CN101781459A - Graphene/polyaniline conductive composite material and preparation method thereof - Google Patents
Graphene/polyaniline conductive composite material and preparation method thereof Download PDFInfo
- Publication number
- CN101781459A CN101781459A CN201010105275A CN201010105275A CN101781459A CN 101781459 A CN101781459 A CN 101781459A CN 201010105275 A CN201010105275 A CN 201010105275A CN 201010105275 A CN201010105275 A CN 201010105275A CN 101781459 A CN101781459 A CN 101781459A
- Authority
- CN
- China
- Prior art keywords
- graphene
- composite material
- polyaniline
- conductive composite
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
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 advantages such as the stable and environmental friendliness of chemical property, it is the conducting polymer composite that a class 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, as 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: on (1) preparation method, 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 can obtain different sour adulterated polyaniline/graphene conductive composite materials with acid soak for some time of routine; (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, the productive rate height, 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 preparation 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 example 1 gained and the IR figure of final product.
Fig. 4 is the intermediate product of example 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, as ethanol, ethylene glycol, 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 potassium 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, being prepared as follows of graphite oxide: 10g Vanadium Pentoxide in FLAKES and 10g Potassium Persulphate joined take out after stirring 30min in 80 ℃, the 30mL vitriol oil, normal temperature filters product behind the reaction 6h down, 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, slowly add the 1L deionized water in system, controlled temperature is no more than 100 ℃, continue to stir 15min, adding 2.8L deionized water and 50mL mass concentration are 30% hydrogen peroxide.Stir behind the 5min gained brown suspension suction filtration, dialysing does not have sulfate ion to filtrate.Product is standby 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 ethylene glycol 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, promptly obtained graphene/polyaniline conductive composite material after 60 ℃ of vacuum-drying.
Structure and pattern characterize:
The sem photograph of gained matrix material is seen Fig. 2 (A), and as shown in the figure, the upper and lower surface of Graphene is covered fully by the polyaniline nano particle, has formed the matrix material of sandwich structure.The products of the 4th, six, seven step gained of the graphite oxide of gained and example 1 have carried out structure and surface-element analysis with IR and XPS, the results are shown in Figure 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 displacement illustrates graphene oxide and polyaniline is organic is combined with each other; The disappearance of the vibration peak of oxy radical such as C=O illustrates that graphene oxide/polyaniline has changed graphene/polyaniline in the 6th and the 7th step product, and the variation of vibration peak and displacement also illustrate between Graphene and the polyaniline and have 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 target product is～10S/cm
-2, good conductivity.
The success of above test result proof target 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 example 1.
In the 5th step, adding NaOH in the 50mL of above-mentioned product aqeous suspension, to make its concentration be 8mol/L, 80 ℃ of heated and stirred 1h;
The 6th step is with the step 6 in the example 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, promptly obtained graphene/polyaniline conductive composite material after 60 ℃ of vacuum-drying.
The transmission electron microscope picture of gained matrix material is seen Fig. 2 (B), and as shown in the figure, the upper and lower surface of Graphene is covered fully by the polyaniline nano particle, has 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 ethylene glycol 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 example 1.
In the 5th step, adding NaOH in the 70mL of above-mentioned product aqeous suspension, to make its concentration be 7mol/L, 90 ℃ of heated and stirred 3h;
The 6th step is with the step 6 in the example 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, promptly obtained graphene/polyaniline conductive composite material after 60 ℃ of vacuum-drying.
The transmission electron microscope picture of gained matrix material is seen Fig. 2 (C), and as shown in the figure, the upper and lower surface of Graphene is covered fully by the polyaniline nano particle, has 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 example 1.
In the 5th step, adding NaOH in the 50mL of above-mentioned product aqeous suspension, to make its concentration be 6mol/L, 90 ℃ of heated and stirred 5h;
The 6th step is with the step 6 in the example 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, promptly obtained graphene/polyaniline conductive composite material after 60 ℃ of vacuum-drying.
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 example 1.
In the 5th step, adding KOH in the 100mL of above-mentioned product aqeous suspension, to make its concentration be 8mol/L, 90 ℃ of heated and stirred 4h;
The 6th step is with the step 6 in the example 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, promptly obtained graphene/polyaniline conductive composite material after 60 ℃ of vacuum-drying.
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 example 1.
In the 5th step, adding NaOH in the 50mL of above-mentioned product aqeous suspension, to make its concentration be 8mol/L, 80 ℃ of heated and stirred 5h;
The 6th step is with the step 6 in the example 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, promptly obtained the graphene/polyaniline conductive polymer composite after 60 ℃ of vacuum-drying.
The transmission electron microscope picture of gained matrix material is seen Fig. 2 (D), and as shown in the figure, the surface of Graphene lamella is covered fully by the polyaniline nano particle, has formed the matrix material of sandwich structure.
Claims (10)
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;
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.
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;
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.
3. the preparation method of graphene/polyaniline conductive composite material according to claim 2 is characterized in that: dispersion agent ethanol, ethylene glycol or Virahol.
4. the preparation method of graphene/polyaniline conductive composite material according to claim 2 is characterized in that: inorganic doping acid is hydrochloric acid, sulfuric acid or perchloric acid, and oxygenant is ammonium persulphate or Potassium Persulphate, and concentrated base is sodium hydroxide or potassium hydroxide.
5. 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.
6. 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.
7. 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.
8. 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.
9. 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.
10. the preparation method of graphene/polyaniline conductive composite material according to claim 2 is characterized in that: the acid in the 7th step is conventional arbitrarily mineral acid, and concentration is 0.1～2mol/L, soak time 11～12h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101052753A CN101781459B (en) | 2010-02-04 | 2010-02-04 | Graphene/polyaniline conductive composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101052753A CN101781459B (en) | 2010-02-04 | 2010-02-04 | Graphene/polyaniline conductive composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101781459A true CN101781459A (en) | 2010-07-21 |
| CN101781459B CN101781459B (en) | 2012-05-23 |
Family
ID=42521617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101052753A Active CN101781459B (en) | 2010-02-04 | 2010-02-04 | Graphene/polyaniline conductive composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101781459B (en) |
Cited By (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102059095A (en) * | 2010-12-09 | 2011-05-18 | 江南大学 | Method for preparing graphene composite material adsorbing polycyclic aromatic hydrocarbon pollutants |
| CN102220027A (en) * | 2011-04-25 | 2011-10-19 | 北京航空航天大学 | Grapheme/electroconductive polymer composite and preparation method thereof |
| CN102492296A (en) * | 2011-11-25 | 2012-06-13 | 江南大学 | Synthesis method of water dispersible polyaniline/graphene composite material |
| CN102558856A (en) * | 2011-12-21 | 2012-07-11 | 天津大学 | Polyaniline/graphite fluoride composite material and preparation method thereof |
| CN102618094A (en) * | 2012-03-08 | 2012-08-01 | 桂林理工大学 | Method for grafting graphene oxide on biphenyl thermotropic liquid crystal compound |
| CN102671549A (en) * | 2012-04-10 | 2012-09-19 | 浙江大学 | Preparation method of graphene-based composite separation membrane device |
| CN102760865A (en) * | 2011-04-26 | 2012-10-31 | 海洋王照明科技股份有限公司 | Preparation method of nitrogen-substituted graphene oxide/polyaniline composite material |
| CN102789842A (en) * | 2012-07-27 | 2012-11-21 | 青岛科技大学 | Preparation method of conducting polymer/grapheme composite nanometer material |
| CN102826538A (en) * | 2012-09-17 | 2012-12-19 | 辽宁科技大学 | Method for preparing nitrogen-doped carbonaceous material by modifying polymer |
| CN102879430A (en) * | 2012-10-15 | 2013-01-16 | 苏州大学 | Graphene/polyaniline hybrid material-based gas sensor and preparation method for same |
| CN102923689A (en) * | 2012-11-06 | 2013-02-13 | 中国科学院宁波材料技术与工程研究所 | Method for preparing grapheme/carbon composite material |
| CN103199267A (en) * | 2013-03-04 | 2013-07-10 | 北京师范大学 | Preparation technology of nano-Fe3O4-V2O5-Au-doped poly-naphthylamine film modified netted glassy carbon electrode |
| CN103230782A (en) * | 2013-04-09 | 2013-08-07 | 甘肃农业大学 | Graphene-doped polyaniline adsorption material preparation and application |
| CN103373724A (en) * | 2012-04-17 | 2013-10-30 | 安炬科技股份有限公司 | Method for preparing graphene composite material |
| CN103507320A (en) * | 2012-06-14 | 2014-01-15 | 国际商业机器公司 | Graphene based structures and methods for shielding electromagnetic radiation |
| CN103980703A (en) * | 2014-06-04 | 2014-08-13 | 福州大学 | Flocculent-polyaniline-coated graphene composite material and preparation method and application thereof |
| CN104031433A (en) * | 2014-06-09 | 2014-09-10 | 大连理工大学 | Low-conductivity flake graphene composite material, and preparation method and application thereof |
| CN104072764A (en) * | 2014-07-08 | 2014-10-01 | 南京邮电大学 | Preparation method of polyaniline-graphene composite material |
| CN104231264A (en) * | 2014-06-19 | 2014-12-24 | 杭州师范大学 | Preparation method and application of graphene oxide/silicon dioxide/polyaniline composite material |
| CN104592857A (en) * | 2014-12-30 | 2015-05-06 | 安科智慧城市技术（中国）有限公司 | Graphene modified polyaniline conductive coating and preparation method thereof |
| CN104629360A (en) * | 2013-11-07 | 2015-05-20 | 中国科学院宁波材料技术与工程研究所 | Conductive polymer-graphene nanocomposite material, and preparation method and use thereof |
| CN104727188A (en) * | 2015-02-08 | 2015-06-24 | 浙江理工大学 | Preparation method of environment-friendly conductive paper |
| CN104910378A (en) * | 2015-05-26 | 2015-09-16 | 浙江理工大学 | Preparation method for polyaniline/graphene oxide nanocomposite |
| CN105136889A (en) * | 2015-10-15 | 2015-12-09 | 田野 | Graphene glucose sensor |
| CN105199134A (en) * | 2015-10-12 | 2015-12-30 | 湖北工业大学 | Polyaniline-modified graphene conductive composite film and preparation method thereof |
| CN105694031A (en) * | 2015-12-27 | 2016-06-22 | 南京新月材料科技有限公司 | Preparation method of graphene-polyaniline composite material |
| CN105807451A (en) * | 2014-12-30 | 2016-07-27 | 北京生美鸿业科技有限公司 | Intelligent light adjusting film based on graphene/organic matter composite transparent conductive film |
| US9413075B2 (en) | 2012-06-14 | 2016-08-09 | Globalfoundries Inc. | Graphene based structures and methods for broadband electromagnetic radiation absorption at the microwave and terahertz frequencies |
| CN106633050A (en) * | 2016-12-22 | 2017-05-10 | 陕西科技大学 | Rodlike polyaniline load modified titanium carbide and low-temperature preparation method thereof |
| CN106633051A (en) * | 2016-12-22 | 2017-05-10 | 陕西科技大学 | Titanium carbide/polyaniline composite material and preparation method thereof |
| CN106674517A (en) * | 2016-12-22 | 2017-05-17 | 陕西科技大学 | Polyaniline surface modified titanium carbide composite material and low-temperature preparation method thereof |
| CN108587446A (en) * | 2018-03-26 | 2018-09-28 | 合肥萃励新材料科技有限公司 | A kind of production method of polyaniline appendix graphite ene coatings |
| CN108659218A (en) * | 2018-05-22 | 2018-10-16 | 温州市赢创新材料技术有限公司 | A kind of intercalated graphite alkene denatured conductive polyaniline and preparation method thereof |
| CN108753045A (en) * | 2018-06-11 | 2018-11-06 | 江苏海田电子材料有限公司 | A kind of electrically conductive ink |
| CN110551393A (en) * | 2019-08-30 | 2019-12-10 | 武汉工程大学 | preparation method of conductive polymer/graphene oxide composite material |
| CN112471798A (en) * | 2020-11-27 | 2021-03-12 | 安徽银禾木业有限公司 | Environment-friendly solid wood board and processing method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492569B (en) * | 2008-07-01 | 2011-01-26 | 南京理工大学 | Oxidized graphite flake layer/polyaniline composite material and method for preparing the same |
-
2010
- 2010-02-04 CN CN2010101052753A patent/CN101781459B/en active Active
Cited By (54)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102059095A (en) * | 2010-12-09 | 2011-05-18 | 江南大学 | Method for preparing graphene composite material adsorbing polycyclic aromatic hydrocarbon pollutants |
| CN102059095B (en) * | 2010-12-09 | 2013-01-23 | 江南大学 | Method for preparing graphene composite material adsorbing polycyclic aromatic hydrocarbon pollutants |
| CN102220027A (en) * | 2011-04-25 | 2011-10-19 | 北京航空航天大学 | Grapheme/electroconductive polymer composite and preparation method thereof |
| CN102760865B (en) * | 2011-04-26 | 2014-10-15 | 海洋王照明科技股份有限公司 | Preparation method of nitrogen-substituted graphene oxide/polyaniline composite material |
| CN102760865A (en) * | 2011-04-26 | 2012-10-31 | 海洋王照明科技股份有限公司 | Preparation method of nitrogen-substituted graphene oxide/polyaniline composite material |
| CN102492296A (en) * | 2011-11-25 | 2012-06-13 | 江南大学 | Synthesis method of water dispersible polyaniline/graphene composite material |
| CN102492296B (en) * | 2011-11-25 | 2014-02-12 | 江南大学 | Synthesis method of water dispersible polyaniline/graphene composite material |
| CN102558856A (en) * | 2011-12-21 | 2012-07-11 | 天津大学 | Polyaniline/graphite fluoride composite material and preparation method thereof |
| CN102618094A (en) * | 2012-03-08 | 2012-08-01 | 桂林理工大学 | Method for grafting graphene oxide on biphenyl thermotropic liquid crystal compound |
| CN102618094B (en) * | 2012-03-08 | 2013-10-30 | 桂林理工大学 | Method for grafting graphene oxide on biphenyl thermotropic liquid crystal compound |
| CN102671549A (en) * | 2012-04-10 | 2012-09-19 | 浙江大学 | Preparation method of graphene-based composite separation membrane device |
| CN103373724B (en) * | 2012-04-17 | 2015-05-20 | 安炬科技股份有限公司 | Method for preparing graphene composite material |
| CN103373724A (en) * | 2012-04-17 | 2013-10-30 | 安炬科技股份有限公司 | Method for preparing graphene composite material |
| US9413075B2 (en) | 2012-06-14 | 2016-08-09 | Globalfoundries Inc. | Graphene based structures and methods for broadband electromagnetic radiation absorption at the microwave and terahertz frequencies |
| US9210835B2 (en) | 2012-06-14 | 2015-12-08 | International Business Machines Corporation | Graphene based structures and methods for shielding electromagnetic radiation |
| US9174413B2 (en) | 2012-06-14 | 2015-11-03 | International Business Machines Corporation | Graphene based structures and methods for shielding electromagnetic radiation |
| CN103507320A (en) * | 2012-06-14 | 2014-01-15 | 国际商业机器公司 | Graphene based structures and methods for shielding electromagnetic radiation |
| US9174414B2 (en) | 2012-06-14 | 2015-11-03 | International Business Machines Corporation | Graphene based structures and methods for shielding electromagnetic radiation |
| CN102789842B (en) * | 2012-07-27 | 2014-12-31 | 青岛科技大学 | Preparation method of conducting polymer/grapheme composite nanometer material |
| CN102789842A (en) * | 2012-07-27 | 2012-11-21 | 青岛科技大学 | Preparation method of conducting polymer/grapheme composite nanometer material |
| CN102826538A (en) * | 2012-09-17 | 2012-12-19 | 辽宁科技大学 | Method for preparing nitrogen-doped carbonaceous material by modifying polymer |
| CN102879430A (en) * | 2012-10-15 | 2013-01-16 | 苏州大学 | Graphene/polyaniline hybrid material-based gas sensor and preparation method for same |
| CN102923689A (en) * | 2012-11-06 | 2013-02-13 | 中国科学院宁波材料技术与工程研究所 | Method for preparing grapheme/carbon composite material |
| CN102923689B (en) * | 2012-11-06 | 2015-08-19 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of graphene/carbon composite material |
| CN103199267B (en) * | 2013-03-04 | 2015-08-12 | 北京师范大学 | Nanometer Fe 3o 4-V 2o 5the preparation technology of the poly-film modified reticulated vitreous carbon electrodes of naphthylamines of-Au doping |
| CN103199267A (en) * | 2013-03-04 | 2013-07-10 | 北京师范大学 | Preparation technology of nano-Fe3O4-V2O5-Au-doped poly-naphthylamine film modified netted glassy carbon electrode |
| CN103230782A (en) * | 2013-04-09 | 2013-08-07 | 甘肃农业大学 | Graphene-doped polyaniline adsorption material preparation and application |
| CN104629360A (en) * | 2013-11-07 | 2015-05-20 | 中国科学院宁波材料技术与工程研究所 | Conductive polymer-graphene nanocomposite material, and preparation method and use thereof |
| CN103980703A (en) * | 2014-06-04 | 2014-08-13 | 福州大学 | Flocculent-polyaniline-coated graphene composite material and preparation method and application thereof |
| CN104031433A (en) * | 2014-06-09 | 2014-09-10 | 大连理工大学 | Low-conductivity flake graphene composite material, and preparation method and application thereof |
| CN104031433B (en) * | 2014-06-09 | 2016-03-09 | 大连理工大学 | Low conduction crystalline flake graphite alkene matrix material, its preparation method and application thereof |
| CN104231264A (en) * | 2014-06-19 | 2014-12-24 | 杭州师范大学 | Preparation method and application of graphene oxide/silicon dioxide/polyaniline composite material |
| CN104072764B (en) * | 2014-07-08 | 2016-08-24 | 南京邮电大学 | A kind of preparation method of polyaniline-graphite alkene composite |
| CN104072764A (en) * | 2014-07-08 | 2014-10-01 | 南京邮电大学 | Preparation method of polyaniline-graphene composite material |
| CN104592857A (en) * | 2014-12-30 | 2015-05-06 | 安科智慧城市技术（中国）有限公司 | Graphene modified polyaniline conductive coating and preparation method thereof |
| CN105807451A (en) * | 2014-12-30 | 2016-07-27 | 北京生美鸿业科技有限公司 | Intelligent light adjusting film based on graphene/organic matter composite transparent conductive film |
| CN104727188A (en) * | 2015-02-08 | 2015-06-24 | 浙江理工大学 | Preparation method of environment-friendly conductive paper |
| CN104910378A (en) * | 2015-05-26 | 2015-09-16 | 浙江理工大学 | Preparation method for polyaniline/graphene oxide nanocomposite |
| CN104910378B (en) * | 2015-05-26 | 2017-06-06 | 浙江理工大学 | A kind of polyaniline/graphene oxide nano composite material preparation method |
| CN105199134A (en) * | 2015-10-12 | 2015-12-30 | 湖北工业大学 | Polyaniline-modified graphene conductive composite film and preparation method thereof |
| CN105136889A (en) * | 2015-10-15 | 2015-12-09 | 田野 | Graphene glucose sensor |
| CN105136889B (en) * | 2015-10-15 | 2018-10-23 | 李友洪 | A kind of graphene glucose sensor |
| CN105694031A (en) * | 2015-12-27 | 2016-06-22 | 南京新月材料科技有限公司 | Preparation method of graphene-polyaniline composite material |
| CN106674517A (en) * | 2016-12-22 | 2017-05-17 | 陕西科技大学 | Polyaniline surface modified titanium carbide composite material and low-temperature preparation method thereof |
| CN106633050A (en) * | 2016-12-22 | 2017-05-10 | 陕西科技大学 | Rodlike polyaniline load modified titanium carbide and low-temperature preparation method thereof |
| CN106633051A (en) * | 2016-12-22 | 2017-05-10 | 陕西科技大学 | Titanium carbide/polyaniline composite material and preparation method thereof |
| CN106633050B (en) * | 2016-12-22 | 2019-04-16 | 陕西科技大学 | A kind of modified titanium carbide of rodlike Polyaniline-Supported and its low temperature preparation method |
| CN106633051B (en) * | 2016-12-22 | 2019-04-16 | 陕西科技大学 | A kind of titanium carbide/polyaniline composite material and preparation method thereof |
| CN106674517B (en) * | 2016-12-22 | 2019-04-19 | 陕西科技大学 | Polyaniline surface modification carbonization titanium composite material and its low temperature preparation method |
| CN108587446A (en) * | 2018-03-26 | 2018-09-28 | 合肥萃励新材料科技有限公司 | A kind of production method of polyaniline appendix graphite ene coatings |
| CN108659218A (en) * | 2018-05-22 | 2018-10-16 | 温州市赢创新材料技术有限公司 | A kind of intercalated graphite alkene denatured conductive polyaniline and preparation method thereof |
| CN108753045A (en) * | 2018-06-11 | 2018-11-06 | 江苏海田电子材料有限公司 | A kind of electrically conductive ink |
| CN110551393A (en) * | 2019-08-30 | 2019-12-10 | 武汉工程大学 | preparation method of conductive polymer/graphene oxide composite material |
| CN112471798A (en) * | 2020-11-27 | 2021-03-12 | 安徽银禾木业有限公司 | Environment-friendly solid wood board and processing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101781459B (en) | 2012-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101781459B (en) | Graphene/polyaniline conductive composite material and preparation method thereof | |
| CN101781458B (en) | Graphene -organic acid doped polyaniline composite material and preparation method thereof | |
| CN104910378B (en) | A kind of polyaniline/graphene oxide nano composite material preparation method | |
| Zhuang et al. | Facile growth of hierarchical SnO2@ PPy composites on carbon cloth as all-solid-state flexible supercapacitors | |
| CN101235199B (en) | Method for preparing carbon nano-tube modified polyaniline nano fiber composite material | |
| Zhang et al. | Influence of metallic oxide on the morphology and enhanced supercapacitive performance of NiMoO4 electrode material | |
| Lai et al. | Flexible hybrid membranes of NiCo2O4-doped carbon nanofiber@ MnO2 core–sheath nanostructures for high-performance supercapacitors | |
| CN105118688B (en) | A kind of preparation method and applications of bacteria cellulose/activated carbon fiber/graphene film material | |
| Tan et al. | Preparation and electrochemical properties of the ternary nanocomposite of polyaniline/activated carbon/TiO2 nanowires for supercapacitors | |
| CN102408712B (en) | Polyaniline nanofiber/manganese dioxide nanorod composite material and preparation method thereof | |
| CN101492569B (en) | Oxidized graphite flake layer/polyaniline composite material and method for preparing the same | |
| CN102832050B (en) | Method for preparing graphene/carbon nanotube hybrid in hierarchical structure | |
| CN106024410B (en) | A kind of graphene-based electrode material for super capacitor of high power capacity and preparation method thereof | |
| CN107256956A (en) | A kind of nitrogen-doped carbon cladding vanadium nitride electrode material and preparation method and application | |
| CN107959006A (en) | A kind of lignin-base hard carbon/carbon nano tube compound material and preparation method thereof and the application in lithium ion battery negative material | |
| CN103113625B (en) | Cyano-containing cellulose derivative and graphene composite material and preparation method thereof | |
| CN105140042B (en) | A kind of preparation method and applications of bacteria cellulose/activated carbon fiber/CNT membrane material | |
| CN102610331A (en) | Preparation method of electrode material of silver/graphene thin film supercapacitor | |
| CN106276848A (en) | A kind of with lignin for raw material nitrogen-doped carbon ball and preparation method and application | |
| CN111883366A (en) | Polypyrrole nanosphere @ titanium carbide composite material and preparation method and application thereof | |
| CN104403275A (en) | Modified grapheme/thermosetting resin composite material and preparation method thereof | |
| CN102760869A (en) | Graphene oxide/polythiophene derivative composite material as well as preparation method and application thereof | |
| CN102631915A (en) | Fuel-cell catalyst with intermediate-phase carbon microspheres load Pt (platinum) and preparation method and application of fuel-cell catalyst | |
| CN103887080B (en) | Nanocomposite material of nitrogen doped with graphene/copper ferrite and preparation method thereof | |
| Zhou et al. | Flexible naphthalene-based polyimide nanofiber cathode with hierarchical micro/nanoporous structure for high-performance organic sodium-ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |