CN102815043B - 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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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, preparation method relating more specifically to grapheme/polyaniline composite paper and products thereof.
Background technology
Ultracapacitor, as a kind of electrochemical energy storage part, has attracted increasing research interest.Graphene has sp
2the monoatomic layer structure that carbon atom is lined up with hexagoinal lattice form, due to excellent properties such as its high electron conduction, high mechanical properties and bigger serfaces, becomes novel and competitive electroactive electrode material.And polyaniline is a kind of conducting polymer being widely used as fake capacitance material, it has cheapness, be easy to synthesize, the advantage of ambient stable and large ratio capacitance value.But when discharge and recharge, in ion insertion and dispose procedure, the swelling and contraction of polyaniline can destroy the skeleton of polymer, and this just greatly compromises its charge and discharge circulation life.Therefore, fully in conjunction with the advantage performance of Graphene and polyaniline, be the thinking having very much scientific meaning and application prospect for constructing a kind of super capacitor material that not only there is large energy density but also there is high power density.
From the domestic and international research tendency of grapheme/polyaniline composite material, most achievement in research concentrates on the preparation of Powdered composite.In the manufacturing process of electrode, in order to by powder adherence in conductive substrates, the use of the adhesives such as thiophene considerably increases energy consumption.Therefore, graphene/polyaniline macroscopic film material or the paper material of preparation self-supporting are not only easy to use, can also overcome the shortcoming that dusty material causes.At present, " U.S.'s nanometer " (ACS Nano, 4 phase in 2010 1963 pages) report and obtain grapheme/polyaniline composite paper by the method for vacuum filtration Graphene and polyaniline mixed dispersion liquid, but owing to lacking real interaction between these two kinds of components, make the capacitance of electrode material on the low side." U.S.'s nanometer " (ACS Nano, 3 phase in 2009 1745 pages) another work about preparation grapheme/polyaniline composite paper of reporting, prepare graphene paper by the method for vacuum filtration, then thereon with the upper polyaniline of method plating of electrochemical polymerization, but because the graphene paper electric conductivity obtained with vacuum filtration is general, cause the capacitive property of material not high.In order to improve the actual application prospect of this type of material as electrode material, be badly in need of development a kind of cheapness, easily technological means prepare a large amount of while possess the grapheme/polyaniline composite paper of high capacitance performance.
Summary of the invention
The present invention mainly provides a kind of preparation method of grapheme/polyaniline composite paper for current limited technical.
For this reason, the invention provides a kind of preparation method of grapheme/polyaniline composite paper, it is characterized in that, comprise the following steps:
A. graphene oxide dispersion is provided;
B. described graphene oxide dispersion is mixed to obtain slurry with reducing agent, then described slurry is coated on substrate, then carry out drying to obtain graphene paper; With
C. described grapheme/polyaniline composite paper is obtained by being deposited in described graphene paper by polyaniline.
In a preferred embodiment, described graphene oxide dispersion is provided by following steps:
A1. by Graphene scale and nitrate, the mixture as sodium nitrate or potassium nitrate joins strong acid as carried out pre-oxidation in the concentrated sulfuric acid, red fuming nitric acid (RFNA), stirs and obtains dispersion liquid;
A2. in the described dispersion liquid of a1, add strong oxidizer as potassium permanganate, stir, place 1-10 days, obtain taupe pastel;
A3. in the described taupe pastel of a2, add deionized water and hydrogen peroxide successively, obtain glassy yellow dispersion liquid;
A4. by centrifugal for the described glassy yellow dispersion liquid of a3, washing and dialysis, obtain described graphene oxide dispersion.
In a preferred embodiment, the reducing agent in described step b is hydroiodic acid, hydrazine hydrate or sodium borohydride.
In a preferred embodiment, in described step b, use hydriodic acid aqueous solution as reducing agent, and the volume ratio of described graphene oxide dispersion and described hydriodic acid aqueous solution is (10 ~ 5): 1.
In a preferred embodiment, the substrate in described step b is Teflon (or polytetrafluoroethylene (PTFE)).
In a preferred embodiment, the bake out temperature in described step b is 60 ~ 90 DEG C.
In a preferred embodiment, the drying time in described step b is 1 ~ 8 hour.
In a preferred embodiment, also comprise in described step b and clean by the graphene paper on the substrate after oven dry with using water and alcohol (as ethanol) successively and dry, thus obtain complete graphene paper from described substrate.
In a preferred embodiment, in described step c, by electrochemical polymerization aniline monomer by polyaniline electroplating deposition in described graphene paper, thus form described grapheme/polyaniline composite paper.
In a preferred embodiment, described electroplating deposition is realized by following steps:
C1. in water and alcohol mixed solvent, prepare the sulfuric acid solution of 1 mol/L;
C2. aniline monomer is joined in the mixed solution of step c1 acquisition; With
C3. carry out electrochemical polymerization with three-electrode method, wherein with described graphene paper for working electrode, be to electrode with platinum electrode, with silver/silver chlorate for reference electrode, and with step c2 obtain mixed solution for electrolyte.
In a preferred embodiment, the water in described water and alcohol mixed solvent and the volume ratio of ethanol are (1-10): 1.
In a preferred embodiment, working concentration is the aniline solution of 0.05 ~ 0.5 mol/L.
In a preferred embodiment, the operating voltage in described electrochemical polymerization process is 0.8 volt.
In a preferred embodiment, the time of described electrochemical polymerization is 2 ~ 30 minutes.
In addition, the invention provides a kind of grapheme/polyaniline composite paper obtained by above-mentioned preparation method.
Method step provided by the invention is simple, operates simple and easy, has economy, fast feature, the advantage that the grapheme/polyaniline composite paper of preparation possesses that electric conductivity is high, good mechanical property and being easy to is processed.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph of the grapheme/polyaniline composite paper according to the embodiment of the present invention 1 preparation;
Fig. 2 is the electron scanning micrograph of the grapheme/polyaniline composite paper according to the embodiment of the present invention 2 preparation;
Fig. 3 is the electron scanning micrograph of the grapheme/polyaniline composite paper according to the embodiment of the present invention 3 preparation;
Fig. 4 is the electron scanning micrograph of the grapheme/polyaniline composite paper according to the embodiment of the present invention 4 preparation; With
Fig. 5 is the discharge and recharge experiment curv of the grapheme/polyaniline composite paper according to the embodiment of the present invention 1 preparation.
Detailed description of the invention
The invention provides a kind of preparation method of grapheme/polyaniline composite paper, concrete steps: the dispersion liquid that first a kind of graphene oxide is provided, then this graphene oxide dispersion and reducing agent such as hydroiodic acid, hydrazine hydrate or sodium borohydride mixed slurry are layered on such as Teflon substrate, tear after oven dry and obtain graphene paper, finally such as in this graphene paper, deposit polyaniline by the method for electrochemical polymerization and obtain grapheme/polyaniline composite paper.
More preferably, the preparation method of a kind of grapheme/polyaniline composite paper of the present invention, comprises the following steps:
A., a kind of graphene oxide dispersion is provided;
B. graphene oxide and reducing agent such as hydroiodic acid mixed slurry are layered on such as Teflon substrate equably, are placed in drying plant as baking oven, take out after drying;
Alternatively, use water and alcohol (as ethanol) repeatedly to clean successively the graphene paper on substrate after drying, and such as dry in room temperature, with complete graphene paper of tearing from substrate;
C. electroplating deposition, in above-mentioned graphene paper, obtains grapheme/polyaniline composite paper by aniline monomer polymerization to use the method for such as electrochemical polymerization.
Preferably, above-mentioned steps a comprises step:
A1. the mixture of Graphene scale and nitrate such as sodium nitrate or potassium nitrate is joined in the strong acid such as concentrated sulfuric acid or red fuming nitric acid (RFNA) and carry out pre-oxidation, stir;
A2. in the dispersion liquid of a1, slowly add strong oxidizer such as potassium permanganate, stir, place 1-10 days;
A3. in the mixture of a2 acquisition, deionized water and hydrogen peroxide is added successively;
A4. graphene oxide dispersion is obtained after many centrifuge washings, dialysis.
Preferably, in above-mentioned steps b, use hydriodic acid aqueous solution as reducing agent, and the volume ratio of graphene oxide dispersion and hydriodic acid aqueous solution is (10 ~ 5): 1.
Preferably, the bake out temperature in above-mentioned steps b is 60 ~ 90 DEG C.
Preferably, the drying time in above-mentioned steps b is 1 ~ 8 hour.
In the optional step of above-mentioned steps b, the size and dimension of obtained graphene paper changes along with the change of Teflon substrate.
Preferably, above-mentioned steps c comprises step:
C1. in water and alcohol mixed solvent, prepare the sulfuric acid solution of 0.5-2 mol/L;
C2. aniline monomer is joined in the mixed solution of above-mentioned c1;
C3. carry out electrochemical polymerization with three-electrode method, be wherein working electrode with graphene paper, platinum electrode is to electrode, and silver/silver chlorate is reference electrode, and with above-mentioned c2 solution for electrolyte, preparation grapheme/polyaniline composite paper.
Preferably, in above-mentioned steps c1, the volume ratio of water and ethanol is (1-10): 1.
Preferably, in above-mentioned steps c2, working concentration is the aniline monomer solution of 0.05 ~ 0.5 mol/L.
Preferably, the operating voltage of electrochemical polymerization in above-mentioned steps c3 is 0.8 volt.
Preferably, the time of electrochemical polymerization in above-mentioned steps c3 is 2 ~ 30 minutes.
The invention has the advantages that and utilize simple operations, one step, prepare the graphene paper of the softness with high conduction performance and mechanical performance in large quantities, with this graphene paper for the grapheme/polyaniline composite paper that substrate is obtained has a good application prospect in electrode material for super capacitor field.
Below in conjunction with embodiment, the specific embodiment of the present invention is described in further detail.Following examples are to further illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
(1) preparation of graphene oxide dispersion: when constantly stirring, by 5 grams of graphite flakes and 3.75 grams of NaNO
3join in 150 milliliters of concentrated sulfuric acids (98%), cool in ice bath after reactant mixing; After stirring half an hour, by 20 grams of KMnO
4join in above-mentioned dispersion within half an hour; Then remove ice bath, the temperature of suspension will be gone up to about 35 DEG C, continue stirring and become taupe pastel after 20 hours; Afterwards, stop stirring, place after 5 days, slowly add 500 ml deionized water and 30 milliliters of H while stirring successively
2o
2, generate glassy yellow suspension; By centrifugal for this suspension, remove supernatant, retain lower sediment, then precipitation is added aqueous dispersion, this process in triplicate, washes away remaining metal ions; Then, the precipitation of acquisition is added aqueous dispersion, centrifugal, collect upper strata centrifugate, lower sediment is continued to add aqueous dispersion centrifugal, collect upper strata centrifugate, so repeatedly, until upper strata centrifugate is limpid, discarded lower sediment.The upper strata centrifugate of collecting merged, then dialyse with the bag filter that molecular weight is 8000-14000, carried out Raman Characterization to the product of gained, it is positioned at 1350cm
-1d be with the intensity of characteristic peak to be less than it to be positioned at 1590cm
-1the G at place is with characteristic peak, and result shows to obtain graphene oxide uniform dispersion.Obtain graphene oxide uniform dispersion.
(2) by the graphene oxide dispersion of 5 mg/ml and hydroiodic acid with after the volume ratio Homogeneous phase mixing of 10: 1, the slurry obtained is layered on Teflon substrate, and put into after 90 DEG C of baking ovens react 2 hours, take out, room temperature cools.
(3) ethanol is added to the substrate being covered with graphene paper, repeatedly after cleaning, dry, to tear graphene paper from substrate, be cut into small pieces for subsequent use.
(4) preparation of grapheme/polyaniline composite paper: with volume ratio be 1: 1 water and alcohol mixed solvent in configure the sulfuric acid solution of 1 mol/L, then aniline is added wherein, obtain the aniline solution of 0.1 mol/L, with this solution for electrolyte, with the graphene paper of above-mentioned preparation for working electrode, be to electrode with platinum electrode, with silver/silver chloride electrode for reference electrode, under the constant voltage of 0.8 volt, electrochemical polymerization 10 minutes, and carried out Raman Characterization to obtaining soft extrusion coating paper, spectrogram occurs be positioned at 515,529,819 and 1153cm
-1the characteristic peak corresponding 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 the vibration of semiquinone group, quinoid carbon carbon is two builds vibration and carbon-carbon single bond vibration, and is positioned at 1481-1509cm
-1quinoid carbon nitrogen two build vibration and 1259cm
-1the polarize carbon nitrogen singly-bound vibration at place, these results show that obtained product is grapheme/polyaniline composite paper.Fig. 1 is the electron scanning micrograph of the grapheme/polyaniline composite paper prepared according to the present embodiment, finds out that uniform polyaniline nano-rod length is on graphene paper from stereoscan photograph shown in Fig. 1.
Embodiment 2
Repeat embodiment 1, have following difference: in graphene paper during electrochemical polymerization polyaniline, the aniline monomer containing 0.05 mol/L in electrolyte.The stereoscan photograph of the grapheme/polyaniline composite paper that Fig. 2 obtains for the present embodiment 2, as can be seen from Figure 2, the polyaniline particles length of a thin layer is in graphene paper.The stereoscan photograph (see Fig. 1) shown with the extrusion coating paper prepared by embodiment 1 compares visible, and the microstructure of extrusion coating paper is relevant with the concentration of aniline.
Embodiment 3
Repeat embodiment 1, there is following difference: in graphene paper during electrochemical polymerization polyaniline, the electrochemical polymerization time is 5 minutes, the stereoscan photograph of the grapheme/polyaniline composite paper that Fig. 3 obtains for the present embodiment 3, its result is similar to Example 1, but because polymerization time is slightly short, so the polyaniline nano-rod of growth is less.
Embodiment 4
Repeat embodiment 1, have following difference: in graphene paper during electrochemical polymerization polyaniline, the electrochemical polymerization time is 20 minutes.The stereoscan photograph of the grapheme/polyaniline composite paper that Fig. 4 obtains for the present embodiment 4, as seen from Figure 4, along with the increase of electrochemical polymerization time, polyaniline nano-rod looks more intensive, and along with the density of the growth of polyaniline nano-rod increases, the color of the grapheme/polyaniline composite paper of acquisition also has corresponding change.
Embodiment 5
Repeat embodiment 1, have following difference: in the preparation process of grapheme/polyaniline composite paper with volume ratio be 5: 1 water and alcohol mixed solvent in configure the sulfuric acid solution of 1 mol/L.Result is similar to embodiment 1.
Embodiment 6
Repeat embodiment 1, have following difference: in the preparation process of grapheme/polyaniline composite paper with volume ratio be 10: 1 water and alcohol mixed solvent in configure the sulfuric acid solution of 0.5 mol/L.Result is similar to embodiment 1.
Embodiment 7
Repeat embodiment 1, have following difference: by the graphene oxide dispersion of 5 mg/ml and hydroiodic acid with after the volume ratio Homogeneous phase mixing of 5: 1, the slurry obtained is layered on Teflon substrate, put into after 90 DEG C of baking ovens react 2 hours, take out, room temperature cooling.Result is similar to embodiment 1.
Embodiment 8
Repeat embodiment 1, have following difference: by the graphene oxide dispersion of 5 mg/ml and hydroiodic acid with after the volume ratio Homogeneous phase mixing of 10: 1, the slurry obtained is layered on Teflon substrate, put into after 60 DEG C of baking ovens react 5 hours, take out, room temperature cooling.Result is similar to embodiment 1.
Embodiment 9
Repeat embodiment 1, have following difference: by the graphene oxide dispersion of 5 mg/ml and hydrazine hydrate with after the volume ratio Homogeneous phase mixing of 10: 1, the slurry obtained is layered on Teflon substrate, put into after 90 DEG C of baking ovens react 2 hours, take out, room temperature cooling.Result is similar to embodiment 1.
Embodiment 10
Repeat embodiment 1, there is following difference: by the sodium borohydride solution of the graphene oxide dispersion of 5 mg/ml and 1 mol/L with after the volume ratio Homogeneous phase mixing of 10: 1, the slurry obtained is layered on Teflon substrate, put into after 90 DEG C of baking ovens react 2 hours, take out, room temperature cools.Result is similar to embodiment 1.
In addition, grapheme/polyaniline composite paper prepared by preparation method by grapheme/polyaniline composite paper of the present invention is measured as the performance of the electrode material of ultracapacitor, result discharge and recharge shown in Figure 5 (time m-voltage) curve, as can be seen from Figure 5, its capacitance can reach 753F/g, therefore, the grapheme/polyaniline composite paper that prepared by the present invention has excellent electrical property.
Should be understood that; the above is only the preferred embodiment of the present invention, to those skilled in the art, under the prerequisite not departing from the technology of the present invention principle and scope; can realize the multiple change to these embodiments or conversion, and these amendments also should be considered as in protection scope of the present invention.
Claims (13)
1. a preparation method for grapheme/polyaniline composite paper, is characterized in that, comprises the following steps:
A. graphene oxide dispersion is provided;
B. described graphene oxide dispersion is mixed to obtain slurry with reducing agent, then described slurry is coated on substrate, then carry out drying to obtain graphene paper; With
C. described grapheme/polyaniline composite paper is obtained by being deposited in described graphene paper by polyaniline,
The reducing agent used in wherein said step b is hydroiodic acid, hydrazine hydrate or sodium borohydride, and the bake out temperature in described step b is 60 ~ 90 DEG C.
2. the preparation method of grapheme/polyaniline composite paper according to claim 1, is characterized in that, described graphene oxide dispersion is provided by following steps:
A1. the mixture of graphite flakes and nitrate is joined in strong acid and carry out pre-oxidation, stir and obtain dispersion liquid;
A2. in the described dispersion liquid of a1, add strong oxidizer, stir, place 1-10 days, obtain taupe pastel;
A3. in the described taupe pastel of a2, add deionized water and hydrogen peroxide successively, obtain glassy yellow suspension;
A4. by centrifugal for the described glassy yellow suspension of a3, washing and dialysis, obtain described graphene oxide dispersion.
3. the preparation method of grapheme/polyaniline composite paper according to claim 1, it is characterized in that, use hydriodic acid aqueous solution as reducing agent in described step b, and the volume ratio of described graphene oxide dispersion and described hydriodic acid aqueous solution is (10 ~ 5): 1.
4. the preparation method of grapheme/polyaniline composite paper according to claim 1, is characterized in that, the substrate in described step b is Teflon.
5. the preparation method of grapheme/polyaniline composite paper according to claim 1, is characterized in that, the drying time in described step b is 1 ~ 8 hour.
6. the preparation method of grapheme/polyaniline composite paper according to claim 1, it is characterized in that, in described step b, also comprise and clean to the graphene paper on the substrate after oven dry with water and alcohol successively and dry, thus obtain complete graphene paper from described substrate.
7. the preparation method of grapheme/polyaniline composite paper according to claim 1, it is characterized in that, in described step c, by electrochemical polymerization aniline monomer by polyaniline electroplating deposition in described graphene paper, thus form described grapheme/polyaniline composite paper.
8. the preparation method of grapheme/polyaniline composite paper according to claim 7, is characterized in that, described electroplating deposition is realized by following steps:
C1. in water and alcohol mixed solvent, prepare the sulfuric acid solution of 0.5-2 mol/L;
C2. aniline monomer is joined in the mixed solution of step c1 acquisition;
C3. carry out electrochemical polymerization with three-electrode method, wherein with described graphene paper for working electrode, be to electrode with platinum electrode, with silver/silver chlorate for reference electrode, and with step c2 obtain mixed solution for electrolyte.
9. the preparation method of grapheme/polyaniline composite paper according to claim 8, is characterized in that, the water in described water and alcohol mixed solvent and the volume ratio of ethanol are (1-10): 1.
10. the preparation method of grapheme/polyaniline composite paper according to claim 8, is characterized in that, working concentration is the aniline monomer solution of 0.05 ~ 0.5 mol/L.
The preparation method of 11. grapheme/polyaniline composite paper according to claim 8, is characterized in that, the operating voltage in described electrochemical polymerization process is 0.8 volt.
The preparation method of 12. grapheme/polyaniline composite paper according to claim 8, is characterized in that, the time of described electrochemical polymerization is 2 ~ 30 minutes.
13. 1 kinds of grapheme/polyaniline composite paper obtained by the preparation method according to any one of claim 1-12.
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| CN103903877B (en) * | 2012-12-26 | 2016-06-29 | 海洋王照明科技股份有限公司 | A kind of preparation method of graphene/graphene oxide composite current collector |
| CN103265013B (en) * | 2013-04-26 | 2014-12-10 | 华中科技大学 | Preparation methods of flexible substrate-based graphene film and flexible substrate-based graphene composite film |
| CN103966644B (en) * | 2014-04-10 | 2016-08-17 | 同济大学 | A kind of preparation method of graphene/polymer emulsion composite film material |
| CN103963403A (en) * | 2014-04-25 | 2014-08-06 | 无锡格菲电子薄膜科技有限公司 | Composite of graphene and conducting polymer and preparation method of composite |
| CN104211960B (en) * | 2014-09-30 | 2017-01-25 | 中原工学院 | One-step chemical preparation method for graphene and polyaniline composite materials |
| CN104495811B (en) * | 2014-12-12 | 2017-01-11 | 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 |
| 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 |
| CN105735047B (en) * | 2016-02-01 | 2017-12-05 | 东南大学 | A kind of preparation method of conductive and super-hydrophobic graphene functional paper |
| 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 |
| 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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