CN101781459B - Graphene/polyaniline conductive composite material and preparation method thereof - Google Patents
Graphene/polyaniline conductive composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses graphene/polyaniline conductive composite material and a preparation method thereof. The composite material is prepared through the following steps: adding graphite oxide to alcoholic dispersing agent for ultrasonic dispersion to form evenly dispersed graphene oxide liquid mixture; adding aniline to the liquid mixture for dispersion; dripping oxidizer and inorganic solution to the liquid mixture under low temperature and blending for polymerization; centrifuging and washing to get graphene oxide /polyaniline composite material; and adding concentrated alkaline to the water suspension of the graphene oxide /polyaniline composite material, heating and blending, separating, soaking the composite material in aqueous acid, separating and drying to get graphene/polyaniline conductive composite material. The invention takes the advantage of the big specific surface area of graphene oxide to oxidize the aniline adsorbed on the graphite oxide sheet in an organic system to form sandwiched polyaniline/ graphene oxide/ polyaniline compound.
Description
Technical field
The present invention relates to a kind of organic and inorganic conducing composite material, refer more particularly to the preparation method of a kind of Graphene and polyaniline composite material.
Background technology
Conducting polymers such as polyaniline are owing to have excellent electric performance and chemical property; Especially also have chemical property stable with advantage such as environmental friendliness; It is one type of conducting polymer composite that receives much concern; Polyaniline is considered to that one of conductive polymers of actual application prospect is arranged most, and it has broad application prospects at ultracapacitor, chemical power source, antistatic, electrochromism, electromagnetic shielding and aspects such as biological and chemical sensor.Graphene and carbon nanotube belong to new carbon family together, are the materials the thinnest in the known materials, that hardness is maximum, toughness is maximum.Graphene has unique physical and chemical performances, like electroconductibility (its electric transmission speed is than fast tens of times of silicon), thermal conductivity and the mechanicalness etc. of excellence.Chinese patent CN1887965A and CN100441634 adopt the method for in-situ deposition or galvanic deposit polyaniline or other conducting polymer to prepare matrix material respectively on carbon nanotube; This material has than the better electrochemical properties of single composition material; But mixture prepares from the aqueous solution; Compound is inhomogeneous, also can influence giving full play to of two constituent materials performances.Therefore it is very important how to prepare even compound graphene/polyaniline conductive composite material, and this conducing composite material has bigger theory and actual application value in various fields such as ultracapacitor, battery equal energy source field and transmitters.
Summary of the invention
The object of the invention is to provide a kind of preparation technology is simple and cost is relatively low in-situ polymerization, reduction method to prepare good, the even method of compound graphene/polyaniline conductive composite material of electroconductibility.
The technical solution that realizes the object of the invention is: a kind of graphene/polyaniline conductive composite material is characterized in that being got by the following steps preparation:
The first step is added to dispersant for ultrasonic dispersion with graphite oxide, forms homodisperse graphene oxide liquid mixture;
Second step under the room temperature, added aniline monomer in the first step gained mixed solution, continue ultra-sonic dispersion and form mixed solution, restir;
The 3rd step under the low temperature, dropwise added the dispersant solution of oxygenant and inorganic doping acid in the second step gained mixed solution, stir polymerization;
In the 4th step, the mixed solution that the 3rd step obtained is centrifugal, washing obtains graphene oxide/polyaniline conductive polymer composite material;
The 5th step added concentrated base in the aqeous suspension of above-mentioned product, the heated and stirred reaction;
In the 6th step, the mixture that the 5th step obtained is centrifugal, washing obtains the graphene/polyaniline matrix material;
The 7th step, the 6th matrix material that obtain of step to be soaked in aqueous acid, centrifugal, washing, drying obtain graphene/polyaniline conductive composite material.
The present invention compared with prior art; Its remarkable advantage: (1) preparation method is last; The big specific surface area that makes full use of graphene oxide is adsorbed on the oxidized graphite flake surface with aniline in organic system, form sandwich-like polyaniline/graphene oxide/polyaniline mixture through polymerization; (2) utilize concentrated base under heating condition, to make the cancellation of graphene oxide surface oxy radical break away from; Thereby obtain the graphene/polyaniline matrix material; Polyaniline is gone to mix by alkali simultaneously, and the later stage only need use conventional soak for some time can obtain different sour adulterated polyaniline/graphene conductive composite materials; (3) realized that polyaniline is deposited on the graphene film both sides equably, thereby reduced the agglomeration of Graphene, improved the utilization ratio of its specific surface area; (4) it is easy, with short production cycle to prepare the operating process of this product, and productive rate is high, and not high to equipment requirements, cost is lower.
Below in conjunction with accompanying drawing the present invention is described in further detail.
Description of drawings
Fig. 1 is the preparing method's of a graphene/polyaniline matrix material of the present invention schematic flow sheet.
Fig. 2 is the Electronic Speculum figure of the graphene/polyaniline conductive composite material for preparing of the present invention.
Fig. 3 is the intermediate product of instance 1 gained and the IR figure of final product.
Fig. 4 is the intermediate product of instance 1 gained and the xps figure of final product.
Embodiment
Graphene/polyaniline conductive composite material of the present invention and preparation method thereof is got by the following steps preparation:
The first step is added to dispersant for ultrasonic dispersion with graphite oxide, forms homodisperse graphene oxide liquid mixture;
Second step under the room temperature, added aniline monomer in the first step gained mixed solution, continue ultra-sonic dispersion and form mixed solution, restir;
The 3rd step under the low temperature, dropwise added the dispersant solution of oxygenant and inorganic doping acid in the second step gained mixed solution, stir polymerization;
In the 4th step, the mixed solution that the 3rd step obtained is centrifugal, washing obtains graphene oxide/polyaniline conductive polymer composite material;
The 5th step added concentrated base in the aqeous suspension of above-mentioned product, the heated and stirred reaction;
In the 6th step, the mixture that the 5th step obtained is centrifugal, washing obtains the graphene/polyaniline matrix material;
The 7th step, the 6th matrix material that obtain of step to be soaked in aqueous acid, centrifugal, washing, drying obtain graphene/polyaniline conductive composite material.
Among the preparation method of graphene/polyaniline conductive composite material of the present invention, dispersion agent is an alcohol, like ethanol, terepthaloyl moietie, Virahol.Inorganic doping acid is hydrochloric acid, sulfuric acid, perchloric acid etc., and oxygenant is ammonium persulphate or Potassium Persulphate, and concentrated base is sodium hydroxide or Pottasium Hydroxide.The ratio of dispersion agent and the consumption of graphite oxide 10: 1～100: 1; Aniline monomer is 0.001: 1～50: 1 with the ratio of the consumption of graphite oxide; The ratio of aniline monomer and the mole dosage of oxygenant 1: 1～4: 1, oxygenant is 1: 2～1: 5 with the ratio of the mole dosage of dopant acid.Wherein, the consumption of dispersion agent, aniline monomer is in microlitre; The consumption of oxygenant, graphite oxide is in milligram; The consumption of dopant acid is in milliliter.Ultrasonic time is ultrasonic 20～120min in the first step.Ultrasonic time is ultrasonic 10～60min in second step, stirs 30～120min.Temperature when adding the oxygenant stirring in the 3rd step is 0～5 ℃, stirs 1～4 hour.The temperature that adds the concentrated base heating in the 5th step is 80～90 ℃, stirs 1～5 hour.Acid in the 7th step can be conventional arbitrarily mineral acid example hydrochloric acid, sulfuric acid, perchloric acid etc., and concentration is 0.1～2mol/L, soak time 12h.
Wherein, the preparation of graphite oxide is following: 10g Vanadium Pentoxide in FLAKES and 10g Potassium Persulphate are joined take out after stirring 30min in 80 ℃, the 30mL vitriol oil, normal temperature down behind the reaction 6h with product filter, washing is to neutral and dry to constant weight at normal temperatures.Above-mentioned product is joined in the vitriol oil of 0 ℃ of 460mL, stir and the slow potassium permanganate that adds, hierarchy of control temperature is no more than 15 ℃ simultaneously; Be warming up to 35 ± 3 ℃ after stirring; After continuing to stir certain hour, in system, slowly add the 1L deionized water, controlled temperature is no more than 100 ℃; Continue to stir 15min, adding 2.8L deionized water and 50mL mass concentration are 30% ydrogen peroxide 50.After stirring 5min gained brown suspension suction filtration, dialysis there is not sulfate ion to filtrating.Product is subsequent use at 60 ℃ of following vacuum dryings.
Embodiment 1
The method of graphene/polyaniline Composite Preparation of the present invention may further comprise the steps:
The first step is added to ultra-sonic dispersion in the 40mL terepthaloyl moietie with the 5mg graphite oxide, forms homodisperse graphene oxide liquid mixture, ultrasonic 20～120min;
Second step joined the 0.46mL aniline monomer in the second step product, and ultrasonic 10～60min disperses to form mixed solution, restir 30～120min.
In the 3rd step, under 0～5 ℃, in the second step gained system, dropwise add the ethylene glycol solution 10mL of 1.141g ammonium persulphate and 0.85mL 37% concentrated hydrochloric acid, and continue to stir 1h.
The 4th step, the 3rd mixed solution that obtain of step is centrifugal, with obtaining graphene oxide/polyaniline conductive polymer composite material behind ethanol, the water repetitive scrubbing.
In the 5th step, in the 60mL of above-mentioned product aqeous suspension, add 6mol/LNaOH, 90 ℃ of heated and stirred 5h;
In the 6th step, the mixture that the 5th step obtained is centrifugal, water repetitive scrubbing obtains the graphene/polyaniline matrix material.
The 7th step was immersed in 12h in the 0.3mol/L aqueous hydrochloric acid with the 6th matrix material that obtain of step, centrifugal, washing, after 60 ℃ of vacuum-drying, promptly obtained graphene/polyaniline conductive composite material.
Structure and pattern characterize:
The sem photograph of gained matrix material is seen Fig. 2 (A), and is as shown in the figure, and the upper and lower surfaces of Graphene is covered by the polyaniline nano particle fully, formed the matrix material of sandwich structure.The product of the 4th, six, seven step gained of the graphite oxide of gained and instance 1 has carried out structure and surface-element analysis with IR and XPS, and the result sees Fig. 3 and Fig. 4.
Fig. 3: among the infrared figure of graphite oxide respectively 1726,1620,1390cm
-1The vibration peak that C=O, C-O-H, C-O-C have occurred, be used for correlated pure polyaniline then 1560,1472cm
-1Phenyl ring and quinone ring skeletal vibration peak appear, 1200,1400cm
-1The C-N vibration peak.And the peak of C=O and polyaniline has appearred in the vibration peak of the 4th step product, and wave number has taken place, and graphene oxide is explained in displacement and polyaniline is organic is combined with each other; The disappearance of the vibration peak of oxy radical such as C=O explains that graphene oxide/polyaniline has changed graphene/polyaniline in the 6th and the 7th step product, and the variation of vibration peak and displacement are also explained between Graphene and the polyaniline and had interaction force.
Fig. 4: the XPS result of the product of the 4th step gained shows that the higher explanation of the content of oxygen contains graphene oxide in the mixture, the formation of the existence explanation polyaniline of chlorine and nitrogen element, and the doped hydrochloride attitude; The reduction greatly of the disappearance of chlorine and oxygen level explanation polyaniline is gone to mix in the product in the 6th step, and graphene oxide is reduced; The final product that the 7th step obtained is because the doping of acid demonstrates the existence of dopant ion chlorine.
In addition, the four probe method specific conductivity of having tested title product is～10S/cm
-2, good conductivity.
The success of above test result proof title product is synthetic.
The method of graphene/polyaniline Composite Preparation of the present invention may further comprise the steps:
The first step is added to ultra-sonic dispersion in the 50mL ethanol with the 1.1mg graphite oxide, forms homodisperse graphene oxide liquid mixture, ultrasonic 20～120min;
Second step joined the 1.1mL aniline monomer in the second step product, and ultrasonic 10～60min disperses to form mixed solution, restir 30～120min.
In the 3rd step, under 0～5 ℃, in the second step gained system, dropwise add the ethanolic soln 10mL of the concentrated hydrochloric acid of 1.37g ammonium persulphate and 1.02mL 37%, and continue to stir 2h.
The 4th step is with the step 4 in the instance 1.
In the 5th step, in the 50mL of above-mentioned product aqeous suspension, adding NaOH, to make its concentration be 8mol/L, 80 ℃ of heated and stirred 1h;
The 6th step is with the step 6 in the instance 1.
The 7th step was immersed in 12h in the 0.1mol/L aqueous sulfuric acid with the 6th matrix material that obtain of step, centrifugal, washing, after 60 ℃ of vacuum-drying, promptly obtained graphene/polyaniline conductive composite material.
The transmission electron microscope picture of gained matrix material is seen Fig. 2 (B), and is as shown in the figure, and the upper and lower surfaces of Graphene is covered by the polyaniline nano particle fully, formed the matrix material of sandwich structure, simultaneously has polyaniline fiber to link to each other between sheet and sheet.
Embodiment 3
The method of graphene/polyaniline Composite Preparation of the present invention may further comprise the steps:
The first step is added to ultra-sonic dispersion in the 100mL terepthaloyl moietie with the 0.018mg graphite oxide, forms homodisperse graphene oxide liquid mixture, ultrasonic 20～120min;
Second step joined the 0.913mL aniline monomer in the second step product, and ultrasonic 10～60min disperses to form mixed solution, restir 30～120min.
In the 3rd step, under 0～5 ℃, in the second step gained system, dropwise add the ethylene glycol solution 5mL of 0.761g ammonium persulphate and 0.947mL perchloric acid, and continue to stir 3h.
The 4th step is with the step 4 in the instance 1.
In the 5th step, in the 70mL of above-mentioned product aqeous suspension, adding NaOH, to make its concentration be 7mol/L, 90 ℃ of heated and stirred 3h;
The 6th step is with the step 6 in the instance 1.
The 7th step was immersed in 12h in the 0.2mol/L aqueous hydrochloric acid with the 6th matrix material that obtain of step, centrifugal, washing, after 60 ℃ of vacuum-drying, promptly obtained graphene/polyaniline conductive composite material.
The transmission electron microscope picture of gained matrix material is seen Fig. 2 (C), and is as shown in the figure, and the upper and lower surfaces of Graphene is covered by the polyaniline nano particle fully, formed the matrix material of sandwich structure.
Embodiment 4
The method of graphene/polyaniline Composite Preparation of the present invention may further comprise the steps:
The first step is added to ultra-sonic dispersion in the 45mL ethanol with the 10mg graphite oxide, forms homodisperse graphene oxide liquid mixture, ultrasonic 20～120min;
Second step joined the 0.01mL aniline monomer in the second step product, and ultrasonic 10～60min disperses to form mixed solution, restir 30～120min.
In the 3rd step, under 0～5 ℃, in the second step gained system, dropwise add the ethanolic soln 5mL of the vitriol oil of 0.025g Potassium Persulphate and 0.018mL98%, and continue to stir 3h.
The 4th step is with the step 4 in the instance 1.
In the 5th step, in the 50mL of above-mentioned product aqeous suspension, adding NaOH, to make its concentration be 6mol/L, 90 ℃ of heated and stirred 5h;
The 6th step is with the step 6 in the instance 1.
The 7th step was immersed in 12h in the 0.5mol/L aqueous sulfuric acid with the 6th matrix material that obtain of step, centrifugal, washing, after 60 ℃ of vacuum-drying, promptly obtained graphene/polyaniline conductive composite material.
Embodiment 5
The method of graphene/polyaniline Composite Preparation of the present invention may further comprise the steps:
The first step is added to ultra-sonic dispersion in the 120mL ethanol with the 5mg graphite oxide, forms homodisperse graphene oxide liquid mixture, ultrasonic 20～120min;
Second step joined the 3.4mL aniline monomer in the second step product, and ultrasonic 10～60min disperses to form mixed solution, restir 30～120min.
In the 3rd step, under 0～5 ℃, in the second step gained system, dropwise add the ethanolic soln 30mL of 2.5g ammonium persulphate and 2.77ml37% concentrated hydrochloric acid, and continue to stir 1h.
The 4th step is with the step 4 in the instance 1.
In the 5th step, in the 100mL of above-mentioned product aqeous suspension, adding KOH, to make its concentration be 8mol/L, 90 ℃ of heated and stirred 4h;
The 6th step is with the step 6 in the instance 1.
The 7th step was immersed in 12h in the 1mol/L aqueous sulfuric acid with the 6th matrix material that obtain of step, centrifugal, washing, after 60 ℃ of vacuum-drying, promptly obtained graphene/polyaniline conductive composite material.
Embodiment 6
The method of graphene/polyaniline Composite Preparation of the present invention may further comprise the steps:
The first step is added to ultra-sonic dispersion in the 30mL Virahol with the 1mg graphite oxide, forms homodisperse graphene oxide liquid mixture, ultrasonic 20～120min;
Second step joined the 1.83mL aniline monomer in the second step product, and ultrasonic 10～60min disperses to form mixed solution, restir 30～120min.
In the 3rd step, under 0～5 ℃, in the second step gained system, dropwise add the aqueous isopropanol 10mL of the concentrated hydrochloric acid of 2.0g Potassium Persulphate and 3.38mL 37%, and continue to stir 2h.
The 4th step is with the step 4 in the instance 1.
In the 5th step, in the 50mL of above-mentioned product aqeous suspension, adding NaOH, to make its concentration be 8mol/L, 80 ℃ of heated and stirred 5h;
The 6th step is with the step 6 in the instance 1.
The 7th step was immersed in 12h in the 2mol/L aqueous hydrochloric acid with the 6th matrix material that obtain of step, centrifugal, washing, after 60 ℃ of vacuum-drying, promptly obtained the graphene/polyaniline conductive polymer composite.
The transmission electron microscope picture of gained matrix material is seen Fig. 2 (D), and is as shown in the figure, and the surface of Graphene lamella is covered by the polyaniline nano particle fully, formed the matrix material of sandwich structure.
Claims (8)
1. graphene/polyaniline conductive composite material is characterized in that by the following steps preparation and gets:
The first step is added to dispersant for ultrasonic dispersion with graphite oxide, forms homodisperse graphene oxide liquid mixture, and wherein dispersion agent is ethanol, terepthaloyl moietie or Virahol;
Second step under the room temperature, added aniline monomer in the first step gained mixed solution, continue ultra-sonic dispersion and form mixed solution, restir;
In the 3rd step, under the low temperature, in the second step gained mixed solution, dropwise add the dispersant solution of oxygenant and inorganic doping acid; Stir polymerization; Wherein oxygenant is ammonium persulphate or Potassium Persulphate, and dispersion agent is ethanol, terepthaloyl moietie or Virahol, and inorganic doping acid is hydrochloric acid, sulfuric acid or perchloric acid;
In the 4th step, the mixed solution that the 3rd step obtained is centrifugal, washing obtains graphene oxide/polyaniline conductive polymer composite material;
The 5th step added sodium hydroxide or Pottasium Hydroxide in the aqeous suspension of above-mentioned product, the heated and stirred reaction;
In the 6th step, the mixture that the 5th step obtained is centrifugal, washing obtains the graphene/polyaniline matrix material;
The 7th step, the 6th matrix material that obtain of step, concentration is soaked in being the conventional inorganic acid aqueous solution of 0.1～2mol/L, and centrifugal, washing, drying obtain graphene/polyaniline conductive composite material, and wherein conventional mineral acid is hydrochloric acid, sulfuric acid or perchloric acid.
2. the preparation method of a graphene/polyaniline conductive composite material is characterized in that may further comprise the steps:
The first step is added to dispersant for ultrasonic dispersion with graphite oxide, forms homodisperse graphene oxide liquid mixture, and wherein dispersion agent is ethanol, terepthaloyl moietie or Virahol;
Second step under the room temperature, added aniline monomer in the first step gained mixed solution, continue ultra-sonic dispersion and form mixed solution, restir;
In the 3rd step, under the low temperature, in the second step gained mixed solution, dropwise add the dispersant solution of oxygenant and inorganic doping acid; Stir polymerization; Wherein oxygenant is ammonium persulphate or Potassium Persulphate, and dispersion agent is ethanol, terepthaloyl moietie or Virahol, and inorganic doping acid is hydrochloric acid, sulfuric acid or perchloric acid;
In the 4th step, the mixed solution that the 3rd step obtained is centrifugal, washing obtains graphene oxide/polyaniline conductive polymer composite material;
The 5th step added sodium hydroxide or Pottasium Hydroxide in the aqeous suspension of above-mentioned product, the heated and stirred reaction;
In the 6th step, the mixture that the 5th step obtained is centrifugal, washing obtains the graphene/polyaniline matrix material;
The 7th step, the 6th matrix material that obtain of step, concentration is soaked in being the conventional inorganic acid aqueous solution of 0.1～2mol/L, and centrifugal, washing, drying obtain graphene/polyaniline conductive composite material, and wherein conventional mineral acid is hydrochloric acid, sulfuric acid or perchloric acid.
3. the preparation method of graphene/polyaniline conductive composite material according to claim 2; It is characterized in that: the ratio of dispersion agent and the consumption of graphite oxide 10: 1～100: 1; Aniline monomer is 0.001: 1～50: 1 with the ratio of the consumption of graphite oxide; The ratio of aniline monomer and the mole dosage of oxygenant 1: 1～4: 1, oxygenant is 1: 2～1: 5 with the ratio of the mole dosage of dopant acid; Wherein, the consumption of dispersion agent, aniline monomer is in microlitre; The consumption of oxygenant, graphite oxide is in milligram; The consumption of dopant acid is in milliliter.
4. the preparation method of graphene/polyaniline conductive composite material according to claim 2, it is characterized in that: ultrasonic time is ultrasonic 20～120min in the first step.
5. the preparation method of graphene/polyaniline conductive composite material according to claim 2 is characterized in that: ultrasonic time is ultrasonic 10～60min in second step, stirs 30～120min.
6. the preparation method of graphene/polyaniline conductive composite material according to claim 2 is characterized in that: adding the temperature of oxygenant when stirring in the 3rd step is 0～5 ℃, stirs 1～4 hour.
7. the preparation method of graphene/polyaniline conductive composite material according to claim 2 is characterized in that: the temperature that adds the concentrated base heating in the 5th step is 80～90 ℃, stirs 1～5 hour.
8. the preparation method of graphene/polyaniline conductive composite material according to claim 2 is characterized in that: the soak time 11～12h in the 7th step.
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| CN101492569A (en) * | 2008-07-01 | 2009-07-29 | 南京理工大学 | Oxidized graphite flake layer/polyaniline composite material and method for preparing the same |
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