CN106084775B - Three layers of vesica shape polyaniline/graphene composite material and preparation method thereof - Google Patents
Three layers of vesica shape polyaniline/graphene composite material and preparation method thereof Download PDFInfo
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- CN106084775B CN106084775B CN201610416258.9A CN201610416258A CN106084775B CN 106084775 B CN106084775 B CN 106084775B CN 201610416258 A CN201610416258 A CN 201610416258A CN 106084775 B CN106084775 B CN 106084775B
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- 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
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/02—Polyamines
Abstract
The invention discloses a kind of three layers of vesica shape polyaniline/graphene composite material and preparation method thereof, the adjustable SiO of the number of plies is prepared first2, by the adjustable SiO of the number of plies2It is that raw material is prepared for the adjustable SiO of the number of plies using situ aggregation method as hard template, aniline2/ polyaniline composite material；Etch SiO2After obtain three layers of vesica shape polyaniline, three layers of vesica shape polyaniline/graphene oxide composite are prepared using graphene oxide self-assembly method, three layers of vesica shape polyaniline/graphene composite material are finally obtained using high-temperature water thermal reduction.The adjustable SiO of the number of plies can be passed through in the present invention2Regulation and control obtain vesica shape polyaniline/graphene composite material of the same number of plies.During this, it is not required to add any oxidant, reducing agent, it is green.For this method during three layers of vesica shape polyaniline/graphene composite material are prepared, preparation method is simple, and safe preparation process, energy consumption is low, workable.
Description
Technical field
The present invention relates to three layers of vesica shape polyaniline/graphene composite material and preparation method thereof, belong to organic/inorganic and receive
The crossing domain of rice compound and functional high molecule material.
Background technology
Ultracapacitor is a kind of novel green energy-storage travelling wave tube, and it is because possess larger specific surface area, good conduction
The advantages that property, multilayered structure, is by extensive concern.And conducting polymer, carbon material are to realize the storage release of ultracapacitor electric charge
Mainstay material, wherein polyaniline because having the advantages that good heat endurance, chemical stability and electrochemical reversibility,
One of most fast conducting polymer composite of present progress is turned into；Graphene be by carbon atom it is tightly packed formed have
Hexagonal structure unit two-dimension plane structure, have the advantages that specific surface area is big, electron mobility is high and good conductivity.But
Single polyaniline, such as pattern are that nano wire, nanometer rods and nanofiber have higher a specific surface area and specific capacitance, and
Degradable and cause polyaniline structure to change during charge-discharge, specific capacitance reduces rapidly.Graphene with polyaniline is compound can
Make the Stability Analysis of Structures of polyaniline, and increase the properties such as its specific capacitance, forthright again and cycle life, improve in electrochemical field
Using.And the preparation method of existing polyaniline/graphene composite material, the polyphenyl of hollow-core construction in obtained composite
The pattern of polyaniline is hollow ball in amine/graphene composite material, is easily reunited；And needed during graphene oxide reduces
Hydrazine hydrate reduction agent is added, this reducing agent is not only poisonous but also big to environmental hazard.
For example, the A of application publication number CN 105131596 (application number 201510581961.0) Chinese patent literature discloses
A kind of preparation method of graphene/polyaniline compound hollow microballoon, it is the method by using Pickering emulsion polymerizations
Graphene/polyaniline compound hollow microballoon is prepared, the factor such as dosage, oil-water ratio and shear rate that can be by adjusting emulsifying agent,
Obtain various sizes of emulsion droplets, but this method obtained using polystyrene spheres as hard template simply hollow ball graphene/
The composite of polyaniline.The A of application publication number CN 103311428 (application number 201310236524.6) Chinese patent literature
A kind of preparation method of graphene/polyaniline thermal electric film is disclosed, in the preparation method of the patent：Prepare first graphene/
Polyaniline composite material, then orientated deposition prepare thermal electric film.But graphene is by hydrazine hydrate reduction oxygen in the patent
Prepared by graphite alkene, hydrazine hydrate is not only poisonous but also big to environmental hazard.
The content of the invention
It is an object of the invention to provide a kind of preparation method of three layers of vesica shape polyaniline/graphene composite material, with heat
Stability is good, specific surface area is big and the adjustable SiO of the number of plies2For hard template, three layers of vesica shape polyaniline/graphene composite wood are prepared
Material.The preparation method of the present invention is simple, and safe preparation process, energy consumption is low, workable.
The present invention is achieved by the following technical solutions：
The preparation method of three layers of vesica shape polyaniline/graphene composite material, comprises the following steps：Preparing the number of plies first can
The vesica shape SiO of tune2；Then with the adjustable SiO of the number of plies2For hard template, using aniline as raw material, using in-situ polymerization legal system
The adjustable SiO of the standby number of plies2/ polyaniline composite material；The adjustable SiO of the number of plies is etched using HF again2/ polyaniline composite material
In the adjustable SiO of the number of plies2, obtain three layers of vesica shape polyaniline；Finally aoxidized in three layers of vesica shape polyaniline surface self-organization
Graphene obtains three layers of vesica shape polyaniline/graphene oxide composite；And obtain three using the method for high temperature hydrothermal reduction
Layer vesica shape polyaniline/graphene composite material.
In this method, SiO that the first step obtains2Pattern is vesica shape, can be by controlling cetyl trimethylammonium bromide
(CTAB) number of plies is regulated and controled with the mol ratios of double dodecyl dimethyl bromine ammoniums (DDAB)；Second step is with the adjustable SiO of the number of plies2For
Hard template, aniline are raw material, and the adjustable SiO of the number of plies is prepared using situ aggregation method2/ polyaniline composite material；3rd step will be upper
State the adjustable SiO of the number of plies2/ polyaniline composite material etches SiO with HF2Obtain three layers of vesica shape polyaniline；4th step at room temperature,
Three layers of vesica shape polyaniline/graphene oxide composite wood are obtained in three layers of vesica shape polyaniline surface self-organization graphene oxide
Material；And three layers of vesica shape polyaniline/graphene composite material are obtained using the method for high temperature hydrothermal reduction.During this, it is not required to
Add any oxidant, reducing agent, it is green.The pattern of three layers of vesica shape polyaniline/graphene prepared by this method is graphite
Alkene coats three layers of vesica shape polyaniline.
In the present invention, the adjustable vesica shape SiO of the number of plies2Preparation method can routinely make for those skilled in the art
It is standby to obtain.But because polyaniline has certain flexibility, in order to maintain the stabilization of vesica wall, so as to get better three
Layer vesica shape polyaniline/graphene composite material, the present invention preferably following adjustable vesica shape SiO of the number of plies2, the number of plies is adjustable
Vesica shape SiO2To be adjustable in number of plies 7-2, particle diameter 60-100nm, thickness and interlamellar spacing are all 2-3nm, and preparation method includes：
Using tetraethyl orthosilicate (TEOS) as silicon source, CTAB and DDAB as surfactant, synthesized using hydro-thermal method in number of plies 7-2
Adjustable, particle diameter 60-100nm, thickness and interlamellar spacing are all the 2-3nm adjustable SiO of the number of plies2。
The adjustable vesica shape SiO of the number of plies2Specific preparation method is as follows：
1. CTAB is dissolved in water, stir to clear solution；
2. by DDAB be added to step 1. gained clear solution in, stir to whole dissolvings；
3. ammoniacal liquor is added drop-wise into step 2. in prepared suspension, stirring obtains suspension；
4. TEOS is added dropwise in 3. suspension that step is prepared, stirring obtains white precipitate；
5. 4. white precipitate that step is prepared is transferred in autoclave, hydro-thermal reaction is carried out, will after hydro-thermal process
Autoclave is cooled to room temperature, obtains white precipitate；
6. 5. white precipitate that step is obtained is filtered, washs, dried, calcined after grinding and obtain adjustable in number of plies 7-2, grain
The adjustable SiO of the number of plies that footpath is 60-100nm, thickness and interlamellar spacing are all 2-3nm2。
Wherein, raw materials used CTAB, DDAB, ammoniacal liquor, TEOS mol ratio are 1：0.55477-1.6640：13.669-
136.69：12.320-36.959 the adjustable SiO of the number of plies2Number of plies when being 6-7 layers, be preferably in a proportion of 1：0.62135：
94.317：24.639；The adjustable SiO of the number of plies2Number of plies when being 3-4 layers, be preferably in a proportion of 1：0.83216：94.317：
24.639；The adjustable SiO of the number of plies2Number of plies when being layer 2-3, be preferably in a proportion of 1：1.1095：94.317：24.639.
Described CTAB, DDAB and TEOS molecular weight are respectively 364.45g/mol, 462.63g/mol and 208.33g/
mol。
Step 1. in, reaction temperature be 25-30 DEG C, optimal reaction temperature be 30 DEG C.
Step 2. in, mixing time 6-18h, optimal mixing time is 12h.
Step 3. in, mixing time 1-3h, optimal mixing time is 2h.
Step 4. in, 12-36h is stirred at 25-30 DEG C, optimal mixing time is 24h.
Step 5. in, hydrothermal condition is：12-36h is reacted at 100-120 DEG C, hydrothermal condition is preferably 100 DEG C of insulation 24h.
Step 6. in, calcination condition is to calcine 5-6h at 500-600 DEG C, and calcining heat is preferably 550 DEG C of calcining 6h.
In the present invention, the adjustable vesica shape SiO of the number of plies2Mass ratio with aniline is 0.0100：(0.0500-
0.4500)。
The adjustable SiO of the number of plies2The preparation method of/polyaniline composite material is：
1. by the adjustable SiO of the number of plies2It is added to lauryl sodium sulfate (SDS) in HCl solution, it is ultrasonic to completely molten
Solution, the number of plies；
2. aniline is dispersed in HCl solution, stirring is to being uniformly dispersed；
3. 2. 1. solution that step is prepared is transferred to step in, stirring；
4. ammonium persulfate (APS) is dissolved in water；
5. 4. solution addition step that step is prepared is 3. in the solution of gained, solution becomes blackish green after a period of time,
And stir；
6. 5. sediment that step is prepared is filtered, washs, dried, grinding, the adjustable SiO of the number of plies is obtained2/ polyaniline is multiple
Condensation material, it is stand-by to be put into sample cell；
Above step order can be adjusted as the case may be.
Wherein, the adjustable SiO of the number of plies used2, SDS, aniline, APS mol ratio be 1：0.02080-0.20806：
0.32857-2.9572：0.20508-1.8457, it is preferably in a proportion of 1：0.10403：0.65714：0.41017.
Further, the adjustable SiO of the number of plies2, SDS, step 1. in HCl solution, aniline, step 2. in HCl
Solution A PS, step 4. in the adding proportion of water be 0.0100g：(0.0010-0.0100)g：(25-35)mL：(0.0500-
0.4500)g：(8-12)mL：(0.7800-7.0200)g：(8-12)g.
The SDS, aniline, APS molecular weight are respectively 288.38g/mol, 93.13g/mol, 228.20g/mol.HCl
The molar concentration of solution is about 1mol L-1。
Step 1. in, the ultrasonic time is 0.5-1h, and optimal ultrasonic time is 1h.
Step 3. in, at room temperature stirring be 1-2h, optimum reacting time 1h.
Step 5. in, stir 12-36h, optimum reacting time 24h at room temperature.
In the present invention, the SiO2/ polyaniline composite material and HF adding proportion are (0.0100-0.1000) g：(1-
10)mL。
The preparation method of three layers of vesica shape polyaniline is：
1. by the adjustable SiO of the number of plies2/ polyaniline composite material is dispersed in tetrahydrofuran (THF), stirring；
2. HF is added drop-wise to dropwise in above-mentioned dispersion liquid and stirred；
3. by the suspension 2. obtained centrifugation, washing, drying, three layers of vesica shape polyaniline are obtained after grinding.
Wherein, the adjustable SiO of the number of plies2/ polyaniline composite material, tetrahydrofuran, HF adding proportion are
(0.0100-0.1000)g：(15-25)mL：(1-10)mL.
Step 1. in, the mixing time is 0.5-2h, and optimal mixing time is 0.5h.
Step 2. in, stir 12-48h at room temperature, optimal mixing time is 24h.
In the present invention, the mass ratio of three layers of vesica shape polyaniline and graphene oxide is (0.0100-0.1000)：
(0.0010-0.0100)。
The preparation method of the three layers of vesica shape polyaniline/graphene composite material is：
1. graphene oxide powder is dispersed in water, it is stirred by ultrasonic, obtains the dispersion liquid of graphene oxide；
2. by three layers of vesica shape dispersing polyaniline in absolute ethyl alcohol, ultrasonic agitation；
3. the dispersion liquid of step 1. is added under ultrasound condition in the dispersion liquid of step 2., it is stirred by ultrasonic；
4. it is multiple to be obtained into three layers of vesica shape polyaniline/graphene through centrifuging, washing, dry for obtained sediment after grinding
Condensation material preliminary sedimentation starch.
5. by step, 4. middle preliminary sedimentation starch is put into reactor, and hydrothermal reduction reaction occurs in a kettle, obtains three layers
Vesica shape polyaniline/graphene composite material sediment.
6. by step 5. in three layers of vesica shape polyaniline/graphene composite material sediment through centrifuging, washing, dry,
Three layers of vesica shape polyaniline/graphene composite material are obtained after grinding.
Above step order can be adjusted as the case may be.
Wherein, the graphene oxide, water, three layers of vesica shape polyaniline, the adding proportion of absolute ethyl alcohol are (0.0010-
0.0100)g：(8-12)mL：(0.0100-0.1000)g：(45-55)mL.
Step 1. in, the ultrasonic time is 0.5-2h, and optimal ultrasonic time is 0.5h.
Step 2. in, the ultrasonic time is 0.5-2h, and optimal ultrasonic time is 0.5h.
Step 3. in, the ultrasonic time is 1-4h, and optimal ultrasonic time is 2h.
Step 5. in, the reaction temperature be 100-120 DEG C, reaction time 12-48h.Optimal reaction temperature is 100
DEG C, reaction time 24h.Three layers of vesica shape polyaniline/graphene composite material, the material have been prepared using the above method
In, the number of plies of vesica shape polyaniline is 3 layers, and particle diameter 30-60nm, vesica shape Polyaniline-Supported is on the surface of graphene.
The present invention also protection includes the ultracapacitor of above-mentioned material.
The present invention is with the adjustable SiO of the number of plies2For hard template, the adjustable SiO of the number of plies is prepared for using situ aggregation method2/ polyphenyl
Amine composite, and etch SiO with HF2Three layers of vesica shape polyaniline are obtained, graphite oxide is prepared with improved Hummers methods
Alkene, three layers of vesica shape polyaniline/graphene oxide composite are then prepared using self-assembly method, finally using high temperature hydro-thermal
The method of reduction obtains three layers of vesica shape polyaniline/graphene composite material.
The invention has the advantages that：
1st, vesica shape polyaniline/graphene composite material produced by the present invention, the number of plies of vesica shape polyaniline is 3 layers, capsule
Blister Polyaniline-Supported is had a good application prospect in electrochemical field on the surface of graphene.
2nd, four steps of the present invention point prepare three layers of vesica shape polyaniline/graphene composite material, three layers of vesica shape polyaniline/stone
Black alkene composite will not be due to the SiO etched away2And recurring structure changes.
3rd, when the present invention prepares three layers of vesica shape polyaniline/graphene composite material, preparation method is simple, preparation process peace
Entirely, energy consumption is low, workable.
4th, the composite wood of three layers of vesica shape polyaniline/graphene is obtained using the method for high temperature hydrothermal reduction in the present invention
Material, this method safe preparation process are Environmental good.
5th, the pattern compared to polyaniline in polyaniline/graphene composite material of the prior art is hollow ball, this hair
In bright composite, the number of plies of vesica shape polyaniline is 3 layers, and vesica shape Polyaniline-Supported is overcome on the surface of graphene
The problem of polyaniline is easily reunited in the prior art.
Brief description of the drawings
Fig. 1 is scanning probe microscopy (SEM), and wherein a is vesica shape SiO2The SEM of/polyaniline composite material, b tri-
The SEM of layer vesica shape polyaniline；C is the SEM of three layers of vesica shape polyaniline/graphene composite material；
Fig. 2 is the adjustable SiO of the number of plies prepared2The transmission electron microscope picture (TEM) of/polyaniline composite material, wherein a are implementation
The vesica shape SiO of 6-7 layers prepared by example 12The TEM of/polyaniline, b are the vesica shape SiO of 3-4 layers prepared by embodiment 22/ polyphenyl
The TEM of amine；C is the vesica shape SiO of layer 2-3 prepared by embodiment 32The TEM of/polyaniline；
Fig. 3 is the TEM of the three layers of vesica shape polyaniline prepared；
Fig. 4 is the TEM of the three layers of vesica shape polyaniline/graphene composite material prepared.
Embodiment
Further illustrated with reference to specific embodiment.
Embodiment 1
(1) the vesica shape SiO of 6-7 layers is prepared235mL distilled water is measured in 100mL beakers, is subsequently added into 0.1420g
CTAB stirs to clarify into beaker, adds 0.1126g DDAB, stirs 24h at 30 DEG C, obtain mixed dispersion liquid；Will be mixed
Close dispersion liquid to be transferred in the autoclave of polytetrafluoroethyllining lining, autoclave is tightened and is put into baking oven, at 100 DEG C
Under the conditions of react 24h, autoclave is naturally cooled into room temperature after hydro-thermal process, obtains sediment；The sediment that will be obtained
Filter separation, dry, calcining 6h at 550 DEG C after grinding obtains the vesica shape SiO of 6-7 layers2。
(2) the vesica shape SiO of 6-7 layers is prepared2/ polyaniline composite material, if Fig. 1 a are by 30mL 1mol L-1HCl solution,
The vesica shape SiO of 0.0100g 6-7 layers2, 0.0500g SDS be added sequentially in beaker, ultrasonic 30min obtains to being completely dissolved
To mixed dispersion liquid；Mixed dispersion liquid is transferred to in the aniline dispersion liquid to stir (0.1000g aniline is added to 10mL
1mol L-1In HCl solution, it is stirred until homogeneous), 1h is stirred at room temperature；0.1560g APS are added in 10mL distilled water, it is complete
After fully dissolved, APS solution is quickly poured into above-mentioned aniline dispersion liquid, the color of suspension becomes blackish green after 5min, stirs at room temperature
Mix 24h and obtain sediment；Sediment is filtered, washed, is dried, SiO is obtained after grinding2/ polyaniline composite material.
(3) three layers of vesica shape polyaniline are prepared, if Fig. 1 b are by the vesica shape SiO of the 50mg 6-7 layers of above-mentioned preparation2/ poly-
Aniline composite is dispersed in 20mL solvents THF, and after stirring 30min, 5mL HF are added dropwise, and then proceedes to stir 24h；It will obtain
Suspension centrifugation, washing, dry, obtained after grinding vesica shape polyaniline the number of plies be 3 layers, such as Fig. 3.
(4) prepare three layers of vesica shape polyaniline/graphene composite material, as Fig. 1 c by 5mg with improve Hummers methods preparation
Good graphene oxide is added in 10mL distilled water, and ultrasound obtains graphene oxide dispersion to scattered；By tri- layers of 50mg
Vesica shape polyaniline is added in 50mL absolute ethyl alcohols, ultrasound, obtains three layers of vesica shape polyaniline composite material dispersion liquid；By oxygen
Graphite alkene dispersion liquid is slowly added under ultrasound in three layers of vesica shape dispersing polyaniline liquid, and ultrasonic 2h, obtains sediment；
Mixed dispersion liquid is transferred in the autoclave of polytetrafluoroethyllining lining, autoclave is tightened and is put into baking oven,
It is incubated 24h under the conditions of 100 DEG C, autoclave is naturally cooled into room temperature after hydro-thermal process, obtains sediment；It is heavy by what is obtained
After starch centrifuges, washed, centrifuged using ethanol, dried, three layers of vesica shape polyaniline/graphene composite wood are obtained after grinding
Material, such as Fig. 4.
Embodiment 2
(1) the vesica shape SiO of 3-4 layers is prepared235mL distilled water is measured in 100mL beakers, is subsequently added into 0.1420g
CTAB stirs to clarify into beaker, adds 0.1500g DDAB, stirs 24h at 30 DEG C, obtain mixed dispersion liquid；Will be mixed
Close dispersion liquid to be transferred in the autoclave of polytetrafluoroethyllining lining, autoclave is tightened and is put into baking oven, at 100 DEG C
Under the conditions of react 24h, autoclave is naturally cooled into room temperature after hydro-thermal process, obtains sediment；The sediment that will be obtained
Filter after separating, dry, calcining 6h at 550 DEG C after grinding obtains the vesica shape SiO of 3-4 layers2。
(2) the vesica shape SiO of 3-4 layers is prepared2/ polyaniline composite material is by 30mL 1mol L-1HCl solution, 0.0100g
The vesica shape SiO of 3-4 layers2, 0.0500g SDS be added sequentially in beaker, ultrasonic 30min to being completely dissolved, obtain mixing point
Dispersion liquid；Mixed dispersion liquid is transferred to in the aniline dispersion liquid to stir (0.1000g aniline is added to 10mL 1molL-1HCl
In solution, it is stirred until homogeneous), 1h is stirred at room temperature；0.1560g APS are added in 10mL distilled water, will after being completely dissolved
APS solution fast transfer is into above-mentioned mixed liquor, and the color of suspension becomes blackish green after 5min, stirs 24h at room temperature and is precipitated
Thing；Sediment is filtered, washed, is dried, SiO is obtained after grinding2/ polyaniline composite material.
(3) three layers of vesica shape polyaniline are prepared by the vesica shape SiO of the 50mg 3-4 layers of above-mentioned preparation2/ polyaniline is compound
Material is dispersed in 20mL solvents THF, and after stirring 30min, 5mL HF are added dropwise, and then proceedes to stir 24h；The suspension that will be obtained
Centrifugation, washing, dry, the number of plies that vesica shape polyaniline is obtained after grinding is 3 layers.
(4) three layers of vesica shape polyaniline/graphene composite material are prepared by 5mg to improve the oxygen that Hummers methods prepare
Graphite alkene is added in 10mL distilled water, and ultrasound obtains graphene oxide dispersion to scattered；By tri- layers of vesica shapes of 50mg
Polyaniline is added in 50mL absolute ethyl alcohols, ultrasound, obtains three layers of vesica shape polyaniline composite material dispersion liquid；By graphite oxide
Alkene dispersion liquid is slowly added under ultrasound in three layers of vesica shape dispersing polyaniline liquid, and ultrasonic 2h, obtains sediment；Will mixing
Dispersion liquid is transferred in the autoclave of polytetrafluoroethyllining lining, and autoclave is tightened and is put into baking oven, in 100 DEG C of bars
It is incubated 24h under part, autoclave is naturally cooled into room temperature after hydro-thermal process, obtains sediment；By obtained sediment from
After heart separation, washed, centrifuged using ethanol, dried, three layers of vesica shape polyaniline/graphene composite material are obtained after grinding.
Embodiment 3
(1) the vesica shape SiO of layer 2-3 is prepared235mL distilled water is measured in 100mL beakers, is subsequently added into 0.1420g
CTAB stirs to clarify into beaker, adds 0.2000g DDAB, stirs 24h at 30 DEG C, obtain mixed dispersion liquid；Will be mixed
Close dispersion liquid to be transferred in the autoclave of polytetrafluoroethyllining lining, autoclave is tightened and is put into baking oven, at 100 DEG C
Under the conditions of react 24h, autoclave is naturally cooled into room temperature after hydro-thermal process, obtains sediment；The sediment that will be obtained
Filter after separating, dry, calcining 6h at 550 DEG C after grinding obtains the vesica shape SiO of layer 2-32。
(2) the vesica shape SiO of layer 2-3 is prepared2/ polyaniline composite material is by 30mL 1mol L-1HCl solution, 0.0100g
The vesica shape SiO of layer 2-32, 0.0500g SDS be added sequentially in beaker, ultrasonic 30min to being completely dissolved, obtain mixing point
Dispersion liquid；Mixed dispersion liquid is transferred to in the aniline dispersion liquid to stir (0.1000g aniline is added to 10mL 1molL-1HCl
In solution, it is stirred until homogeneous), 1h is stirred at room temperature；0.1560g APS are added in 10mL distilled water, will after being completely dissolved
APS solution fast transfer is into above-mentioned mixed liquor, and the color of suspension becomes blackish green after 5min, stirs 24h at room temperature and is precipitated
Thing；Sediment is filtered, washed, is dried, SiO is obtained after grinding2/ polyaniline composite material.
(3) three layers of vesica shape polyaniline are prepared by the vesica shape SiO of the 50mg layer 2-3s of above-mentioned preparation2/ polyaniline is compound
Material is dispersed in 20mL solvents THF, and after stirring 30min, 5mL HF are added dropwise, and then proceedes to stir 24h；The suspension that will be obtained
Centrifugation, washing, dry, the number of plies that vesica shape polyaniline is obtained after grinding is 3 layers.
(4) three layers of vesica shape polyaniline/graphene composite material are prepared by 5mg to improve the oxygen that Hummers methods prepare
Graphite alkene is added in 10mL distilled water, and ultrasound obtains graphene oxide dispersion to scattered；By tri- layers of vesica shapes of 50mg
Polyaniline is added in 50mL absolute ethyl alcohols, ultrasound, obtains three layers of vesica shape polyaniline composite material dispersion liquid；By graphite oxide
Alkene dispersion liquid is slowly added under ultrasound in three layers of vesica shape dispersing polyaniline liquid, and ultrasonic 2h, obtains sediment；Will mixing
Dispersion liquid is transferred in the autoclave of polytetrafluoroethyllining lining, and autoclave is tightened and is put into baking oven, in 100 DEG C of bars
It is incubated 24h under part, autoclave is naturally cooled into room temperature after hydro-thermal process, obtains sediment；By obtained sediment from
After heart separation, washed, centrifuged using ethanol, dried, three layers of vesica shape polyaniline/graphene composite material are obtained after grinding.
The number of plies of vesica shape polyaniline/graphene composite material made from embodiment 1~3 is 3 layers, particle diameter 30-60nm,
But vesica shape SiO2The number of plies it is different, the wherein vesica shape SiO of the gained of embodiment 12The number of plies be 6-7 layers, it is real such as Fig. 2 a
Apply the vesica shape SiO of the gained of example 22The number of plies be 3-4 layers, such as Fig. 2 b, the vesica shape SiO of the gained of embodiment 32The number of plies be 2-3
Layer, such as Fig. 2 c.
Four steps of the present invention point prepare three layers of vesica shape polyaniline/graphene composite material, three layers of vesica shape polyaniline/graphite
Alkene composite will not be due to the SiO etched away2And recurring structure changes.
Embodiment 4
(1) the vesica shape SiO of layer 2-3 is prepared2With embodiment 3.
(2) the vesica shape SiO of layer 2-3 is prepared2/ polyaniline composite material is by 30mL 1mol L-1HCl solution, 0.0100g
The vesica shape SiO of layer 2-32, 0.0010g SDS be added sequentially in beaker, ultrasonic 45min to being completely dissolved, obtain mixing point
Dispersion liquid；Mixed dispersion liquid is transferred to in the aniline dispersion liquid to stir (0.0800g aniline is added to 10mL 1molL-1HCl
In solution, it is stirred until homogeneous), 1.5h is stirred at room temperature；0.7800g APS are added in 10mL distilled water, after being completely dissolved,
By APS solution fast transfer into above-mentioned mixed liquor, the color of suspension becomes blackish green after 5min, stirs 12h at room temperature and is sunk
Starch；Sediment is filtered, washed, is dried, SiO is obtained after grinding2/ polyaniline composite material.
(3) three layers of vesica shape polyaniline are prepared by the vesica shape SiO of the 20mg layer 2-3s of above-mentioned preparation2/ polyaniline is compound
Material is dispersed in 20mL solvents THF, and after stirring 30min, 2mL HF are added dropwise, and then proceedes to stir 12h；The suspension that will be obtained
Centrifugation, washing, dry, the number of plies that vesica shape polyaniline is obtained after grinding is 3 layers.
(4) three layers of vesica shape polyaniline/graphene composite material are prepared by 2mg to improve the oxygen that Hummers methods prepare
Graphite alkene is added in 10mL distilled water, and ultrasound obtains graphene oxide dispersion to scattered；By tri- layers of vesica shapes of 20mg
Polyaniline is added in 50mL absolute ethyl alcohols, ultrasonic 0.5h, obtains three layers of vesica shape polyaniline composite material dispersion liquid；Will oxidation
Graphene dispersing solution is slowly added under ultrasound in three layers of vesica shape dispersing polyaniline liquid, and ultrasonic 1h, obtains sediment；Will
Mixed dispersion liquid is transferred in the autoclave of polytetrafluoroethyllining lining, and autoclave is tightened and is put into baking oven, 110
It is incubated 24h under the conditions of DEG C, autoclave is naturally cooled into room temperature after hydro-thermal process, obtains sediment；The precipitation that will be obtained
After thing centrifuges, washed, centrifuged using ethanol, dried, three layers of vesica shape polyaniline/graphene composite wood are obtained after grinding
Material.
Embodiment 5
(1) the vesica shape SiO of layer 2-3 is prepared2With embodiment 3.
(2) the vesica shape SiO of layer 2-3 is prepared2/ polyaniline composite material is by 30mL 1mol L-1HCl solution, 0.0100g
The vesica shape SiO of layer 2-32, 0.0100g SDS be added sequentially in beaker, ultrasonic 60min to being completely dissolved, obtain mixing point
Dispersion liquid；Mixed dispersion liquid is transferred to in the aniline dispersion liquid to stir (0.4000g aniline is added to 10mL 1molL-1HCl
In solution, it is stirred until homogeneous), 2h is stirred at room temperature；7.0200g APS are added in 10mL distilled water, will after being completely dissolved
APS solution fast transfer is into above-mentioned mixed liquor, and the color of suspension becomes blackish green after 5min, stirs 36h at room temperature and is precipitated
Thing；Sediment is filtered, washed, is dried, SiO is obtained after grinding2/ polyaniline composite material.
(3) three layers of vesica shape polyaniline are prepared by the vesica shape SiO of the 100mg layer 2-3s of above-mentioned preparation2/ polyaniline is multiple
Condensation material is dispersed in 20mL solvents THF, and after stirring 30min, 10mL HF are added dropwise, and then proceedes to stir 148h；It is outstanding by what is obtained
Supernatant liquid centrifugation, washing, dry, the number of plies that vesica shape polyaniline is obtained after grinding is 3 layers.
(4) three layers of vesica shape polyaniline/graphene composite material are prepared by 8mg to improve the oxygen that Hummers methods prepare
Graphite alkene is added in 10mL distilled water, and ultrasound obtains graphene oxide dispersion to scattered；By tri- layers of vesicas of 100mg
Shape polyaniline is added in 50mL absolute ethyl alcohols, ultrasonic 2h, obtains three layers of vesica shape polyaniline composite material dispersion liquid；Will oxidation
Graphene dispersing solution is slowly added under ultrasound in three layers of vesica shape dispersing polyaniline liquid, and ultrasonic 4h, obtains sediment；Will
Mixed dispersion liquid is transferred in the autoclave of polytetrafluoroethyllining lining, and autoclave is tightened and is put into baking oven, 120
It is incubated 12h under the conditions of DEG C, autoclave is naturally cooled into room temperature after hydro-thermal process, obtains sediment；The precipitation that will be obtained
After thing centrifuges, washed, centrifuged using ethanol, dried, three layers of vesica shape polyaniline/graphene composite wood are obtained after grinding
Material.
Embodiment 6
A kind of ultracapacitor, its electrode material use three layers of vesica shape polyaniline/graphene composite wood in embodiment 1
Material, by verification experimental verification, the ultracapacitor has good application in electrochemical field.
Although above-mentioned the embodiment of the present invention is described with reference to accompanying drawing, model not is protected to the present invention
The limitation enclosed, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not
Need to pay various modifications or deformation that creative work can make still within protection scope of the present invention.
Claims (20)
1. the preparation method of three layers of vesica shape polyaniline/graphene composite material, it is characterized in that, comprise the following steps：Make first
The adjustable vesica shape SiO of the standby number of plies2 ；Then with the SiO2For hard template, using aniline as raw material, prepared using situ aggregation method
The adjustable SiO of the number of plies2/ polyaniline composite material；The SiO is etched using HF again2SiO in/polyaniline composite material2, obtain
Three layers of vesica shape polyaniline；Finally three layers of vesica shape polyphenyl are obtained in three layers of vesica shape polyaniline surface self-organization graphene oxide
Amine/graphene oxide composite material；And to obtain three layers of vesica shape polyaniline/graphene compound using the method for high temperature hydrothermal reduction
Material.
2. preparation method as claimed in claim 1, it is characterized in that, the adjustable vesica shape SiO of the number of plies2With the quality of aniline
Ratio is 0.0100：（0.0500-0.4500）, its preparation method is：
1. by the adjustable SiO of the number of plies2It is added to lauryl sodium sulfate (SDS) in HCl solution, ultrasound is to being completely dissolved, layer
Number；
2. aniline is dispersed in HCl solution, stirring is to being uniformly dispersed；
3. 2. 1. solution that step is prepared is transferred to step in, stirring；
4. ammonium persulfate (APS) is dissolved in water；
5. 3. 4. solution addition step that step is prepared in the solution of gained, stirs；
6. 5. sediment that step is prepared is filtered, washs, dried, grinding, the adjustable SiO of the number of plies is obtained2/ polyaniline composite wood
Material.
3. preparation method as claimed in claim 2, it is characterized in that：The adjustable SiO of the number of plies used2, SDS, aniline, APS rub
You are than being 1： 0.02080-0.20806： 0.32857-2.9572：0.20508-1.8457.
4. preparation method as claimed in claim 3, it is characterized in that：The adjustable SiO of the number of plies used2, SDS, aniline, APS rub
You are than being 1： 0.10403： 0.65714： 0.41017；
Step 1. in, the ultrasonic time is 0.5-1 h；
Step 3. in, stir 1-2 h at room temperature；
Step 5. in, stir 12-36 h at room temperature.
5. preparation method as claimed in claim 4, it is characterized in that：Step 1. in, the ultrasonic time is 1 h.
6. preparation method as claimed in claim 4, it is characterized in that：Step 3. in, stir 1 h at room temperature.
7. preparation method as claimed in claim 4, it is characterized in that：Step 5. in, stir 24h at room temperature.
8. preparation method as claimed in claim 1, it is characterized in that, the SiO2The adding proportion of/polyaniline composite material and HF
For（0.0100-0.1000）g：（1-10）ML, wherein the preparation method of three layers of vesica shape polyaniline is：
1. by the adjustable SiO of the number of plies2/ polyaniline composite material is dispersed in tetrahydrofuran (THF), stirring；
2. HF is added drop-wise to dropwise in above-mentioned dispersion liquid and stirred；
3. by the suspension 2. obtained centrifugation, washing, drying, three layers of vesica shape polyaniline are obtained after grinding.
9. preparation method as claimed in claim 8, it is characterized in that：The adjustable SiO of the number of plies2/ polyaniline composite material, four
Hydrogen furans, HF adding proportion are（0.0100-0.1000）g：（15-25）mL：（1-10）mL；
Step 1. in, the mixing time is 0.5-2 h；
Step 2. in, stir 12-48 h at room temperature.
10. preparation method as claimed in claim 9, it is characterized in that：Step 1. in, the mixing time is 0.5h.
11. preparation method as claimed in claim 9, it is characterized in that：Step 2. in, stir 24h at room temperature.
12. preparation method as claimed in claim 1, it is characterized in that, three layers of vesica shape polyaniline and graphene oxide
Mass ratio is（0.0100-0.1000）：（0.0010-0.0100）, wherein the three layers of vesica shape polyaniline/graphene is compound
The preparation method of material is：
1. graphene oxide powder is dispersed in water, it is stirred by ultrasonic, obtains the dispersion liquid of graphene oxide；
2. by three layers of vesica shape dispersing polyaniline in absolute ethyl alcohol, ultrasonic agitation；
3. the dispersion liquid of step 1. is added under ultrasound condition in the dispersion liquid of step 2., it is stirred by ultrasonic；
4. obtained sediment is obtained into three layers of vesica shape polyaniline/graphene composite wood through centrifuging, washing, dry after grinding
Expect preliminary sedimentation starch；
5. by step, 4. middle preliminary sedimentation starch is put into reactor, and hydrothermal reduction reaction occurs in a kettle, obtains three layers of vesica
Shape polyaniline/graphene composite material sediment；
6. by step 5. in three layers of vesica shape polyaniline/graphene composite material sediment through centrifuging, washing, dry, grinding
After obtain three layers of vesica shape polyaniline/graphene composite material.
13. preparation method as claimed in claim 12, it is characterized in that：The graphene oxide, water, three layers of vesica shape polyphenyl
Amine, the adding proportion of absolute ethyl alcohol are（0.0010-0.0100）g：（8-12）mL：（0.0100-0.1000）g：（45-55）mL.
14. preparation method as claimed in claim 12, it is characterized in that：Step 1. in, the ultrasonic time is 0.5-2 h；
Step 2. in, the ultrasonic time is 0.5-2 h；
Step 3. in, the ultrasonic time is 1-4 h；
Step 5. in, the reaction temperature be 100-120 °C, the reaction time is 12-48 h.
15. preparation method as claimed in claim 14, it is characterized in that：Step 1. in, the ultrasonic time is 0.5h.
16. preparation method as claimed in claim 14, it is characterized in that：Step 2. in, the ultrasonic time is 0.5 h.
17. preparation method as claimed in claim 14, it is characterized in that：Step 3. in, the ultrasonic time is 2 h.
18. preparation method as claimed in claim 14, it is characterized in that：Step 5. in, the reaction temperature be 100 °C, instead
It is 24 h between seasonable.
It is compound that 19. three layers of vesica shape polyaniline/graphene are prepared using the method any one of claim 1-18
Material.
A kind of 20. ultracapacitor of three layers of vesica shape polyaniline/graphene composite material comprising described in claim 19.
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| CN103109391A (en) * | 2010-09-24 | 2013-05-15 | 加利福尼亚大学董事会 | Nanowire-polymer composite electrodes |
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