the nitrogen adsorption desorption of G-S-COFs electrode material is tested
As shown in figure 9, being characterized at 77 K to G-S-COF using nitrogen adsorption desorption isothermal curve.It can be seen from the figure that
In nitrogen partial pressure (P/P0) < 0.1 when, as the increase adsorbance of nitrogen partial pressure increases suddenly, illustrate that the material contains a large amount of micropore, belong to
In typical I class adsorption desorption isothermal curve.It is according to the specific surface area that G-S-COF material is calculated in BET method
838.9846 m2/g, pore volume are 0.539188 cm3/g, and aperture is mainly distributed on 2.5 nm or so.
, G-S-COFs X-ray diffraction analysis
As shown in Figure 10, G-S-COFs observes a main strong peak at 2 θ=3.24 °, its peak position corresponds to (100)
Crystal face.In 2 θ=5.8 ° and 26.7 ° or so two weak peaks then appearance location matches with (110) and (001) crystal face respectively, and
Since the PXRD peak intensity between (100) and (001) crystal face is higher, it is more regular to show that the π-π of the material is stacked, promotes micro-
Growth of the crystalline substance along Z-direction.
, to the heat stability testing of G-S-COFs electrode material
It is as shown in figure 11 G-S-COFs thermogravimetric test chart, it can be seen from the figure that the composite material is kept at 100-450 DEG C
, there is not the distinctive distillation phenomenon of anthraquinone monomer (near 250 DEG C), illustrates that monomer sufficiently reacts in good thermal stability.
π-π between adjacent layer is stacked or dipolar interaction improves its thermal stability.
, G-S-COFs electrode material cyclic voltammetry curve (CV)
Figure 15 is G-S-COFs in the different cyclic voltammograms swept under speed, it can be seen from the figure that in the current potential of -0.6 ~ 0.6 V
Under window, G-S-COFs shows two pairs of apparent redox peaks, and it is quinone/quinhydrones divalent that this, which is directed at reversible redox peaks,
The redox reaction peak of anion conversion process shows the successful synthesis of G-S-COFs.According in Figure 14 cyclic voltammetry,
The identical rectangular integration area for sweeping G-S-COFs under speed is maximum, is 5mV s when sweeping speed-1When, by the ratio electricity for calculating G-S-COFs
Holding is 335.4 F g-1
7, the cyclical stability of G-S-COFs electrode material is tested
It as shown in figure 17, is the cyclical stability test chart of G-S-COFs electrode material, it can be seen from the figure that by 50,000
After circle circulation, the capacity retention of the substance is 97.2%, illustrates it with good electrochemical cycle stability.
Embodiment 2
A kind of controllable method for preparing based on covalent organic frame, by the trihydroxy benzene trioxin of 0.42 g(0.2 mmol) and
0.65 g(0.3 mmol) 2,6- diamino-anthraquinone be added be equipped with 12 mL mesitylene and dioxanes (1:1) solution ampoule
It is in bottle (about 25 mL of volume, long 20 cm of pipe shaft), mixture ultrasonic disperse is uniform, and the 6 mol/L vinegar of 0.6mL are added dropwise
Acid solution.Then by system liquid nitrogen frozen, tube sealing is sealed 96 in the baking oven for be put into 120 DEG C after being evacuated to vacuum with flame gun
H guarantees without any interference.Ampoule bottle is taken out after baking oven is cooled to room temperature, product is obtained and uses tetrahydrofuran, dichloromethane respectively
Alkane washs repeatedly, is put into dry 12 h of 85 DEG C of vacuum drying ovens and obtains having the flower-shaped C-S-COFs electrode material of emulation.
2 products therefrom of embodiment is tested for the property and is characterized:
1, C-S-COFs electrode material infrared spectroscopy
It will be seen from figure 1 that polymer C-S-COFs is in 3100-3300 cm-1- the NH at place2Stretching vibration disappears, In
3440cm-1There is wide absorption peak in place, illustrates consumption of raw materials abundance.In addition, in 1235-1250 cm-1Occurs C-N in range
Stretching vibration absworption peak, can further demonstrate that the formation of C-S-COFs.
2, the scanning electron microscope of C-S-COFs electrode material
It is scanning electron microscope (SEM) photograph of the C-S-COFs under different amplification as shown in Fig. 3,5.It can be seen from the figure that C-S-
COFs is the emulation floral structure assembled by individual nanometer sheet petal in common center, and each emulation flower diameter is
10-15 μm。
3, the nitrogen adsorption desorption of C-S-COFs electrode material is tested
As shown in figure 9, equally being characterized at 77 K to C-S-COFs using nitrogen adsorption desorption isothermal curve.It can be with from figure
Find out, in nitrogen partial pressure (P/P0) < 0.1 when, as the increase adsorbance of nitrogen partial pressure increases suddenly, it is a large amount of micro- to illustrate that the material contains
Hole belongs to typical I class adsorption desorption isothermal curve.It is 663.1098 m2/g that specific surface area, which is calculated, according to BET method,
Pore volume is 0.435495 cm3/g.In addition, the aperture of the C-S-COFs material of synthesis is mainly distributed on 2.6 nm or so.
4, the X-ray diffraction analysis of C-S-COFs
As shown in Figure 10, C-S-COFs observes a strong peak at 2 θ=3.24 °, its peak position corresponds to (100) crystal face.
(110) and (001) crystal face is then corresponded respectively in 2 θ=5.8 ° and 26.7 ° or so two weak peaks.Since C-S-COFs is in (001)
(100) peak intensity of crystal face is weaker, shows that its crystallite under solvent-induced effect becomes apparent from along planar growth trend.
5, to the heat stability testing of C-S-COFs electrode material
Figure 11 is C-S-COFs thermogravimetric test chart.It can be seen from the figure that the composite material maintains well at 100-450 DEG C
Thermal stability, there is not the distinctive distillation phenomenon of anthraquinone monomer (near 250 DEG C), illustrate that monomer sufficiently reacts.Building is single
Between member firmly be covalently attached andβThe distinctive tautomerism of -one amide causes COFs to show excellent thermal stability.
6, the cyclic voltammetry curve (CV) of C-S-COFs electrode material
Figure 16 is C-S-COFs in the different cyclic voltammograms swept under speed, it can be seen from the figure that in the current potential of -0.6 ~ 0.6 V
Under window, C-S-COFs shows a pair of apparent redox peaks, and it is quinone/quinhydrones divalent that this, which is directed at reversible redox peaks,
The redox reaction peak of anion conversion process.The high surface area and reversible redox process of the COFs material are for counterfeit electricity
It is meaningful to hold energy storage device.According to Figure 14 cyclic voltammetry it is found that being 5mV s when sweeping speed-1When, rectangular integration area meter
Calculating and obtaining the specific capacitance of C-S-COFs is 311.7 F g-1
7, the cyclical stability of C-S-COFs electrode material is tested
Figure 18 is the cyclical stability test chart of C-S-COFs electrode material, it can be seen from the figure that by 50,000 circle circulation
Afterwards, the capacity retention of the substance is 97.0%, illustrates that it has good cyclical stability as super capacitor material.
Embodiment 3-5
In addition to polymer solvent is different, other conditions are same as Example 2, probe into influence of the polymer solvent polarity to COFs.
By the trihydroxy benzene trioxin and 0.65 g(0.3 mmol of 0.42 g(0.2 mmol)) 2,6- diamino-anthraquinone
It is added in the ampoule bottle equipped with 12 mL mesitylene solution (about 25 mL of volume, long 20 cm of pipe shaft), by mixture ultrasonic disperse
Uniformly, and the 6 mol/L acetums of 0.6mL are added dropwise.Then by system liquid nitrogen frozen, tube sealing uses fire after being evacuated to vacuum
The sealing of flame spray gun is put into 24 h in 120 DEG C of baking oven and guarantees without any interference.Ampoule bottle is taken after baking oven is cooled to room temperature
Out, it obtains product (M-COFs) and uses tetrahydrofuran respectively, methylene chloride washs repeatedly, is put into dry 12 h of 85 DEG C of vacuum drying ovens.
As shown in fig. 6, can be seen that M-COFs is assembled into thorniness ball along face outside direction by scanning electron microscopic observation.According to Figure 19 cyclic voltammetric
Test is it is found that be 5mV s when sweeping speed-1When, the specific capacitance that rectangular integration areal calculation obtains M-COFs is 267.1 F g-1.It is (real
Apply example 3).
By the trihydroxy benzene trioxin and 0.65 g(0.3 mmol of 0.42 g(0.2 mmol)) 2,6- diamino-anthraquinone
It is added in the ampoule bottle equipped with 12 mL dioxanes (about 25 mL of volume, long 20 cm of pipe shaft), mixture ultrasonic disperse is equal
It is even, and the 6 mol/L acetums of 0.6mL are added dropwise.Then by system liquid nitrogen frozen, tube sealing uses flame after being evacuated to vacuum
Spray gun sealing is put into 120 h in 120 DEG C of baking oven and guarantees without any interference.Ampoule bottle is taken out after baking oven is cooled to room temperature,
It obtains product (D-COFs) and uses tetrahydrofuran respectively, methylene chloride washs repeatedly, is put into dry 12 h of 85 DEG C of vacuum drying ovens.Such as
Shown in Fig. 7, it can be seen that D-COFs is shown as the Filamentous pattern along planar growth at one end by scanning electron microscopic observation.According to figure
20 cyclic voltammetries are it is found that be 5mV s when sweeping speed-1When, the specific capacitance that rectangular integration areal calculation obtains D-COFs is 203.3
F g-1.(embodiment 4)
By the trihydroxy benzene trioxin and 0.65 g(0.3 mmol of 0.42 g(0.2 mmol)) 2,6- diamino-anthraquinone be added
It is in ampoule bottle (about 25 mL of volume, long 20 cm of pipe shaft) equipped with 12 mL acetonitrile solutions, mixture ultrasonic disperse is uniform, and
The 6 mol/L acetums of 0.6mL are added dropwise.Then by system liquid nitrogen frozen, tube sealing uses flame gun after being evacuated to vacuum
Sealing is put into 120 h in 120 DEG C of baking oven and guarantees without any interference.Ampoule bottle is taken out after baking oven is cooled to room temperature, is obtained
Product (A-COFs) uses tetrahydrofuran respectively, and methylene chloride washs repeatedly, is put into dry 12 h of 85 DEG C of vacuum drying ovens.Such as Fig. 7 institute
Show, can be seen that A-COFs is shown as the Filamentous pattern along planar growth at one end by scanning electron microscopic observation.It 1 follows according to fig. 2
The test of ring volt-ampere is it is found that be 5mV s when sweeping speed-1When, the specific capacitance that rectangular integration areal calculation obtains A-COFs is 218.5 F
g-1.(embodiment 5)
Claims (10)
1. a kind of controllable method for preparing based on covalent organic frame, it is characterised in that: withβ-one amide connects covalent organic
Based on skeleton COFs material, COFs material is introduced using anthraquinone molecular as energy storage component, is existed by mechanical lapping and reaction dissolvent
Double inducing actions during organic frame unit molecule pre-polymerization or by directlying adopt solvent method polymerization, realize that COFs material exists
The oriented growth of different dimensions obtains the novel C OFs energy storage material with diverse microcosmic appearance.
2. a kind of controllable method for preparing based on covalent organic frame according to claim 1, it is characterised in that: with three hydroxyls
Base benzene trioxin and diamino-anthraquinone are as COFs structural molecule, using pre- poly- solvent heat two-step method, first to monomer material into
Row external force mechanical intervention, subsequent complex reaction solvent carry out double inductions, change the growth pattern of oligomer, in high temperature polymerization condition
Lower guidance COFs crystal obtains the covalent organic crystal material G-S- that microscopic appearance is stick tufted in different dimensions oriented growth
COFs。
3. a kind of controllable method for preparing based on covalent organic frame according to claim 2, it is characterised in that: specific packet
Include following steps:
Step (1) passes through external force mechanical intervention and reaction dissolvent polarity using trihydroxy benzene trioxin and diamino-anthraquinone as raw material
Adjusting, obtain oligomer G-COFs during monomer molecule pre-polymerization；
Under the conditions of 90-120 DEG C of solvent heat, reversible schiff base reaction occurs step (2) for oligomer G-COFs, passes through self assembly
Process is changed into the covalent organic crystal material G-S-COFs of high-sequential, stick cluster pattern of uniform size.
4. a kind of controllable method for preparing based on covalent organic frame according to claim 3, it is characterised in that: described outer
Power mechanical intervention is mechanical lapping.
5. a kind of controllable method for preparing based on covalent organic frame according to claim 3 or 4, it is characterised in that: step
Suddenly in (1), trihydroxy benzene trioxin and diamino-anthraquinone molecule monomer according to 0.4-4.2: 0.6-5.0 mixed grinding of mass ratio,
Mesitylene and dioxanes mixed solvent and catalyst are slowly added dropwise in process of lapping.
6. a kind of controllable method for preparing based on covalent organic frame according to claim 5, it is characterised in that: step
(2) in, specific position are as follows: by step (1) oligomer G-COFs, 3-12 mL mesitylene and dioxanes mixed solvent and 0.6-
1.2 mL catalyst are placed in system liquid nitrogen frozen in ampoule bottle, then are evacuated to vacuum, and subsequent flame sealing rises to room to system
Wen Shi, is put into 24-120 h in 90-120 DEG C of baking oven, collects solid to centrifuge tube, respectively with tetrahydrofuran, methylene chloride,
Acetone, dehydrated alcohol and deionized water washing, drying, obtain the covalent organic crystal material G-S-COFs.
7. a kind of controllable method for preparing based on covalent organic frame according to claim 1, it is characterised in that: with three hydroxyls
Base benzene trioxin and diamino-anthraquinone molecule are raw material, directly adopt solvent method polymerization, finally obtain the flower being made of nanometer sheet
The covalent organic crystal material C-S-COFs of shape.
8. a kind of controllable method for preparing based on covalent organic frame according to claim 7, it is characterised in that: described three
Hydroxy benzenes trioxin 0.4-4.2 g and diamino-anthraquinone monomer 0.6-5.0 g are directly added into 3-12 mL mesitylene and dioxanes
Mixed solvent and 0.6-1.2 mL catalyst, mixture ultrasonic disperse is uniform, it is subsequently transferred to static 0.5 h in ampoule bottle,
It by system liquid nitrogen frozen, then vacuumizes, subsequent flame sealing, when system is warmed to room temperature, is put into 90-120 DEG C of baking oven
24-120 h collects solid to centrifuge tube, uses tetrahydrofuran, methylene chloride, acetone, dehydrated alcohol and deionization washing respectively
It washs, dry, finally obtain covalent organic crystal material C-S-COFs.
9. a kind of controllable method for preparing based on covalent organic frame, feature according to claim 3,4,6 or 8 exist
In: the catalyst be acetic acid, deionized water, propionic acid, any one in 2- crassitude.
10. one kind of preparation is based on covalent organic frame according to the method for claim 9, it is characterised in that: as super
The stored energy application of capacitor electrode material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004532A (en) * | 2021-02-22 | 2021-06-22 | 浙江大学 | Metamaterial based on covalent organic framework and application of metamaterial in optical device |
| CN113461887A (en) * | 2021-01-28 | 2021-10-01 | 渤海大学 | One-dimensional nanochannel self-supporting covalent organic framework membrane for salt difference power generation and application thereof |
| CN114005980A (en) * | 2021-10-19 | 2022-02-01 | 珠海冠宇电池股份有限公司 | Negative electrode material and lithium ion battery containing same |
| CN114373969A (en) * | 2022-01-10 | 2022-04-19 | 中国石油大学(北京) | Composite nanofiber modified proton exchange membrane and preparation method and application thereof |
| CN114551818A (en) * | 2021-07-08 | 2022-05-27 | 万向一二三股份公司 | Nano silicon composite particle, negative plate and solid lithium battery |
| CN114628649A (en) * | 2021-07-20 | 2022-06-14 | 万向一二三股份公司 | Preparation method and application of cobalt-supplement type high-nickel low-cobalt ternary cathode material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017031062A1 (en) * | 2015-08-14 | 2017-02-23 | Cornell University | Conducting-polymer modified covalent organic frameworks and methods of making same |
| CN107180968A (en) * | 2017-03-24 | 2017-09-19 | 北京理工大学 | A kind of raising COFs materials as electrode active material performance method |
| CN107230556A (en) * | 2016-03-25 | 2017-10-03 | 华北电力大学（保定） | A kind of pillar super capacitor |
| CN109921076A (en) * | 2019-01-23 | 2019-06-21 | 西安交通大学 | A kind of high temperature proton-conducting material and preparation method thereof with meso-hole structure |
-
2019
- 2019-08-30 CN CN201910815016.0A patent/CN110483799B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017031062A1 (en) * | 2015-08-14 | 2017-02-23 | Cornell University | Conducting-polymer modified covalent organic frameworks and methods of making same |
| CN107230556A (en) * | 2016-03-25 | 2017-10-03 | 华北电力大学（保定） | A kind of pillar super capacitor |
| CN107180968A (en) * | 2017-03-24 | 2017-09-19 | 北京理工大学 | A kind of raising COFs materials as electrode active material performance method |
| CN109921076A (en) * | 2019-01-23 | 2019-06-21 | 西安交通大学 | A kind of high temperature proton-conducting material and preparation method thereof with meso-hole structure |
Non-Patent Citations (4)
| Title |
|---|
| CATHERINE R. DEBLASE等: ""β‑Ketoenamine-Linked Covalent Organic Frameworks Capable of Pseudocapacitive Energy Storage"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| RUI WEN等: ""Graphene-synergized 2D covalent organic framework for adsorption: A mutual promotion strategy to achieve stabilization and functionalization simultaneously"", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| SHAN WANG等: ""Exfoliation of Covalent Organic Frameworks into Few-Layer Redox-Active Nanosheets as Cathode Materials for Lithium-Ion Batteries"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| SHUAI GU: ""Tunable Redox Chemistry and Stability of Radical Intermediates in 2D Covalent Organic Frameworks for High Performance Sodium Ion Batteries"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461887A (en) * | 2021-01-28 | 2021-10-01 | 渤海大学 | One-dimensional nanochannel self-supporting covalent organic framework membrane for salt difference power generation and application thereof |
| CN113461887B (en) * | 2021-01-28 | 2023-12-05 | 渤海大学 | One-dimensional nano-channel self-supporting covalent organic framework film for salt-tolerant power generation and application thereof |
| CN113004532A (en) * | 2021-02-22 | 2021-06-22 | 浙江大学 | Metamaterial based on covalent organic framework and application of metamaterial in optical device |
| CN113004532B (en) * | 2021-02-22 | 2022-07-15 | 浙江大学 | Metamaterial based on covalent organic framework and application of metamaterial in optical device |
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| CN114628649B (en) * | 2021-07-20 | 2023-10-03 | 万向一二三股份公司 | Preparation method and application of cobalt-supplementing high-nickel low-cobalt ternary cathode material |
| CN114005980A (en) * | 2021-10-19 | 2022-02-01 | 珠海冠宇电池股份有限公司 | Negative electrode material and lithium ion battery containing same |
| CN114005980B (en) * | 2021-10-19 | 2022-11-22 | 珠海冠宇电池股份有限公司 | Negative electrode material and lithium ion battery containing same |
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