CN110498920A - Conducting polymer and the nano-complex of graphene and preparation method thereof - Google Patents
Conducting polymer and the nano-complex of graphene and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 134
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 59
- 239000002322 conducting polymer Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 57
- 239000010439 graphite Substances 0.000 claims abstract description 57
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 62
- 238000002604 ultrasonography Methods 0.000 claims description 33
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000007800 oxidant agent Substances 0.000 claims description 19
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- 238000006243 chemical reaction Methods 0.000 claims description 16
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- 235000011130 ammonium sulphate Nutrition 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to conducting polymers and the nano-complex of graphene and preparation method thereof.The characteristic that the present invention is matched with surface tension needed for removing graphite just using the surface tension of conducting polymer monomer, serves as remover for liquid conductive polymer monomer, removing solvent and subsequent polymerized monomer is united, and making the two is same component.Compared with prior art, the present invention removes polymerization system and does not introduce any other second of solvent or stabilizer or surfactant, it relies solely on same component and plays removing and polymerization double action, it fundamentally ensure that the pure property of gained nano-complex, to solve the residue problem that graphene prepared by other liquid phase stripping methods is inevitably present removing solvent and auxiliary additive.Polymerized monomer is used as remover, and such design has not been reported to prepare graphene nanometer composite.
Description
Technical field
The present invention relates to graphene complex preparation technical fields, more particularly, to the nanometer of conducting polymer and graphene
Compound and preparation method thereof.
Background technique
Graphene is by single layer SP2Hydbridized carbon atoms arrange the honeycomb hexaplanar crystal to be formed, and have excellent electricity
Learn performance, thermal property and mechanical property.The single-layer graphene of its atom level level was studied by Geimy small for the first time in 2004
Group by micromechanics stripping method be made (Novoselov K S, Geim A K, Morozov S V, Jiang D, Zhang Y,
Dubonos S V,Grigorieva I V,Firsov A.A.Electric field effect in atomically
Thin carbon films.Science, 2004,306 (5696): 666-669), the new century that graphene is studied is opened from this
Member.In the two major classes preparation method of graphene --- in-" from bottom to top " (Bottom-Up) and " from top to bottom " (Top-Down),
Being related to micro-processing technology approach the former more, it is easily prepared, the single layer of better quality can also be made and lack layer graphene, but item
Part harshness (high temperature, high vacuum), it is difficult to volume production.And the latter is then using graphite as raw material, also by intercalation, liquid phase removing, oxidation
Graphene is made in the approach such as original, has volume production potentiality.Liquid phase stripping method among these has preparation cost cheap, easy to operate easy
The advantages that row, gained graphene defect are few and paid high attention to.Effective liquid phase release system includes various organic molten
Agent (Hernandez Y, NicoloSsiv, Lotya M, et al.High-yield production of graphene by
liquid-phase exfoliation of graphite.Nature Nanotechnology 2008,3:563-568；
Coleman J N.Liquid exfoliation of defect-Free graphene.Account Chemical
Research 2013,46 (1): 14-22) and added with various surfactants water-based system (Lotya M, Hernandez Y,
King P J.et al.Liquid Phase Production of Graphene by Exfoliation of Graphite
in Surfactant/Water Solutions.J.Am.Chem.Soc.2009,131:3611–3620；Chinese patent
201110456632.5).The concentration of some graphene dispersing solutions can also be reached very high concentration and be realized by various techniques
Rapid dispersion (Khan U, Porwal H, O ' Neill A, et al.Solvent-Exfoliated Graphene at
Extremely High Concentration.Langmuir 2011,27:9077–9082；Barwich S,Khan U,
Coleman J N.J.Phys.Chem.C2013,117:19212-19218).However, graphene obtained in this way or meeting
Because the boiling point of used organic solvent is high, steam forces down and can live there are dissolvent residual or because of added surface
Strong effect between property agent and the big pi bond of graphene and not can be removed.Although these impurity amount is few, its property to graphene
Can influence be fatal, if further preparing graphene complex as raw material, the original performance of graphene is by nothing
The abundant system of method comes out.
Building and general as a branch of conducting polymer, with the nano-complex or nano hybridization body of graphene
It is applied to efficient electric chemical capacitor and has become one of hot spot of current nano-complex area research (Bae J, Park
J Y,Kwon O S,Lee C S.Energy Efficient Capacitors based on Graphene/conducting
Polymer Hybrids.J.Ind.Eng.Chem.2017,51:1-11.).For being used as the nano-complex of electrode sensor,
Conducting polymer thereon and graphene nanometer composite can by electrochemical method successively electropolymerization in situ into (Raj M,
Gupta P, Goyal R N, Shim Y.B.Graphene/conducting polymer nano-composite loaded
screen printed carbon sensor for simultaneous determination of dopamine and
5-hydroxytryptamine.Sensors Actuators is B.2017,239:993-1002) this kind of compound of is without requirement
It produces, is also limited by electrode area and be difficult to volume production.Therefore, conducting polymer/graphene compound of electrochemistry preparation does not exist
This is discussed in scope.
And the nano-complex of the graphene/ conductive polymer with scale volume production potentiality can be according to conducting polymer
Polymerization order of priority, and the preparation method of this kind of nano-complex is divided into three kinds:
(1) direct blending, i.e., by the two it is well prepared in advance respectively after be blended together (Wu, Q. again；Xu,Y.X.；Yao,
Z.Y.；Liu,A.R.；Shi,G.Q.Supercapacitors Based on Flexible Graphene/Polyaniline
Nanofiber Composite Films.ACS Nano 2010,4(4),1963-1970.).Obvious direct blending be difficult by
The two is evenly dispersed, it more difficult to reach the compound of Nano grade, this method uses few.
(2) reduction method after first polymerizeing again restores rGO after carrying out in-situ polymerization that is, in GO nanometer sheet, this method letter
It is single easy, it is a kind of relatively conventional complex method.Aniline monomer is added into the ethylene glycol dispersion liquid of GO, oxidant mistake is added
After the ethylene glycol solution of ammonium sulfate and hydrochloric acid, it is compound that aniline monomer carries out in-situ polymerization acquisition GO/PANI on GO chip immediately
Object.It is handled at 90 DEG C with 8M NaOH solution again, so that wherein GO is restored, obtains polyaniline/graphene complex (Wang, H.；
Hao,Q.；Yang,X.；Lu,L.；Wang,X.A Nanostructured Graphene/Polyaniline Hybrid
Material for Supercapacitors.Nanoscale 2010,2(10),2164-2170.Zhang,K.；Zhang,
L.L.；Zhao,X.S.；Wu,J.Graphene/Polyaniline Nanofiber Composites as
Supercapacitor Electrodes.Chem.Mater.2010,22(4),1392-1401.).But graphene oxide is also
Hydrophobic property after original make its it is extremely difficult keep extended position in hydrophilic solution, therefore the rGO after restoring easily is rolled into a ball in the liquid phase
Poly- and stacking, addition surfactant can make moderate progress, but system component, which has, becomes complicated impure.In the process, graphite
The rear reduction of alkene causes inevitable destruction to the structure of compound, while the laminated structure of stacked in multi-layers is for aoxidizing stone
The reduction of black alkene also produces certain obstruction, the graphene that cannot be restored completely because oxygen-containing group residual so that electric conductivity
It declines to a great extent.
(3) synchronous in-situ polymerization reduction method, i.e., carry out the in-situ polymerization of conducting polymer while nanometer rGO is restored.
Nano-graphene can be two-dimensional surface shape and be also possible to 3 D stereo configuration, and the latter can more be easy answering for nanoscale
It closes.But its preparation process is complicated, has certain uncertainty.It is living that the rGO being formed in situ simultaneously is equally also required to addition surface
Property agent stablize, to guarantee that the graphene after reduction being capable of fine dispersion (Mao, L. in aqueous solution；Zhang,K.；On Chan,
H.S.；Wu,J.Surfactant-Stabilized Graphene/Polyaniline Nanofiber Composites for
High Performance Supercapacitor Electrode.J.Mater.Chem.2012,22(1),80-85.).This
Undoubtedly make reactive component complicated, there is the risk for being difficult to thoroughly remove.
As it can be seen that the method for preparing graphene complex by raw material of rGO, which exists, forms unpurified hidden danger.It is only not added and appoints
The direct liquid phase removing of the graphite of what additive can just overcome this drawback.In fact, directly liquid phase stripping method is not only one
Industrialized preparation method may be implemented in kind, and is also applied for preparing graphene composite material.However, if removing solvent choosing
It is improper to select, then obtained compound equally has the unpurified hidden danger of composition.Only select those will not remaining solvent
System can just overcome the problems, such as this.As it can be seen that although there are many method of preparation liquid phase removing graphene, it is compound for graphene
All exist when the preparation of object containing drawbacks such as impurity, particularly redisperse difficulty such as residual solvent and metallic elements, the stone reported
The preparation of black alkene compound not can be implemented simultaneously it is easy to operate, be easy to volume production, removing sufficiently, the features such as nanoscale is compound.Cause
This, find it is a kind of it is simple and easy, can high yield, scale obtain the system of the remaining high-quality graphene complex of pure free from admixture
Preparation Method is of great significance.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of conducting polymer with
Nano-complex of graphene and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions:
First aspect present invention: providing a kind of preparation method of graphene, and conducting polymer monomer is added into graphite and makees
It for organic solvent, is sealed against impregnating, continuous ultrasound or the fresh conducting polymer monomer of replacement carry out more wheel ultrasounds after taking-up, will
Product centrifuge separation arrives graphene after drying.
The conducting polymer monomer is selected from aniline, methylaniline, ethyl aniline, propyl aniline, methylphenylamine, N- second
One of base aniline or N propyl aniline are a variety of；Or,
The conducting polymer monomer is selected from one of pyrroles or a variety of.
The graphite is natural flake graphite or expansible graphite, preferably expansible graphite.
The proportion of the graphite and conducting polymer monomer is no more than 10/1 (mg/mL), preferably 0.5/1 (mg/mL).
The soaking time of the graphite be 1h~8 week, preferably 1 week；
The soaking temperature of the graphite is room temperature~60 DEG C, preferably room temperature.
It is described ultrasound when temperature control be room temperature~60 DEG C, preferably 40 DEG C；
The ultrasound selection two ways, rod-type ultrasound or water bath sonicator；
The ultrasonic frequency range is 20kHz to 70kHz, preferably 53kHz；
The ultrasonic time is 1h~100h, regards graphite in conducting polymer monomer depending on content, and content is higher, ultrasonic
Time is longer；
When carrying out more wheel ultrasounds, ultrasonic number is 1 time~5 times, and depending on content of graphite, content is higher, and ultrasound wheel number is got over
It is more.
The drying includes freeze-dried and vacuum drying.
Second aspect of the present invention: a kind of preparation method of the nano-complex of conducting polymer and graphene, Xiang Shi are provided
Conducting polymer monomer is added in ink as organic solvent, is sealed against impregnating, continuous ultrasound or the fresh conduction of replacement after taking-up
Polymer monomer carries out more wheel ultrasounds, system after ultrasound is centrifuged, the excess of solvent in Aspirate supernatant obtains graphene and leads
The co-mixing system of electric polymer monomer, it is molten to graphene and addition oxidizer salt sour water in the co-mixing system of conducting polymer monomer
Liquid is stirred to react, centrifugation, and abandonings is sucked out in upper liquid suction pipe, and HCl concussion washing is added in lower sediment, washes away oligomer and instead
By-product is answered, is finally centrifuged, suspension is dry, obtain the nano-complex of conducting polymer and graphene.
One preferred embodiment are as follows: conducting polymer monomer is added into graphite as organic solvent, is sealed against
It impregnates, continuous ultrasound or the fresh conducting polymer monomer of replacement carry out more wheel ultrasounds after taking-up, and system after ultrasound is centrifuged, is drawn
Excess of solvent in supernatant obtains the co-mixing system of graphene Yu conducting polymer monomer,
Have ultrasound or without ultrasound under oxidant hydrochloric acid is added dropwise in co-mixing system to graphene and conducting polymer monomer
Aqueous solution, then it is stirred to react 6~for 24 hours, obtain aterrimus suspension.Reaction was completed, is centrifuged 90 under 4000rpm~10000rpm
Minute, upper liquid suction pipe is sucked out abandoning and washs 5 repeatedly after the hand violent concussion washing of 1M HCl is added in lower sediment
~6 times, oligomer and byproduct of reaction are thoroughly washed away, finally centrifugation obtains black suspension and be placed in culture dish be freeze-dried
8h is pre-chilled in the cold-trap of machine at -60 DEG C, then the dry 40h under 10Pa vacuum, obtains receiving for conducting polymer and graphene
Rice compound, weighing calculate the weight ratio of the two in conducting polymer yield and compound.
The conducting polymer monomer is selected from aniline, methylaniline, ethyl aniline, propyl aniline, methylphenylamine, N- second
One of base aniline or N propyl aniline are a variety of；Or,
The conducting polymer monomer is selected from one of pyrroles or a variety of.
The graphite is natural flake graphite or expansible graphite, preferably expansible graphite.
The proportion of the graphite and conducting polymer monomer is no more than 10/1 (mg/mL), preferably 0.5/1 (mg/mL).
The soaking time of the graphite be 1h~8 week, preferably 1 week；
The soaking temperature of the graphite is room temperature~60 DEG C, preferably room temperature.
It is described ultrasound when temperature control be room temperature~60 DEG C, preferably 40 DEG C；
The ultrasound selection two ways, rod-type ultrasound or water bath sonicator；
The ultrasonic frequency range is 20kHz to 70kHz, preferably 53kHz；
The ultrasonic time is 1h~100h, regards graphite in conducting polymer monomer depending on content, and content is higher, ultrasonic
Time is longer；
When carrying out more wheel ultrasounds, ultrasonic number is 1 time~5 times, and depending on content of graphite, content is higher, and ultrasound wheel number is got over
It is more.
The drying includes freeze-dried and vacuum drying.
The oxidant is ammonium persulfate or ferric trichloride.
The combined weight ratio of the nano-complex of the conducting polymer and graphene is 60/40~99.9/0.1, preferably
Than being classified as 80/20~99/1.
Graphite in the actual yield and conducting polymer/graphene nanometer composite of gained conducting polymer in the present invention
The actual weight percentage calculation formula of alkene derives as follows in detail:
Due to being 1M HCl because of polymerization system, in addition removing sour in polymerization process, entire polymerization system is in acidity, therefore
The conducting polymer of generation is doped.And the sulfate radical maximum concentration generated is be only concentration of hydrochloric acid 1/10 or so, therefore
Outer dopant is mainly HCl, and conducting polymer calculates yield Y with doped hydrochloridedCP:
YdCP=WRdCP/WTdCP=(WTotal–Gw)/WTdCP。。。。。。。。。。。。(1)
RCP/G=(WTotal–Gw)/Gw。。。。。。。。。。。。(2)
YdCP: the yield of doped conducting polymer
RCP/G: the compound ratio of the weight of doped conducting polymer and graphene
WRdCP: doped conducting polymer actual weight；
WTdCP: doped conducting polymer theoretical weight；
WTotal: the total weight of gained compound
Gw: graphene puts into weight
Third aspect present invention: the nano combined of the conducting polymer and graphene for using the above method to be prepared is provided
Object.
Innovative point of the invention: the present invention using liquid conducting polymer monomer surface tension just with removing graphite
The characteristic that required surface tension matches is used as remover, while the micro oligomerisation generated by monomer in ultrasonic procedure
Object promotes the intercalation between more effective graphite to increase graphite charge stripping efficiency.Organic solvent after completing removing is removing margin
After can be transformed into the desired amount of reaction initial monomers dosage, and stay at this time the residual monomer in system with graphene π
Conjugation interaction has occurred between plane, has reached the compound of molecular level.It therefore, can in-situ polymerization after addition oxidant
Generate polymer nanocomposite.This removing polymerization system does not introduce any other second of solvent or stabilizer or surface
Activating agent relies solely on same component and plays removing and polymerization double action, fundamentally ensure that gained nano-complex
Pure property, so that solving graphene prepared by other liquid phase stripping methods is inevitably present removing solvent and auxiliary addition
The residue problem of agent.Polymerized monomer is used as remover, and such design has not been reported to prepare graphene nanometer composite.
Beneficial effects of the present invention: liquid phase stripping method is a kind of method that industrialized production may be implemented, and is also applied for giving birth to
Produce graphene composite material.And this method is different from other liquid phase stripping means mainly in terms of the selection of remover.Its function
Can feature be will remove solvent and subsequent polymerized monomer is united, both make for same component.Stripping process can be continuous
Carry out, as wish to obtain high-quality lack layer so that single-layer graphene can also take out the graphene being stripped halfway after progress it is more
Wheel removing.Only more wheels removing of finite number of time, removing yield up to 100wt%, i.e., whole graphite be stripped into single layer and
The graphene of few layer.Conducting polymer can be homopolymer, be also possible to copolymer.This nanostructured composites composite construction
Finely, it can achieve the compound of nanoscale truly.This compound preparation method is not only easy to operate, Er Qiesuo
It is pure to obtain compound composition, does not influence the residual of the high boiling solvent of electric conductivity.Meanwhile method economy of the invention has
Effect and can realize prepare with scale at simple process.
Detailed description of the invention
Fig. 1 is ultraviolet-visible spectrum of the 11 gained graphene dispersing solution of embodiment after 6 times of dilutions；
Fig. 2 is the TG curve of the nano-complex of aniline copolymer prepared by embodiment 5 and graphene；
Fig. 3 is that the scanning electron microscope of the nano-complex of aniline copolymer prepared by embodiment 5 and embodiment 8 and graphene is shone
Piece.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Examples 1 to 2
Using instantaneous high-temperature plavini come expanded graphite.0.5g graphite is weighed, is put into porcelain crucible, heating is put it into and rises
It is taken out immediately after seeing its expansion in the Muffle furnace of temperature to 950 DEG C, after the several seconds, is placed on heatproof experimental bench, closes the lid, cool
It is cooling to being put in close to after room temperature in the drier equipped with blue silica gel.Expanded graphite is obtained, is weighed, volume is measured, according to public affairs
Formula (3) calculates expansion rate (mL/g), 2 graphene kinds parallel laboratory test the results are shown in Table 1 three times respectively, the graphite after expansion
1 is also shown in Table with the conductivity that four probe method measures after tabletting.
Expansion rate (mL/g)=V2/m2 (3)
The variation and its expansion rate of volume and quality before and after 1 graphite high-temperature expansion of table
Embodiment 3
6.5mg commercial graphite alkene powder is placed in the 1M hydrochloric acid solution of 100mL, water-bath interval ultrasound 2h (53kHz, 180W,
100%) 0.9mL aniline and 0.5g o-aminophenol sulfonic acid, is added, continues ultrasound 15min；50mL separately is added in 3.0g ammonium persulfate
Water is made into oxidizing agent solution, and ultrasonic 15min accelerates dissolution, adds dropwise the ammonium persulfate oxidizing agent solution to monomer solution
In.Reaction was completed after continuing to be stirred to react for 24 hours, and 30min is centrifuged under 3000rpm, and abandoning, lower sediment is sucked out in supernatant liquor suction pipe
1M HCl is added and seals the hand violent concussion washing of bottleneck, washs 5~6 times repeatedly, thoroughly washes away oligomer and reaction is secondary
Product, centrifugation obtain black suspension and are placed in culture dish, be put into the cold-trap of freeze drier and 8h is pre-chilled at -60 DEG C, with
The dry 40h under 10Pa vacuum afterwards, obtains the nano-complex of aniline copolymer and graphene, and weighing calculates the polymerization of aniline copolymer
Yield is 51.8%, and it is 0.0142S/cm that four probe of pressed disc method, which measures conductivity,.
Embodiment 4
Show the advantage of water bath sonicator supplemental polymeric.
It keeps graphene and monomer dosage and other experiment conditions in embodiment 3 constant, but oxidizing agent solution will be added dropwise
Agitating mode is changed to water bath sonicator mode (53kHz, 180W, 100%), during which pays attention to reinforcing water-bath temperature control, keeps below it
50℃.But increases ultrasonic procedure when oxidant is added dropwise, aniline copolymer and graphene nanometer composite can be prepared.It is copolymerized
The nano-complex of aniline and graphene, the polymerization yield rate that weighing calculates aniline copolymer is 50.0%, and four probe of pressed disc method measures
Conductivity is 0.223S/cm.The conductivity of gained compound increases 15.8 times after ultrasonic wave added polymerization process.
Embodiment 5
13mg expanded graphite is added in the bottle of known accurate weight and 20mL aniline, SK3300HP supersonic cleaning machine exist
Under 180W and 53kHz, water bath sonicator 48h is carried out.Be centrifuged 90min at 3,000 rpm later, by all graphenes include single layer and
Double-deck all settles down, and Aspirate supernatant abandons it, but to retain surplus materials weight in bottle is just 13+744.8=
757.8mg, (removing empty bottle weight), then obtain dispersion liquid of the 13mg graphene in 0.73mL aniline.By 378.4mg hydroxyl sulphur
Sour aniline is added in 100mL 1M HCl, rocks and is added in above-mentioned graphene dispersing solution after making it dissolve.Separately by 2.28g persulfuric acid
Ammonium is added 50mL hydrochloric acid and is made into oxidizing agent solution, and it is molten to monomer that ammonium persulfate oxidizing agent solution is added dropwise dropwise under water bath sonicator auxiliary
In liquid.Reaction was completed after continuing to be stirred to react for 24 hours, and 90min is centrifuged under 4000rpm, and abandoning is sucked out in supernatant liquor suction pipe, and lower layer is heavy
The addition 1M HCl that forms sediment seals the hand violent concussion washing of bottleneck, then is centrifuged 90min at 3,000 rpm, washs 5~6 repeatedly
It is secondary, oligomer and byproduct of reaction are thoroughly washed away, centrifugation obtains black suspension and is placed in culture dish, is put into freeze drier
8h is pre-chilled in cold-trap at -60 DEG C, then the dry 40h under 10Pa vacuum, obtains the nano combined of aniline copolymer and graphene
Object 645.6mg, the polymerization yield rate for calculating aniline copolymer is 50.2%, and the compound ratio of copolymer and graphene is 98/ in compound
2, it is 9.73 × 10 that four probe of pressed disc method, which measures conductivity,-2S/cm.The specific test data of tabletting each point conductivity is shown in Table 2.
The pressed powder each point conductivity of aniline copolymer prepared by 2 embodiment 5 of table and graphene complex
Embodiment 6
Embodiment 5 is repeated, but after the completion of graphite removing, original organic solvent is all taken out into abandoning, uses institute instead
The fresh organic monomer of requirement carries out the synthesis of copolymer, finally obtains the nano-complex of aniline copolymer and graphene
522.2mg, the polymerization yield rate for calculating aniline copolymer is 40.3%, and the compound ratio of copolymer and graphene is 98/2 in compound,
It is 3.06 × 10 that four probe of pressed disc method, which measures conductivity,-3S/cm, on an equal basis under compound ratio, the conductivity of gained compound is less than original
1/3 come.The specific test data of tabletting each point conductivity is shown in Table 3.As it can be seen that graphene occurs to be conjugated phase interaction with monomer after removing
With the contribution to aniline copolymer conductivity.
Pressed powder (with a thickness of 0.376mm) each point of aniline copolymer prepared by 3 embodiment 6 of table and graphene complex
Conductivity
Embodiment 7
Embodiment 5 is repeated, but graphene dosage is changed to 3mg, finally obtains the nano combined of aniline copolymer and graphene
Object 533.1mg, the polymerization yield rate for calculating aniline copolymer is 41.5%, and the compound ratio of copolymer and graphene is in compound
99.5/0.5, it is 1.1 × 10 that four probe of pressed disc method, which measures conductivity,-3S/cm。
Embodiment 8
6.5mg EG and 20mL aniline is added in the 30mL teat glass of known accurate weight, is placed in SK3300HP ultrasound
In cleaning machine (180W, 53kHz), 100% power carries out water bath sonicator 20h, after completing first round removing, 900rpm centrifugation
45min, draw 70% upper liquid 14mL to 100mL teat glass in, cover tightly bottle cap keep well it is spare.For not shelling for former bottom of bottle portion
The fresh aniline of 14mL is added from graphite and carries out the second wheel 20h removing, collects the 2nd wheel supernatant into above-mentioned 100mL teat glass；
So carry out 5 wheel removings.Tube wall is without remaining expanded graphite solid after being centrifuged after 5th wheel removing.
All these being collected into 5 are taken turns into supernatant 76mL, 90min is centrifuged in 4000rpm, includes single layer by all graphenes
It all settles down with double-deck, gradually Aspirate supernatant abandons it, and making surplus materials weight in bottle is just 6.5+744.8=
751.3mg then obtains dispersion liquid of the 6.5mg graphene in 0.73mL aniline.378.4mg hydroxyl sulfoacid phenylamine is added
In 100mL 1M HCl, rocks and be added after making it dissolve in above-mentioned graphene dispersing solution.50mL separately is added in 2.28g ammonium persulfate
Hydrochloric acid is made into oxidizing agent solution, and ammonium persulfate oxidizing agent solution is added dropwise dropwise into monomer solution under water bath sonicator auxiliary.Continue
Reaction was completed after being stirred to react for 24 hours, and 90min is centrifuged under 4000rpm, and abandoning is sucked out in supernatant liquor suction pipe, and 1M is added in lower sediment
HCl seals the hand violent concussion washing of bottleneck, then 90min is centrifuged at 4000rpm, washs 5~6 times, thoroughly washes repeatedly
Remove oligomer and byproduct of reaction, centrifugation obtains black suspension and is placed in culture dish, be put into the cold-trap of freeze drier in-
8h is pre-chilled at 60 DEG C, then the dry 40h under 10Pa vacuum, obtains the nano-complex of aniline copolymer and graphene
630.72mg, the polymerization yield rate for calculating aniline copolymer is 56.2%, and the compound ratio of copolymer and graphene is 99/1 in compound,
It is 1.2S/cm that four probe of pressed disc method, which measures conductivity,.
The comparison nano-complex that commodity in use graphene is done in example 4, discovery is using the present invention in embodiment 8
In the conductivity of the prepared obtained nano-complex of graphene to be higher by 5.4 times (1.2S/cm Vs.0.223S/cm),
Embody the value of removing polymerization in situ.
Embodiment 9
Embodiment 8 is repeated, but graphene dosage is changed to 35mg, the nanometer for finally obtaining aniline copolymer and graphene is multiple
Conjunction object is 539.8mg, and the polymerization yield rate for calculating aniline copolymer is 42.0%, and the compound ratio of copolymer and graphene is in compound
94/6, it is 10.9S/cm that four probe of pressed disc method, which measures conductivity,.
Embodiment 10
Embodiment 8 is repeated, but graphene dosage is changed to 50mg, the nanometer for finally obtaining aniline copolymer and graphene is multiple
Conjunction object is 527.6mg, and the polymerization yield rate for calculating aniline copolymer is 41.0%, and the compound ratio of copolymer and graphene is in compound
91/9, it is 63.7S/cm that four probe of pressed disc method, which measures conductivity,.
Embodiment 11
Impregnate in-situ polymerization after removing in aniline 3 weeks
It takes 20mg graphite to pour into 30mL teat glass, addition 20mL aniline, seals infiltration 3 weeks up for safekeeping at room temperature, impregnate
Be conducive to wetting of the solvent to graphite worm shape cellular structure, or even fully wet by the capillary phenomenon in vermiform duct
Graphite microcrystal, to promote the removing of graphite.Immersion terminates, and carries out take turns according to embodiment 8 more and removes, and 6 wheel of discovery can be completed
The removing of whole graphite, removing rate reach 100%.The UV, visible light after 6 times of dilutions of every wheel removing graphene dispersing solution
Light map is shown in Fig. 1, it is seen that absorbance A of the graphene of 6 times of dilution to 660nm6602.4659 are reached as high as, according to the stone surveyed
The absorptivity 4388L/ (g.m) of black alkene, it is estimated that the concentration of graphene is 0.337mg/mL.
All these being collected into 6 wheel supernatant 110mL is centrifuged 90min in 4000rpm, includes single layer by all graphenes
It all settles down with double-deck, gradually Aspirate supernatant abandons it, and making surplus materials weight in bottle is just 20+744.8=
764.8mg then obtains dispersion liquid of the 20mg graphene in 0.73mL aniline.50mL hydrochloric acid separately is added in 2.28g ammonium persulfate
It is made into oxidizing agent solution, ammonium persulfate oxidizing agent solution is added dropwise dropwise into monomer solution under water bath sonicator auxiliary.Continue to stir
Reaction was completed after reaction for 24 hours, and 90min is centrifuged under 4000rpm, and abandoning is sucked out in supernatant liquor suction pipe, and 1MHCl envelope is added in lower sediment
The firmly hand violent concussion washing of bottleneck, then 90min is centrifuged at 4000rpm, it washs 5~6 times repeatedly, thoroughly washes away oligomerisation
Object and byproduct of reaction, centrifugation obtain black suspension and are placed in culture dish, be put into the cold-trap of freeze drier at -60 DEG C
8h is pre-chilled, then the dry 40h under 10Pa vacuum, obtains the nano-complex 977.82mg of aniline copolymer and graphene, calculate
The polymerization yield rate of aniline copolymer is 74.5%, compound than being 98/2, four probe of pressed disc method of copolymer and graphene in compound
Measuring conductivity is 17.6S/cm.
Embodiment 12
Removing of the graphite in pyrroles
6.5mg EG will be taken to be placed in 100mL round-bottomed flask, 13mL pyrroles is added, being made into EG content is 0.5mg/mL, close
Envelope, which is impregnated 52 days, to be placed in SK3300HP supersonic cleaning machine (180W, 53kHz), and 100% power carries out water bath sonicator 20h, complete
After removing at the first round, 900rpm is centrifuged 90min, draws in 70% upper liquid 10.0mL to 100mL teat glass, covers tightly bottle cap
It keeps well spare.The fresh pyrroles of 10.0mL is added for the unstripped graphite in former bottom of bottle portion and carries out the 2nd wheel 45h removing, collects the 2nd wheel
Supernatant is into above-mentioned 100mL teat glass.It is collected into graphene pyrroles's dispersion liquid 30mL altogether after so carrying out 3 wheel removings.It will
Its ultrasound 30min restores, and 50 μ L is taken to carry out ultraviolet-visible map scanning (fresh pyrrole after 6 times of dilutions (1:5) of fresh pyrroles
Cough up reference), absorbance at 660nm is measured, it is dense that gained graphene pyrroles's dispersion liquid is calculated using 4419L/ (g.m) as absorptivity
Degree, the results are shown in Table 4.
More wheel peel results of 4 graphene of table in pyrroles
Embodiment 13
Graphene dispersing solution 13.0mL after removing 50h is transferred in centrifuge tube, 10000rpm is centrifuged 90min, by institute
There is graphene all to settle down, gradually Aspirate supernatant abandons it, and making surplus materials weight in bottle is just 6.5+332.8=
339.3mg then obtains 6.5mg graphene in 0.343mL pyrroles (density 0.967g/cm3) in dispersion liquid.This dispersion liquid is turned
It moves to stand-by in the conical flask for filling 100mL 1M HCl.25mL 1M HCl separately is added in 1.131g (0.554g) ammonium persulfate
It is made into oxidizing agent solution, ammonium persulfate oxidizing agent solution is added dropwise dropwise into monomer solution under water bath sonicator auxiliary.Continue room temperature
Lower ultrasonic reaction 6h, then reaction was completed by magnetic agitation 18h at room temperature, and 90min is centrifuged under 4000rpm, and supernatant liquor suction pipe is inhaled
It is abandoned out, and lower sediment is added 1M HCl and seals the hand violent concussion washing of bottleneck, then is centrifuged 90min at 4000rpm, so
It washs 5~6 times repeatedly, thoroughly washes away oligomer and byproduct of reaction, the nanometer of polypyrrole and graphene is obtained after freeze-drying
Compound 355.22mg, the polymerization yield rate for calculating polypyrrole is 84.4%, and polymer and graphene answers in see Table 5 for details compound
Composition and division in a proportion is 98/2, and it is respectively 0.018S/cm that four probe of pressed disc method, which measures conductivity,.See Table 6 for details
The polypyrrole/graphene nano-complex of 5 in-situ polymerization of table preparation
The pressed powder each point conductivity of polypyrrole prepared by 6 embodiment 13 of table and graphene complex
Embodiment 14
With embodiment 13, only compound is compound than different.Make surplus materials in bottle after all graphenes are all settled
Weight is just 6.5+163.0=169.5mg, then obtains dispersion liquid of the 6.5mg graphene in 0.168mL pyrroles.It polymerize
To the nano-complex 177.0mg of polypyrrole and graphene, the polymerization yield rate for calculating polypyrrole is 78.3%, is polymerize in compound
The compound ratio of object and graphene is 96/4, and it is respectively 0.13S/cm that four probe of pressed disc method, which measures conductivity,.It the results are shown in Table 5.
Embodiment 15
Thermogravimetric analysis
It is added in crucible, the compound 13.4mg of aniline copolymer prepared by embodiment 5 and graphene with 10 DEG C/min
Heating speed heated in air atmosphere, obtain thermal gravimetric analysis curve TG and its differential curve DTG see Fig. 2.As can be seen that with
The weight of the raising of heating temperature, nano-complex is being gradually reduced, and when temperature reaches 100 DEG C or so, a weightlessness occurs
Peak, caused by this is the loss of the natural equilibrium water in main nano-complex；The weight of subsequent nano-complex is with temperature
Rise further decline, weight loss rate is relatively uniform, and when 530 DEG C, compound is all decomposed.
Embodiment 16:SEM
The nano-complex of compound aniline copolymer and graphene than for 99/1 prepared by embodiment 8 is a small amount of, it is added
On silicon wafer, the metal spraying after ethyl alcohol volatilization is placed in FEI Co., U.S. Quanta 200 and scans electricity drop after dehydrated alcohol ultrasonic disperse
It is observed under mirror (SEM), SEM photograph is shown in Fig. 3.It can be seen that the aniline copolymer particle for the sub-micron being freely present, while
There is aniline copolymer particle to be attached on graphene, being especially observed that also has inserting for aniline copolymer in graphene nanometer sheet interlayer
Enter, form be coated with graphene wafer meet structure.The composite construction of this form is to be difficult in common complex method
It realizes.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of preparation method of graphene, which is characterized in that conducting polymer monomer is added into graphite as organic solvent,
It is sealed against impregnating, continuous ultrasound or the fresh conducting polymer monomer of replacement carry out more wheel ultrasounds after taking-up, by product centrifugation point
From, it is dry after to get arriving graphene.
2. a kind of preparation method of the nano-complex of conducting polymer and graphene, which is characterized in that be added and lead into graphite
Electric polymer monomer is sealed against impregnating as organic solvent, continuous ultrasound or the fresh conducting polymer monomer of replacement after taking-up
More wheel ultrasounds are carried out, system after ultrasound are centrifuged, the excess of solvent in Aspirate supernatant obtains graphene and conducting polymer list
The co-mixing system of body,
To oxidizer salt aqueous acid is added in the co-mixing system of graphene and conducting polymer monomer, it is stirred to react, is centrifuged, on
Abandoning is sucked out in layer liquid suction pipe, and lower sediment is added HCl concussion washing, washes away oligomer and byproduct of reaction, be finally centrifuged, will
Suspension is dry, obtains the nano-complex of conducting polymer and graphene.
3. preparation method according to claim 1 or claim 2, which is characterized in that the conducting polymer monomer is selected from aniline, methyl
Aniline, ethyl aniline, propyl aniline, one of methylphenylamine, N-ethylaniline or N propyl aniline or a variety of；Or,
The conducting polymer monomer is selected from one of pyrroles or a variety of.
4. preparation method according to claim 1 or claim 2, which is characterized in that the graphite is natural flake graphite or may expand
Graphite, preferably expansible graphite.
5. preparation method according to claim 1 or claim 2, which is characterized in that the proportion of the graphite and conducting polymer monomer
No more than 10/1 (mg/mL), preferably 0.5/1 (mg/mL).
6. preparation method according to claim 1 or claim 2, which is characterized in that the soaking time of the graphite is 1h~8 week, excellent
It is selected as 1 week；
The soaking temperature of the graphite is room temperature~60 DEG C, preferably room temperature.
7. preparation method according to claim 1 or claim 2, which is characterized in that temperature control is room temperature~60 DEG C when the ultrasound,
It is preferred that 40 DEG C；
The ultrasound selection two ways, rod-type ultrasound or water bath sonicator；
The ultrasonic frequency range is 20kHz to 70kHz, preferably 53kHz；
The ultrasonic time is 1h~100h；
When carrying out more wheel ultrasounds, ultrasonic number is 1 time~5 times.
8. preparation method according to claim 2, which is characterized in that the oxidant is ammonium persulfate or ferric trichloride.
9. preparation method according to claim 2, which is characterized in that the nano-complex of the conducting polymer and graphene
Combined weight ratio be 60/40~99.9/0.1, preferably than being classified as 80/20~99/1.
10. using the nano-complex of conducting polymer and graphene that claim 2 the method is prepared.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101746754A (en) * | 2009-10-13 | 2010-06-23 | 中国科学院化学研究所 | Method for preparing grapheme through organic amine solvothermal method |
| CN102464313A (en) * | 2010-11-05 | 2012-05-23 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
| CN102779649A (en) * | 2012-08-01 | 2012-11-14 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of thin layer graphene polymer composite material |
| CN106046369A (en) * | 2016-07-19 | 2016-10-26 | 青岛科技大学 | Preparation of polyaniline-graphene layer-layer composite material assisted by supercritical method |
| CN108529607A (en) * | 2018-01-19 | 2018-09-14 | 同济大学 | A kind of preparation method of graphene |
-
2018
- 2018-05-18 CN CN201810481446.9A patent/CN110498920B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101746754A (en) * | 2009-10-13 | 2010-06-23 | 中国科学院化学研究所 | Method for preparing grapheme through organic amine solvothermal method |
| CN102464313A (en) * | 2010-11-05 | 2012-05-23 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
| CN102779649A (en) * | 2012-08-01 | 2012-11-14 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of thin layer graphene polymer composite material |
| CN106046369A (en) * | 2016-07-19 | 2016-10-26 | 青岛科技大学 | Preparation of polyaniline-graphene layer-layer composite material assisted by supercritical method |
| CN108529607A (en) * | 2018-01-19 | 2018-09-14 | 同济大学 | A kind of preparation method of graphene |
Non-Patent Citations (1)
| Title |
|---|
| XIANGNAN CHEN, ET AL.: "One-step synthesis of graphene/polyaniline hybrids by in situ intercalation polymerization and their electromagnetic properties", 《NANOSCALE》 * |
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