CN110885075B - Conductive graphene composite film capable of enhancing toughness and strength and preparation method thereof - Google Patents
Conductive graphene composite film capable of enhancing toughness and strength and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a conductive graphene composite film capable of enhancing toughness and strength and a preparation method thereof. The preparation method comprises the following steps: the preparation method comprises the steps of carrying out surface modification on carbon nanotubes by using a dopamine-Tris hydrochloride buffer aqueous solution to prepare polydopamine-coated carbon nanotubes, blending the polydopamine-coated carbon nanotubes with a graphene oxide solution, carrying out evaporation induction assembly to prepare a composite film, and further carrying out chemical reduction on the composite film to obtain the conductive graphene composite film. The composite film has high strength, high toughness, high ductility and high conductivity, and the preparation method is green, environment-friendly, simple, convenient and quick, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a conductive graphene composite film and a preparation method thereof.
Background
Graphene is a polymer made of carbon atoms in sp 2 The hybridized orbitals are connected into monoatomic layers of a hexagonal honeycomb structure, 3 sp are formed between 3 of 4 valence electrons of each carbon atom and other carbon atoms 2 The remaining one unbound electron forms a large pi bond with the unbound electron of the other carbon atom throughout the graphene sheet layer on the pz orbital perpendicular to the plane of the layer. The unique structure endows graphene with excellent performance, the graphene is a known material with the highest strength, the theoretical tensile strength can reach 130 GPa, and the Young modulus can reach 1.0 TPa. At the same time, graphiteThe alkene also has excellent thermoelectric properties with a carrier mobility of about 15000 cm at room temperature 2 V.s, thermal conductivity up to 5300W/mK, and electrical conductivity up to 10 8 S/m。
In order to convert the excellent performance, particularly the mechanical property, of graphene into practical application and promote the application of graphene in the fields of aerospace, flexible devices, tissue engineering and the like, in recent years, a series of pearl-like layer graphene composite film materials based on graphene and derivatives thereof, such as Graphene Oxide (GO) and reduced graphene oxide (rGO), are developed. Binary graphene composite film materials such as rGO-polyvinyl alcohol (PVA), rGO-poly (10, 12-penta-diamine-1-ol) (PCDO), rGO-polyacrylic acid (PAA), rGO-1-Aminopyrene (AP) -octanedioic acid bis (N-hydroxysuccinimide ester) (DSS) and the like effectively improve the cross-linking between graphene sheets through covalent interaction, hydrogen bonds or pi-pi interaction and the like, but are limited by the performance of the polymer, the obtained composite film has limited improvement on the mechanical properties, cannot simultaneously improve the strength, toughness and elongation of the film, and the tensile strength and toughness of the composite film are generally 500 MPa and 15 MJ/m 3 The following. The tensile strength of the composite film is effectively improved through two or more actions such as covalent interaction, hydrogen bond or pi-pi interaction, ionic bond and the like, but the elongation of the film is generally low due to the fact that short bonds of the ionic bond are long, so that the toughness of the film is difficult to improve. In addition, organic matter crosslinking needs to be realized through ultraviolet radiation in the preparation processes of rGO-AP-DSS, rGO-PCDO, rGO-AP-PSE and the like, the process is complex and polluted, and the AP-DSS, PCDO and AP-PSE are very expensive and are not beneficial to industrial preparation of the composite film.
Therefore, it is a difficult problem in the art to provide an economical, environment-friendly, simple and convenient method for preparing a graphene composite film having high strength, high toughness and high ductility.
Disclosure of Invention
Aiming at the problems in the prior art, the technical problem to be solved by the invention is to provide the conductive graphene composite film capable of enhancing toughness and strength, which can improve the strength of the graphene composite film, enhance the toughness and have good conductivity. The invention also provides a preparation method of the graphene composite film, which can realize green, environment-friendly, simple and convenient preparation process.
In order to solve the technical problems:
the invention provides a conductive graphene composite film capable of enhancing toughness and strength, which is prepared from reduced graphene oxide and polydopamine-coated carbon nanotubes in percentage by mass: the graphene oxide/polydopamine composite material comprises 85-97.5% of reduced graphene oxide and 2.5-15% of polydopamine-coated carbon nanotubes, wherein reduced graphene oxide lamella and the polydopamine-coated carbon nanotubes are stacked, and the interior of the reduced graphene oxide lamella and the lamellae are crosslinked together with the polydopamine-coated carbon nanotubes.
The Polydopamine (PDA) and the Carbon Nanotubes (CNTs) in the polydopamine coated carbon nanotubes (PDA @ CNTs) play a role in synergistic toughening and enhancing the film through covalent crosslinking and entanglement between the Carbon Nanotubes (CNTs).
The invention also provides a preparation method of the heat-conducting and electric-conducting graphene film, which comprises the following steps
Step 1, preparing dopamine hydrochloride-Tris buffer solution with the concentration of 1-4 mg/ml;
step 4, adding the polydopamine-coated carbon nano tube into the graphene oxide aqueous solution, and stirring and ultrasonically mixing to obtain a corresponding mixed solution;
and 6, soaking the composite film obtained in the step 5 in a reducing agent hydroiodic acid, washing with ethanol and drying to obtain the reduced graphene oxide and polydopamine coated carbon nanotube composite film.
In the step 3, the preparation of the graphene oxide aqueous solution comprises the following steps:
step 1), mixing 3 g of flake graphite with the average size of 325 meshes and 70 ml of concentrated sulfuric acid with the concentration of 98 wt% in an ice-water bath, and reacting for 1 h under stirring;
step 2), slowly adding 9 g of potassium permanganate in the reaction kettle within 6 h, and adding 0 g of potassium permanganate o C, reacting for 8 hours;
step 3), slowly adding 150 ml of prepared ice water within 6 h;
step 4), pouring the mixture into 1500 ml of prepared ice water;
step 5), dropwise adding 20 ml of hydrogen peroxide with the concentration of 3 wt%;
step 6), after standing for at least 24 hours, pouring out supernatant, and washing precipitates by using hydrochloric acid solution with the concentration of 3.7 wt% and deionized water in sequence until the PH value is 6-7;
and 7) centrifuging the obtained product at 3000 rpm for at least 30 min, removing precipitates after several times of centrifugation, obtaining a graphene oxide aqueous solution after ultrasonic stirring for at least 0.5h, and diluting to prepare the graphite oxide aqueous solution with the concentration of 2 mg/mL.
In the step 4, the mass fraction of the polydopamine coated carbon nano tube in the total mass of the polydopamine coated carbon nano tube and the graphene oxide is 2.5-15%, the mixing and stirring time is 1-2 hours, and the ultrasonic time is 10-15 min.
In the step 5, the process of preparing the composite film by evaporation-induced assembly comprises the following steps: pouring 100 ml of prepared polydopamine-coated carbon nanotube and graphene oxide mixed solution into a polystyrene culture surface which is washed in advance and is 10 cm multiplied by 10 cm, assembling the polydopamine-coated carbon nanotube and graphene oxide into a composite film with a laminated structure along with the evaporation of a solvent, and completely drying to obtain the self-supporting polydopamine-coated carbon nanotube and graphene oxide composite film.
In the step 6, the concentration of the hydroiodic acid is 57 wt%, and the reduction temperature is 0 to 30 o C, reducing for at least 6 h; through immersing in absolute alcohol for 5-8 times and vacuum washing for 30-50 times o And C, drying for at least 6 h to obtain the reduced graphene oxide and polydopamine coated carbon nanotube composite film.
Aiming at the problem that the strength and toughness of the composite film in the prior art cannot be compatible, the invention prepares the polydopamine-coated carbon nanotube by modifying the surface of the carbon nanotube by adopting a dopamine-Tris hydrochloride buffer aqueous solution, and then prepares the film by blending the polydopamine-coated carbon nanotube with a graphene oxide solution. The poly-dopamine modification promotes the dispersion of the carbon nano tubes in the graphene oxide aqueous solution and the obtained composite film, the interface coupling between the carbon nano tubes and graphene sheet layers is improved, meanwhile, the poly-dopamine acts with the graphene oxide through amino groups in molecules of the poly-dopamine, the poly-dopamine is chemically reduced by hydroiodic acid, the poly-dopamine acts a crosslinking effect on the reduced graphene oxide sheet layers through the action of the amino groups of the poly-dopamine and the reduced graphene oxide sheet layers, and the crosslinked poly-dopamine simultaneously enhances the entanglement effect between the carbon nano tubes. When the film is stretched by an external force, the cross-linking effect of the polydopamine and the entanglement effect of the carbon nano tubes act synergistically, mutually promote and absorb energy, prevent the slippage of the sheet layer, and effectively improve the tensile strength and the elongation at break of the composite film, so that the comprehensive mechanical properties (tensile strength, elongation at break and toughness) of the composite film are greatly improved at the same time.
The performance indexes of the conductive graphene composite film are as follows: tensile strength of 579 +/-35 MPa, elongation at break of 12.03 +/-0.56 percent and toughness of 34.03 +/-1.60 MJ/m 3 And the conductivity 612. + -.68S/cm. In addition, the conductive graphene composite film of the present invention has excellent structural stability under the condition of continuous ultrasound in deionized water and sulfuric acid solution.
According to the preparation method, firstly, polydopamine is adopted to modify the surface of the carbon nano tube, then the obtained polydopamine-coated carbon nano tube and graphene oxide are blended to prepare a membrane, and further, the composite membrane is obtained through chemical reduction of hydroiodic acid. In the whole preparation process, no organic solvent except hydroiodic acid is used, radiation crosslinking is not needed, the preparation process is environment-friendly, the preparation process is simple to operate, the cost is low, and industrial production is easy to realize.
The invention has the advantages that:
the conductive graphene composite film disclosed by the invention has the advantages that the tensile strength is improved, the toughness is enhanced, the comprehensive mechanical property, the conductivity and the structural stability are excellent, and the conductive graphene composite film has a wider application prospect in the fields of aerospace, flexible devices, tissue engineering and the like.
Drawings
The drawings of the invention are illustrated below:
FIG. 1 is characterization data of the conductive graphene composite film obtained in example 1
(A) Is an XPS spectrum and is a standard spectrum,
(B) The XRD spectrogram of the composite film with different dosage of the polydopamine-coated carbon nano tube,
(C) A physical diagram of the conductive graphene composite film obtained in example 1,
(D) Is a cross-sectional SEM photograph of the conductive graphene composite film obtained in example 1;
fig. 2 shows mechanical properties of the conductive graphene film obtained in example 1 of the present invention;
FIG. 3 is a graph comparing the structural changes of different films in example 4 with constant sonication in DI water;
FIG. 4 is a graph comparing the structural changes of different films in example 4 with constant ultrasound in sulfuric acid solution.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings:
code number description of this patent application: the rGO film was: a pure reduced graphene oxide film; the rGO-PDA film is: reducing the graphene oxide and polydopamine composite film; the rGO-CNTs film is as follows: reducing the graphene oxide and carbon nano tube composite film; the rGO-PDA @ CNTs film is as follows: the composite film of the carbon nano tube is coated by the reduced graphene oxide and the polydopamine.
Example 1
Step 1, preparing dopamine hydrochloride-Tris buffer solution with the concentration of 4 mg/ml;
step 1), mixing 3 g of flake graphite with the average size of 325 meshes and 70 ml of concentrated sulfuric acid with the concentration of 98 wt% in an ice-water bath, and reacting for 1 h under stirring;
step 2), then slowly adding 9 g of potassium permanganate in the reaction kettle for 6 h, and adding the mixture at 0 o C, reacting for 8 hours;
step 3), slowly adding 150 ml of prepared ice water within 6 h;
step 4), pouring the mixture into 1500 ml of prepared ice water;
step 5), dropwise adding 20 ml of hydrogen peroxide with the concentration of 3 wt%;
step 6), after standing for 24 hours, pouring out supernatant, and washing precipitates by using hydrochloric acid solution with the concentration of 3.7 wt% and deionized water in sequence until the PH value is 6-7;
and 7) centrifuging the obtained product for 30 min at 3000 rpm for several times, removing precipitates, performing ultrasonic treatment for 0.5h to obtain a graphene oxide aqueous solution with a specific concentration, and diluting to prepare the graphene oxide aqueous solution with the concentration of 2 mg/mL.
Step 4, adding the polydopamine-coated carbon nano tube into GO aqueous solution according to the amount that the polydopamine-coated carbon nano tube accounts for 7.5 wt% of the total mass of the polydopamine-coated carbon nano tube and the graphene oxide, stirring for 1 h, and performing ultrasonic treatment for 15 min to obtain a mixed solution of the graphene oxide and the polydopamine-coated carbon nano tube;
The conductive graphene composite film of the embodiment has tensile strength of 579 +/-35 MPa, elongation at break of 12.03 +/-0.56% and toughness of 34.03 +/-1.60 MJ/m 3 The conductivity was 612. + -.68S/cm.
As shown in fig. 1 (a), the XPS spectrum of the conductive graphene composite thin film obtained in example 1 has a main peak SP with a binding energy of about 285 eV 2 A C peak, indicating that defects in the graphene sheets were repaired after hydriodic acid reduction, while the presence of C-O, O-C = O, C = O peaks indicates that there are also partial oxygen-containing groups in the composite film that interact with the C-N groups in the polydopamine molecules to effect crosslinking. XRD in FIG. 1 (B) shows at 25 o The reduction effect of hydroiodic acid on graphene oxide is further verified by the left and right 2 theta diffraction peaks. Fig. 1 (C) and (D) show that the conductive graphene composite film has a dense, wrinkled nacreous layer structure.
As can be seen from figure 2, the prepared conductive graphene composite film has excellent comprehensive mechanical properties, and the tensile strength, the elongation at break and the toughness of the conductive graphene composite film respectively reach 579 +/-35 MPa, 12.03 +/-0.56 percent and 34.03 +/-1.60 MJ/m 3 The composite film overcomes the defect that the composite film in the prior art cannot simultaneously obtain high strength, elongation and toughness.
Example 2
Step 1, preparing dopamine hydrochloride-Tris buffer solution with the concentration of 1 mg/ml;
step 4, adding the polydopamine-coated carbon nanotube into a graphene oxide aqueous solution according to the amount that the polydopamine-coated carbon nanotube accounts for 7.5 wt% of the total mass percent of the polydopamine-coated carbon nanotube and the graphene oxide, and stirring for 2 hours and carrying out ultrasonic treatment for 10 minutes to obtain a mixed solution of the graphene oxide and the polydopamine-coated carbon nanotube;
The conductive graphene composite film of the embodiment has the tensile strength of 485 +/-28 MPa, the elongation at break of 13.84 +/-0.56% and the toughness of 32.54 +/-2.50 MJ/m 3 The conductivity was 476. + -.42S/cm.
Example 3 (comparative example)
The difference from example 1 is: in step 4, the poly dopamine coated carbon nanotubes have different mass percentages, and the properties of the prepared composite film are listed as follows:
TABLE 1
| Content of poly-dopamine-coated carbon nanotube (wt%) | Tensile Strength (MPa) | Elongation at Break (%) | Toughness (MJ/m) 3 ） | Conductivity (S/cm) |
| 0 | 256±24 | 5.83±0.37 | 6.89±0.76 | 832±101 |
| 2.5 | 299±22 | 7.76±1.67 | 11.41±1.65 | 796±80 |
| 5 | 380±17 | 10.13±1.48 | 20.41±2.85 | 735±65 |
| 7.5 | 579±35 | 12.03±0.56 | 34.03±1.60 | 612±68 |
| 10 | 534±15 | 13.21±0.82 | 32.21±1.95 | 478±105 |
| 15 | 354±38 | 15.99±0.38 | 28.19±2.70 | 365±42 |
As seen from table 1: the conductive graphene composite film without the poly-dopamine-coated carbon nanotube (with the poly-dopamine-coated carbon nanotube content being 0) has the lowest tensile strength, elongation at break and toughness and the highest electrical conductivity.
With the increase of the content of the polydopamine-coated carbon nanotube, the mechanical properties (tensile strength, elongation at break and toughness) of the conductive graphene composite film are increased, and the conductivity is reduced. When the content of the polydopamine-coated carbon nano tube is 7.5 wt%, the tensile strength and the toughness reach the highest. When the content of the polydopamine-coated carbon nanotubes is further increased, the tensile strength and the toughness are gradually reduced, and the conductivity is further reduced.
The content of the conductive graphene composite film in the polydopamine-coated carbon nanotube ranges from 2.5 wt% to 15 wt%, the tensile strength, the elongation at break and the toughness of the conductive graphene composite film are far higher than those of a rGO film, and the conductivity of the conductive graphene composite film is lower than that of the rGO film. When the content of the polydopamine-coated carbon nanotube is 7.5 wt%, the mechanical property and the conductivity of the conductive graphene composite film obtain the best effect.
Example 4 (comparative example)
The difference from example 1 is: in example 1, 7.5 wt% polydopamine-coated carbon nanotubes were used to be compounded with a graphene oxide solution. In this example, rGO films were prepared, and an rGO-PDA film, an rGO-CNTs film, and an rGO-PDA CNTs film were prepared by compounding 7.5 wt% of polydopamine, carbon nanotubes, polydopamine-coated carbon nanotubes, and graphene oxide solution. The mechanical properties of each composite film are tabulated below:
TABLE 2
| Tensile Strength (MPa) | Elongation at Break (%) | Toughness (MJ/m) 3 ） | |
| rGO film | 256±24 | 5.83±0.37 | 6.89±0.76 |
| rGO-PDA thin films | 365±32 | 4.72±0.35 | 8.89±1.05 |
| rGO-CNTs thin films | 330±44 | 14.57±0.75 | 25.62±2.28 |
| rGO-PDA @ CNTs film | 579±35 | 12.03±0.56 | 34.03±1.60 |
As seen from table 2: the tensile strength and toughness of the composite film added with PDA or CNTs are increased to different degrees, while the tensile strength, elongation at break and toughness of the composite film added with PDA @ CNTs are obviously improved, and the comprehensive performance is optimal.
Several composite film structures were compared for stability under continuous sonication (150W, 53 KHz) in deionized water and sulfuric acid solution (8 mol/L):
as shown in fig. 3, the rgo film was completely dissolved by continuous sonication in deionized water for 4.5 h; the rGO-PDA film is distributed in a loose particle manner; the rGO-CNTs film is dissolved by 60 percent, and only small films are left; the rGO-PDA @ CNTs film is lost, but still retains a large sheet of film. Therefore, the structural stability of the invention is strongest.
As shown in fig. 4, the rgo film was completely dissolved in sulfuric acid solution (8 mol/L) for 4.5h with continuous sonication; the rGO-PDA film has stronger acid resistance, and the film is completely reserved and becomes thinner; the rGO-CNTs film is partially dissolved, and the film surface is reduced; the rGO-PDA @ CNTs film is thinned, small gaps are formed in the edge of the film, and the sheet-surface state of the film is close to that of the rGO-PDA film. Therefore, the invention has strong acid resistance and good acid resistance.
As can be seen from fig. 3 and 4: the conductive graphene composite film disclosed by the invention has excellent structural stability under the condition of continuous ultrasonic treatment in deionized water and sulfuric acid solution.
Claims (7)
1. A can strengthen electrically conductive graphite alkene composite film of toughness and intensity, characterized by: the reduced graphene oxide and polydopamine coated carbon nanotube comprises the following components in percentage by mass: the graphene oxide/polydopamine composite material comprises 85-97.5% of reduced graphene oxide and 2.5-15% of polydopamine-coated carbon nanotubes, wherein reduced graphene oxide lamella and the polydopamine-coated carbon nanotubes are stacked, and the interior of the reduced graphene oxide lamella and the lamellae are crosslinked together with the polydopamine-coated carbon nanotubes.
2. The conductive graphene composite film according to claim 1, wherein: the mass percentages of the reduced graphene oxide and the polydopamine coated carbon nano tube are 92.5% of the reduced graphene oxide and 7.5% of the polydopamine coated carbon nano tube.
3. The preparation method of the conductive graphene composite film capable of enhancing toughness and strength according to claim 1, which is characterized by comprising the following steps:
step 1, preparing dopamine hydrochloride-Tris buffer solution with the concentration of 1-4 mg/ml;
step 2, adding the carbon nano tubes into the dopamine hydrochloride-Tris buffer solution prepared in the step 1 according to the concentration of 1 mg/ml, stirring and mixing, stirring and reacting for at least 24 hours at room temperature, and filtering and washing for multiple times to obtain polydopamine-coated carbon nano tubes;
step 3, preparing graphene oxide into a graphene oxide aqueous solution;
step 4, adding the polydopamine-coated carbon nano tube into the graphene oxide aqueous solution, and stirring and ultrasonically mixing to obtain a corresponding mixed solution;
step 5, evaporating, inducing and assembling the mixed solution obtained in the step 4 to obtain a graphene oxide and polydopamine coated carbon nanotube composite film;
and 6, soaking the composite film obtained in the step 5 in a reducing agent hydroiodic acid, washing with ethanol and drying to obtain the reduced graphene oxide and polydopamine coated carbon nanotube composite film.
4. The method for preparing the conductive graphene composite film according to claim 3, wherein in the step 3, the preparation of the graphene oxide aqueous solution comprises the following steps:
step 1), mixing 3 g of flake graphite with the average size of 325 meshes and 70 ml of concentrated sulfuric acid with the concentration of 98 wt% in an ice-water bath, and reacting for 1 h under stirring;
step 2), slowly adding 9 g of potassium permanganate in 6 h, and reacting for 8 h at 0 ℃;
step 3), slowly adding 150 ml of prepared ice water within 6 h;
step 4), pouring the mixture into 1500 ml of prepared ice water;
step 5), dropwise adding 20 ml of hydrogen peroxide with the concentration of 3 wt%;
step 6), standing for at least 24 h, pouring out supernatant, and washing precipitates sequentially by using hydrochloric acid solution with the concentration of 3.7 wt% and deionized water until the PH is 6-7;
and 7), centrifuging the obtained product at 3000 rpm for at least 30 min, removing precipitates after several times of centrifugation, ultrasonically stirring for at least 0.5h to obtain a graphene oxide aqueous solution, and diluting to prepare the graphene oxide aqueous solution with the concentration of 2 mg/mL.
5. The method for preparing the conductive graphene composite film according to claim 4, wherein the method comprises the following steps: in the step 4, the mass fraction of the polydopamine coated carbon nano tube in the total mass of the polydopamine coated carbon nano tube and the graphene oxide is 2.5-15%, the stirring and mixing time is 1-2 h, and the ultrasonic time is 10-15 min.
6. The method for preparing a conductive graphene composite film according to claim 5, wherein in the step 5, the evaporation-induced assembly is performed by: pouring 100 ml of prepared polydopamine-coated carbon nanotube and graphene oxide mixed solution into a polystyrene culture surface which is washed in advance and is 10 cm multiplied by 10 cm, assembling the polydopamine-coated carbon nanotube and graphene oxide into a composite film with a laminated structure along with the evaporation of a solvent, and completely drying to obtain the self-supporting polydopamine-coated carbon nanotube and graphene oxide composite film.
7. The method for preparing the conductive graphene composite film according to claim 6, wherein in the step 6, the concentration of the hydroiodic acid is 57 wt%, the reduction temperature is 0-30 ℃, and the reduction time is at least 6 h; the composite film of the reduced graphene oxide and the polydopamine-coated carbon nano tube is obtained by soaking and washing in a large amount of absolute ethyl alcohol for 5-8 times and drying at 30-50 ℃ for at least 6 h under vacuum.
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