CN102815043A - Preparation method of grapheme and polyaniline composite paper, and products thereof - Google Patents
Preparation method of grapheme and polyaniline composite paper, and products thereof Download PDFInfo
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- CN102815043A CN102815043A CN2012102744553A CN201210274455A CN102815043A CN 102815043 A CN102815043 A CN 102815043A CN 2012102744553 A CN2012102744553 A CN 2012102744553A CN 201210274455 A CN201210274455 A CN 201210274455A CN 102815043 A CN102815043 A CN 102815043A
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Abstract
The invention relates to a preparation method of grapheme/polyaniline composite paper, and products thereof. More specifically, the invention provides a preparation method of grapheme/polyaniline composite paper, comprising the following steps: providing dispersion liquid of grapheme oxide; mixing dispersion liquid of grapheme oxide with reducing agents to obtain slurry, then coating a substrate with slurry, and drying to obtain grapheme paper; and depositing polyaniline on grapheme paper to obtain grapheme/polyaniline composite paper. The preparation method provided by the invention has the advantages that flexible grapheme paper with high conductivity and mechanical property can be prepared on a large scale by using simple operations, and therefore, grapheme/polyaniline composite paper prepared by using grapheme as the substrate has good application prospect in the field of electrode materials of super capacitor.
Description
Technical field
The present invention relates to technical field of nano material, relate more specifically to preparation method of graphene/polyaniline extrusion coating paper and products thereof.
Background technology
Ultracapacitor has attracted increasing research interest as a kind of electrochemical energy memory device.Graphene is to have sp
2The monoatomic layer structure that carbon atom is lined up with the hexagoinal lattice form is because excellent properties such as its high electron conduction, high mechanical properties and bigger serface make it become novel and competitive electroactive electrode material.And polyaniline is a kind of conducting polymer that is widely used as the fake capacitance material, and it has cheapness, be easy to synthesize, the advantage of ambient stable and big ratio capacitance.Yet, when discharging and recharging, in ion insertion and dispose procedure, the swelling of polyaniline and the skeleton that shrinks meeting destruction polymer, this has just greatly damaged its charge and discharge circulation life.Therefore, fully combining the advantage performance of Graphene and polyaniline, is the thinking that scientific meaning and application prospect are arranged very much for constructing a kind of super capacitor material that had not only had big energy density but also had a high power density.
From the domestic and international research tendency of graphene/polyaniline composite, the most studies achievement concentrates on the preparation of Powdered composite.In the manufacturing process of electrode, for powder adherence on conductive substrates, the use of adhesives such as thiophene has increased energy consumption greatly.Therefore, the graphene/polyaniline macroscopic view thin-film material of preparation self-supporting or paper material are not only convenient to be used, and can also overcome the shortcoming that dusty material causes.At present; " U.S.'s nanometer " (ACS Nano; 1963 pages of 2010 4 phases) method with vacuum filtration Graphene and polyaniline mixed dispersion liquid of having reported makes the graphene/polyaniline extrusion coating paper, but owing to lack real interaction between these two kinds of components, makes that the capacitance of electrode material is on the low side." U.S.'s nanometer " (ACS Nano; 1745 pages of 2009 3 phases) another work of report about preparation graphene/polyaniline extrusion coating paper; Be that method with vacuum filtration prepares Graphene paper; Electroplate with the method for electrochemical polymerization above that then and go up polyaniline, but, cause the capacitive property of material not high because the Graphene paper electric conductivity that makes with vacuum filtration is general.In order to improve the actual application prospect of this type of material, be badly in need of a kind of cheapness of development, technological means prepares the graphene/polyaniline extrusion coating paper that possesses the high capacitance performance a large amount of the time easily as electrode material.
Summary of the invention
The present invention mainly is the preparation method that a kind of graphene/polyaniline extrusion coating paper is provided to present limited technology.
For this reason, the present invention provides a kind of preparation method of graphene/polyaniline extrusion coating paper, it is characterized in that, may further comprise the steps:
A., the graphene oxide dispersion liquid is provided;
B. said graphene oxide dispersion liquid is mixed with reducing agent to obtain slurry, then said slurry is coated on the substrate, then dry to obtain Graphene paper; With
C. through being deposited on, polyaniline obtains said graphene/polyaniline extrusion coating paper on the said Graphene paper.
In a preferred implementation, said graphene oxide dispersion liquid provides through following steps:
A1. the mixture of Graphene scale and nitrate such as sodium nitrate or potassium nitrate is joined in strong acid such as the concentrated sulfuric acid, the red fuming nitric acid (RFNA) and carry out pre-oxidation, stir and obtain dispersion liquid;
A2. in the said dispersion liquid of a1, add strong oxidizer such as potassium permanganate, stir, placed 1-10 days, obtain the taupe pastel;
A3. in the said taupe pastel of a2, add deionized water and hydrogen peroxide solution successively, obtain the glassy yellow dispersion liquid;
A4. the said glassy yellow dispersion liquid of a3 is centrifugal, the washing and the dialysis, obtain said graphene oxide dispersion liquid.
In a preferred implementation, the reducing agent among the said step b is hydroiodic acid, hydrazine hydrate or sodium borohydride.
In a preferred implementation, use hydriodic acid aqueous solution as reducing agent among the said step b, and the volume ratio of said graphene oxide dispersion liquid and said hydriodic acid aqueous solution is (10～5): 1.
In a preferred implementation, the substrate among the said step b is Teflon (or polytetrafluoroethylene (PTFE)).
In a preferred implementation, the bake out temperature among the said step b is 60～90 ℃.
In a preferred implementation, the drying time among the said step b is 1～8 hour.
In a preferred implementation, in said step b, also comprise the Graphene paper on the dried substrate is cleaned and dries with water and alcohol (like ethanol) successively, thereby obtain complete Graphene paper from said substrate.
In a preferred implementation, among the said step c, through the electrochemical polymerization aniline monomer with the polyaniline electroplating deposition on said Graphene paper, thereby form said graphene/polyaniline extrusion coating paper.
In a preferred implementation, said electroplating deposition is realized through following steps:
C1. in water and alcohol mixed solvent, prepare the sulfuric acid solution of 1 mol;
C2. aniline monomer is joined in the mixed solution of step c1 acquisition; With
C3. carrying out electrochemical polymerization with three-electrode method, is working electrode with said Graphene paper wherein, is to electrode with platinum electrode, is reference electrode with silver/silver chlorate, and the mixed solution that obtains with step c2 is an electrolyte.
In a preferred implementation, the water in said water and the alcohol mixed solvent and the volume ratio of ethanol are (1-10): 1.
In a preferred implementation, working concentration is the aniline solution of 0.05～0.5 mol.
In a preferred implementation, the operating voltage in the said electrochemical polymerization process is 0.8 volt.
In a preferred implementation, the time of said electrochemical polymerization is 2～30 minutes.
In addition, the invention provides a kind of graphene/polyaniline extrusion coating paper that obtains through above-mentioned preparation method.
Method step provided by the invention is simple, operates simple and easyly, has economy, characteristics fast, the advantage that the graphene/polyaniline extrusion coating paper of preparation possesses electric conductivity height, good mechanical property and is easy to process.
Description of drawings
Fig. 1 is the electron scanning micrograph according to the graphene/polyaniline extrusion coating paper of the embodiment of the invention 1 preparation;
Fig. 2 is the electron scanning micrograph according to the graphene/polyaniline extrusion coating paper of the embodiment of the invention 2 preparations;
Fig. 3 is the electron scanning micrograph according to the graphene/polyaniline extrusion coating paper of the embodiment of the invention 3 preparations;
Fig. 4 is the electron scanning micrograph according to the graphene/polyaniline extrusion coating paper of the embodiment of the invention 4 preparations; With
Fig. 5 is for discharging and recharging the measurement curve according to the graphene/polyaniline extrusion coating paper of the embodiment of the invention 1 preparation.
The specific embodiment
The present invention provides a kind of preparation method of graphene/polyaniline extrusion coating paper; Concrete steps: the dispersion liquid that a kind of graphene oxide at first is provided; For example hydroiodic acid, hydrazine hydrate or sodium borohydride mixed slurry for example are layered on the Teflon substrate with this graphene oxide dispersion liquid and reducing agent then; Tearing after the oven dry obtains Graphene paper, last for example on this Graphene paper, deposit polyaniline and obtains the graphene/polyaniline extrusion coating paper with the method for electrochemical polymerization.
More preferably, the preparation method of a kind of graphene/polyaniline extrusion coating paper of the present invention may further comprise the steps:
A., a kind of graphene oxide dispersion liquid is provided;
B. with graphene oxide and reducing agent for example the hydroiodic acid mixed slurry for example be layered on equably on the Teflon substrate, place drying plant such as baking oven, take out the oven dry back;
Alternatively, Graphene paper on substrate after oven dry water successively and alcohol (like ethanol) are repeatedly cleaned, and for example dry, with the Graphene paper of tearing complete from substrate in room temperature;
C. the method for using for example electrochemical polymerization with the aniline monomer polymerization and electroplating deposition on above-mentioned Graphene paper, obtain the graphene/polyaniline extrusion coating paper.
Preferably, comprise step among the above-mentioned steps a:
A1. with Graphene scale and nitrate for example the mixture of sodium nitrate or potassium nitrate join strong acid and for example carry out pre-oxidation in the concentrated sulfuric acid or the red fuming nitric acid (RFNA), stir;
A2. in the dispersion liquid of a1, slowly add for example potassium permanganate of strong oxidizer, stir, placed 1-10 days;
A3. in the mixture that a2 obtains, add deionized water and hydrogen peroxide solution successively;
A4. obtain the graphene oxide dispersion liquid after many centrifuge washings, the dialysis.
Preferably, use hydriodic acid aqueous solution as reducing agent among the above-mentioned steps b, and the volume ratio of graphene oxide dispersion liquid and hydriodic acid aqueous solution is (10～5): 1.
Preferably, the bake out temperature among the above-mentioned steps b is 60～90 ℃.
Preferably, the drying time among the above-mentioned steps b is 1～8 hour.
In the optional step of above-mentioned steps b, the size and dimension of the Graphene paper that makes changes along with the change of Teflon substrate.
Preferably, comprise step among the above-mentioned steps c:
C1. in water and alcohol mixed solvent, prepare the sulfuric acid solution of 0.5-2 mol;
C2. aniline monomer is joined in the mixed solution of above-mentioned c1;
C3. carrying out electrochemical polymerization with three-electrode method, is working electrode with Graphene paper wherein, and platinum electrode is to electrode, and silver/silver chlorate is a reference electrode, and is electrolyte with above-mentioned c2 solution, preparation graphene/polyaniline extrusion coating paper.
Preferably, the volume ratio of water and ethanol is (1-10) among the above-mentioned steps c1: 1.
Preferably, working concentration is the aniline monomer solution of 0.05～0.5 mol among the above-mentioned steps c2.
Preferably, the operating voltage of electrochemical polymerization is 0.8 volt among the above-mentioned steps c3.
Preferably, the time of electrochemical polymerization is 2～30 minutes among the above-mentioned steps c3.
The invention has the advantages that and utilize simple operations; One goes on foot, prepares in large quantities the Graphene paper of the softness with high conduction performance and mechanical performance, is that the graphene/polyaniline extrusion coating paper that substrate makes has a good application prospect in the electrode material for super capacitor field with this Graphene paper.
Below in conjunction with embodiment, specific embodiments of the invention is done and is described in further detail.Following examples are in order to further specify the present invention, but are not used for limiting scope of the present invention.
Embodiment 1
(1) preparation of graphene oxide dispersion liquid: under continuous condition of stirring, with 5 gram graphite scales and 3.75 gram NaNO
3Join in 150 milliliters of concentrated sulfuric acids (98%), reactant mixes the back and in ice bath, cools off; After stirring half an hour, with 20 gram KMnO
4In half an hour, join in the above-mentioned dispersion; Remove ice bath then, the temperature of suspension will be gone up to about 35 ℃, continue to stir after 20 hours to become the taupe pastel; Afterwards, stop to stir, place after 5 days, slowly add 500 ml deionized water and 30 milliliters of H successively while stirring
2O
2, generate glassy yellow suspension; This suspension is centrifugal, remove supernatant, keep lower sediment, then deposition is added aqueous dispersion, this process triplicate, flush away kish ion; Then, the deposition that obtains is added aqueous dispersion, centrifugal, collect upper strata centrifugate, it is centrifugal that lower sediment is continued to add aqueous dispersion, collects upper strata centrifugate, and so repeatedly, centrifugate is limpid until the upper strata, discarded lower sediment.The upper strata centrifugate of collecting is merged, use molecular weight to dialyse as the bag filter of 8000-14000 then, the product of gained has been carried out the Raman spectrum sign, it is positioned at 1350cm
-1The intensity of D band characteristic peak be positioned at 1590cm less than it
-1The G band characteristic peak at place, the result shows and has obtained the even dispersion liquid of graphene oxide.Obtained the even dispersion liquid of graphene oxide.
(2) with the graphene oxide dispersion liquid of 5 mg/ml with after hydroiodic acid evenly mixes with 10: 1 volume ratio, the slurry that obtains is layered on the Teflon substrate, puts into 90 ℃ of baking ovens reactions after 2 hours, takes out, room temperature is cooled off.
(3) add ethanol to the substrate that is covered with Graphene paper, after repeatedly cleaning, drying, from the substrate Graphene paper of tearing, it is subsequent use that it is cut into small pieces.
(4) preparation of graphene/polyaniline extrusion coating paper: be the sulfuric acid solution of configuration 1 mol in 1: 1 water and the alcohol mixed solvent with volume ratio, to wherein adding aniline, obtain the aniline solution of 0.1 mol then; With this solution is electrolyte; Graphene paper with above-mentioned preparation is working electrode, is to electrode with platinum electrode, is reference electrode with silver/silver chloride electrode; Under 0.8 volt constant voltage; Electrochemical polymerization 10 minutes, and carried out the Raman spectrum sign to obtaining soft extrusion coating paper has occurred being positioned at 515,529,819 and 1153cm on spectrogram
-1The characteristic peak that corresponds to azophenlyene, the hydrocarbon vibration of quinoid, the hydrocarbon flexural vibrations of quinoid and the hydrocarbon vibration of phenyl ring at place is positioned at 1326,1583 and 1619cm
-1Correspond to that semiquinone group vibration, quinoid carbon carbon are two builds vibration and carbon-carbon single bond vibration, and be positioned at 1481-1509cm
-1Two vibration and the 1259cm of building of quinoid carbon nitrogen
-1The polarize carbon nitrogen singly-bound vibration at place, these results show that resulting product is the graphene/polyaniline extrusion coating paper.Fig. 1 is according to the electron scanning micrograph of the graphene/polyaniline extrusion coating paper of present embodiment preparation, finds out that from stereoscan photograph shown in Figure 1 uniform polyaniline nano-rod length is on Graphene paper.
Embodiment 2
Repeat embodiment 1, following difference is arranged: on Graphene paper, during the electrochemical polymerization polyaniline, contain the aniline monomer of 0.05 mol in the electrolyte.Fig. 2 is the stereoscan photograph of present embodiment 2 resulting graphene/polyaniline extrusion coating papers, and as can beappreciated from fig. 2, the polyaniline particle length of a thin layer is on Graphene paper.The stereoscan photograph (see figure 1) of showing with embodiment 1 prepared composite paper compares visible, and the microstructure of extrusion coating paper is relevant with the concentration of aniline.
Embodiment 3
Repeat embodiment 1; Following difference is arranged: on Graphene paper during the electrochemical polymerization polyaniline; The electrochemical polymerization time is 5 minutes, and Fig. 3 is the stereoscan photograph of present embodiment 3 resulting graphene/polyaniline extrusion coating papers, and its result and embodiment 1 are similar; But because polymerization time is short slightly, so the polyaniline nano-rod of growth is less.
Embodiment 4
Repeat embodiment 1, following difference is arranged: during the electrochemical polymerization polyaniline, the electrochemical polymerization time is 20 minutes on Graphene paper.Fig. 4 is the stereoscan photograph of present embodiment 4 resulting graphene/polyaniline extrusion coating papers; Can find out by Fig. 4; Increase along with the electrochemical polymerization time; It is more that polyaniline nano-rod is looked intensive, and along with the density of the growth of polyaniline nano-rod increases, the color of the graphene/polyaniline extrusion coating paper of acquisition also has corresponding variation.
Embodiment 5
Repeat embodiment 1, following difference is arranged: in the preparation process of graphene/polyaniline extrusion coating paper, be to dispose the sulfuric acid solution of 1 mol in 5: 1 water and the alcohol mixed solvent with volume ratio.The result is similar to embodiment 1.
Embodiment 6
Repeat embodiment 1, following difference is arranged: in the preparation process of graphene/polyaniline extrusion coating paper, be to dispose the sulfuric acid solution of 0.5 mol in 10: 1 water and the alcohol mixed solvent with volume ratio.The result is similar to embodiment 1.
Embodiment 7
Repeat embodiment 1, following difference is arranged: with after hydroiodic acid evenly mixes with 5: 1 volume ratio, the slurry that obtains is layered on the Teflon substrate, puts into 90 ℃ of baking ovens reactions after 2 hours with the graphene oxide dispersion liquid of 5 mg/ml, taking-up, and room temperature is cooled off.The result is similar to embodiment 1.
Embodiment 8
Repeat embodiment 1, following difference is arranged: with after hydroiodic acid evenly mixes with 10: 1 volume ratio, the slurry that obtains is layered on the Teflon substrate, puts into 60 ℃ of baking ovens reactions after 5 hours with the graphene oxide dispersion liquid of 5 mg/ml, taking-up, and room temperature is cooled off.The result is similar to embodiment 1.
Embodiment 9
Repeat embodiment 1, following difference is arranged: with after hydrazine hydrate evenly mixes with 10: 1 volume ratio, the slurry that obtains is layered on the Teflon substrate, puts into 90 ℃ of baking ovens reactions after 2 hours with the graphene oxide dispersion liquid of 5 mg/ml, taking-up, and room temperature is cooled off.The result is similar to embodiment 1.
Embodiment 10
Repeat embodiment 1; Following difference is arranged: with after the sodium borohydride solution of 1 mol evenly mixes with 10: 1 volume ratio, the slurry that obtains is layered on the Teflon substrate, puts into 90 ℃ of baking ovens and reacts after 2 hours with the graphene oxide dispersion liquid of 5 mg/ml; Take out the room temperature cooling.The result is similar to embodiment 1.
In addition; Preparation method's prepared graphene/polyaniline extrusion coating paper to through graphene/polyaniline extrusion coating paper of the present invention is measured as the performance of the electrode material of ultracapacitor; The result is referring to shown in Figure 5 discharging and recharging (time-voltage) curve, and as can beappreciated from fig. 5, its capacitance can reach 753F/g; Therefore, the graphene/polyaniline extrusion coating paper of the present invention's preparation has excellent electric performance.
Should be understood that; The above only is a preferred implementation of the present invention, to those skilled in the art, and under the prerequisite that does not break away from know-why of the present invention and scope; Can realize multiple change or conversion, and these modifications should be regarded as in protection scope of the present invention also to these embodiment.
Claims (15)
1. the preparation method of a graphene/polyaniline extrusion coating paper is characterized in that, may further comprise the steps:
A., the graphene oxide dispersion liquid is provided;
B. said graphene oxide dispersion liquid is mixed with reducing agent to obtain slurry, then said slurry is coated on the substrate, then dry to obtain Graphene paper; With
C. through being deposited on, polyaniline obtains said graphene/polyaniline extrusion coating paper on the said Graphene paper.
2. the preparation method of graphene/polyaniline extrusion coating paper according to claim 1 is characterized in that, said graphene oxide dispersion liquid provides through following steps:
A1. the mixture of graphite scale and nitrate is joined and carry out pre-oxidation in the strong acid, stir and obtain dispersion liquid;
A2. in the said dispersion liquid of a1, add strong oxidizer, stir, placed 1-10 days, obtain the taupe pastel;
A3. in the said taupe pastel of a2, add deionized water and hydrogen peroxide solution successively, obtain glassy yellow suspension;
A4. the said glassy yellow suspension of a3 is centrifugal, the washing and the dialysis, obtain said graphene oxide dispersion liquid.
3. the preparation method of graphene/polyaniline extrusion coating paper according to claim 1 is characterized in that, the reducing agent that uses among the said step b is hydroiodic acid, hydrazine hydrate or sodium borohydride.
4. the preparation method of graphene/polyaniline extrusion coating paper according to claim 1; It is characterized in that; Use hydriodic acid aqueous solution as reducing agent among the said step b, and the volume ratio of said graphene oxide dispersion liquid and said hydriodic acid aqueous solution is (10～5): 1.
5. the preparation method of graphene/polyaniline extrusion coating paper according to claim 1 is characterized in that, the substrate among the said step b is a Teflon.
6. the preparation method of graphene/polyaniline extrusion coating paper according to claim 1 is characterized in that, the bake out temperature among the said step b is 60～90 ℃.
7. the preparation method of graphene/polyaniline extrusion coating paper according to claim 1 is characterized in that, the drying time among the said step b is 1～8 hour.
8. the preparation method of graphene/polyaniline extrusion coating paper according to claim 1; It is characterized in that; In said step b, also comprise Graphene paper on dried substrate water successively and alcohol being cleaned and dry, thereby obtain complete Graphene paper from said substrate.
9. the preparation method of graphene/polyaniline extrusion coating paper according to claim 1; It is characterized in that; Among the said step c, through the electrochemical polymerization aniline monomer with the polyaniline electroplating deposition on said Graphene paper, thereby form said graphene/polyaniline extrusion coating paper.
10. the preparation method of graphene/polyaniline extrusion coating paper according to claim 9 is characterized in that, said electroplating deposition is realized through following steps:
C1. in water and alcohol mixed solvent, prepare the sulfuric acid solution of 0.5-2 mol;
C2. aniline monomer is joined in the mixed solution of step c1 acquisition;
C3. carrying out electrochemical polymerization with three-electrode method, is working electrode with said Graphene paper wherein, is to electrode with platinum electrode, is reference electrode with silver/silver chlorate, and the mixed solution that obtains with step c2 is an electrolyte.
11. the preparation method of graphene/polyaniline extrusion coating paper according to claim 10 is characterized in that, the water in said water and the alcohol mixed solvent and the volume ratio of ethanol are (1-10): 1.
12. the preparation method of graphene/polyaniline extrusion coating paper according to claim 10 is characterized in that, working concentration is the aniline monomer solution of 0.05～0.5 mol.
13. the preparation method of graphene/polyaniline extrusion coating paper according to claim 10 is characterized in that, the operating voltage in the said electrochemical polymerization process is 0.8 volt.
14. the preparation method of graphene/polyaniline extrusion coating paper according to claim 10 is characterized in that, the time of said electrochemical polymerization is 2～30 minutes.
15. graphene/polyaniline extrusion coating paper that obtains through each described preparation method among the claim 1-14.
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| CN104211960A (en) * | 2014-09-30 | 2014-12-17 | 中原工学院 | One-step chemical preparation method for graphene and polyaniline composite materials |
| CN104495811A (en) * | 2014-12-12 | 2015-04-08 | 盐城市新能源化学储能与动力电源研究中心 | Graphene composite material and preparation method thereof |
| CN104674294A (en) * | 2014-12-18 | 2015-06-03 | 南京航空航天大学 | Preparation method and application of graphene-polyaniline conductive composite |
| CN104674294B (en) * | 2014-12-18 | 2018-02-06 | 南京航空航天大学 | The preparation method and application of graphene-layer/polyaniline conductive compound |
| CN105199134A (en) * | 2015-10-12 | 2015-12-30 | 湖北工业大学 | Polyaniline-modified graphene conductive composite film and preparation method thereof |
| CN105735047A (en) * | 2016-02-01 | 2016-07-06 | 东南大学 | Preparation method of conductive and super-hydrophobic functional graphene paper |
| CN107221447A (en) * | 2017-07-03 | 2017-09-29 | 中国科学院宁波材料技术与工程研究所 | A kind of graphene flexible compound electrode, its preparation method and flexible super capacitor |
| CN107221447B (en) * | 2017-07-03 | 2019-02-19 | 中国科学院宁波材料技术与工程研究所 | A kind of graphene flexible compound electrode, preparation method and flexible super capacitor |
| CN110227396A (en) * | 2019-06-18 | 2019-09-13 | 同济大学 | Graphene with nearly zero dielectric constant/polyolefin elastomer method for preparing microsphere |
| CN110227396B (en) * | 2019-06-18 | 2022-04-05 | 同济大学 | Preparation method of graphene/polyolefin elastomer microspheres with near-zero dielectric constant |
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