CN112017869A - Self-supporting flexible composite film and preparation method thereof - Google Patents
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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Abstract
The invention relates to a self-supporting flexible composite film and a preparation method thereof, belonging to the field of electrode materials of super capacitors. The self-supporting flexible composite film comprises a pseudo-capacitor material and a carbon material which are mixed in an aqueous solution in a physical electrostatic adsorption mode, a pseudo-capacitor material/carbon material uniform mixed solution is obtained through ultrasound, and then the pseudo-capacitor material/carbon material uniform mixed solution is subjected to vacuum filtration to obtain a pseudo-capacitor material/carbon material composite material; and carrying out heat treatment on the obtained pseudo-capacitance material/carbon material composite material at 550-650 ℃ in a tubular furnace under the atmosphere of ammonia gas for nitrogen doping, and reducing the carbon material at 550-650 ℃ under the heat treatment to finally obtain the self-supporting flexible composite film. The preparation method of the self-supporting flexible composite film realizes the removal of the conductive agent and the binder, fully exerts the advantages of the molybdenum trioxide material and the graphene material, and has good application prospect.
Description
Technical Field
The invention relates to a self-supporting flexible composite film and a preparation method thereof, belonging to the field of electrode materials of super capacitors.
Background
The supercapacitor electrode material is generally composed of an active material, a conductive agent and a binder, and the conductivity of the binder is extremely low, so that the performance of the electrode material is obviously reduced, and how to remove the conductive agent and the binder from the electrode material is a main direction of related research at present. The active material plays the most important role in the electrode material, and the electrode active material is mainly selected from carbon materials of an electric double layer energy storage mechanism, conductive polymers of a pseudo-capacitance energy storage mechanism, metal oxides, metal sulfides and the like. The double electric layer material realizes energy storage mainly through adsorption of positive and negative charges, and the energy density of the material is limited by the specific surface area of the material because the physical adsorption process only occurs on the surface of the electrode material; the pseudocapacitance material realizes energy storage through highly reversible redox reaction between electrolyte ions and an electrode material, the reaction can be generated on the surface of the electrode material, and the electrolyte ions can penetrate into the electrode material to react with the electrode material, so that the pseudocapacitance material generally has higher energy density.
Traditional supercapacitor electrode materials are blocky solid materials, and in order to further meet the requirements of flexible wearable electronic equipment, the supercapacitor electrode materials are continuously developed towards flexibility and light weight. The flexible electrode materials of the super capacitor are mainly divided into two types at present, namely flexible substrate structure electrodes and self-supporting flexible electrodes. The flexible substrate electrode is prepared by preparing an electrode material on a flexible, stretchable or compressible flexible substrate, and taking the substrate as a deformation carrier. In the process of causing the deformation of the electrode material, the flexible substrate is used as a main bearing part of stress, so that the damage to the electrode material is relieved to a great extent, the electrode material is kept stable, but the performance of the electrode material is often influenced by the substrate material. The self-supporting flexible electrode does not need to be additionally provided with an additional substrate material, the influence of other materials on the electrode material can be greatly reduced, the advantages of the electrode material can be fully exerted, and the quality of the flexible electrode is improved, so that the overall performance of the device is improved. The self-supporting flexible electrode is mainly prepared by means of chemical vapor deposition or vacuum filtration, generally, the main electrode materials are one-dimensional nanowires and two-dimensional nanosheet structures, and similar nanomaterials are beneficial to formation of self-supporting thin film materials.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a self-supporting flexible composite film and a preparation method thereof, and the self-supporting flexible composite film has the advantages of simple process, flexibility, self-support, excellent electrochemical performance and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a self-supporting flexible composite film comprises the following steps:
(1) mixing the pseudocapacitance material and the carbon material in a physical mode to obtain a mixed solution;
(2) carrying out vacuum filtration on a solution obtained by mixing the pseudocapacitance material and the carbon material to obtain a pseudocapacitance material/carbon material composite material;
(3) and carrying out heat treatment on the obtained pseudo-capacitance material/carbon material composite material at 550-650 ℃ in a tubular furnace under the atmosphere of ammonia gas for nitrogen doping, and reducing the carbon material at 550-650 ℃ under the heat treatment to finally obtain the self-supporting flexible composite film.
The metal oxide material has a larger theoretical specific capacitance due to a unique pseudo-capacitance energy storage mechanism, is commonly used as a pseudo-capacitance material, and can have a larger specific surface area by preparing the material into a nanowire structure, so that the utilization rate of the material is improved, and the nanowire structure is favorable for forming a self-supporting flexible film. alpha-MoO3Due to the unique layered structure of the material, an ion channel which is more beneficial for electrolyte ions to go deep into the electrode material is formed, and the capacitance performance of the electrode material can be greatly improved. The graphene oxide powder can be reduced into a reduced graphene oxide material (rGO) after heat treatment, the graphene material has excellent conductivity and mechanical properties, and the reduced graphene oxide can significantly improve the transmission rate of electrons in the composite material, so that the rate capability of the electrode material is improved. In addition, the existence of the graphene material also greatly enhances the mechanical flexibility of the electrode material.
Preferably, the pseudocapacitive material is a metal oxide material.
Preferably, the pseudocapacitance material is alpha-MoO with a laminated structure3。
Preferably, the alpha-MoO3Is a nanowire material.
Preferably, the alpha-MoO3Prepared by a hydrothermal method.
The nano material prepared by the hydrothermal method has higher purity, good dispersity, good and controllable crystal form and low production cost.
Preferably, the carbon material is graphene oxide powder (GO).
Preferably, the physical mixing is to disperse the pseudocapacitance material in deionized water and then add polydiene dimethyl ammonium chloride solution to make the surface of the pseudocapacitance material positively charged; and adding the carbon material dispersion liquid into the pseudocapacitance material dispersion liquid, adsorbing the pseudocapacitance material and the carbon material through electrostatic interaction, and performing ultrasonic homogenization.
The electrostatic adsorption interaction can enable the pseudocapacitance material and the carbon material to be more uniformly compounded to form a microstructure of the pseudocapacitance material uniformly coated by the carbon material.
Preferably, the nitrogen doping conditions are: carrying out heat treatment at 550-650 ℃ in ammonia atmosphere, wherein the heating rate is 2-5 ℃/min, the heat preservation time is 30-120 min, and naturally cooling to room temperature after the heat treatment is finished.
The method is used for nitrogen doping, the process is simple, and nitrogen atoms can be uniformly doped into MoO3In crystal structure, thereby realizing MoO3And the conductivity of the nanowire is improved.
Compared with the prior art, the invention has the beneficial effects that: (1) the process is simple, and the self-supporting flexible composite film is obtained by adopting a simple vacuum filtration and heat treatment method; (2) the raw materials are environment-friendly, and cannot cause pollution to the environment; (3) the electrochemical performance is superior, and the material has great advantages compared with the self-supporting flexible composite film material reported previously.
Drawings
FIG. 1 is a process for preparing a self-supporting flexible composite film according to the present invention; wherein, (a) is a MoNO/rGO film material flow chart, and (b) is MoO3a/GO composite film material object diagram.
FIG. 2 is a schematic representation of the α -MoO of the present invention3Scanning Electron Microscope (SEM) images at different magnifications; wherein (a) is an amplification of 1k times, (b) is an amplification of 5k times, (c) is an amplification of 13k times, and (d) is an amplification of 30k times.
FIG. 3 shows α -MoO in the present invention3X-ray diffraction spectrum (XRD) pattern of (a).
FIG. 4 (a-d) is a MoO according to the present invention3A characterization SEM picture of the/GO self-supporting flexible composite film after heat treatment at 550-650 ℃ in ammonia gas, (e) is an X-ray energy spectrum analysis (EDS energy spectrum) picture, and (f) is a Transmission Electron Microscope (TEM) picture.
FIG. 5 shows a MoNO/rGO flexible self-supporting composite film of the present invention at 1M H2SO4Electrochemical test results in aqueous electrolyte; wherein (a) is a cyclic voltammetry curve (CV curve) obtained at different scanning rates, (b) is a constant current charging and discharging curve at different current densities, (c) is a curve of area specific capacitance changing along with current density, and (d) is an Electrochemical Impedance Spectroscopy (EIS) test.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
Traditional supercapacitor electrode material is cubic solid material, and in order to further satisfy flexible wearable electronic equipment's demand, supercapacitor electrode material is constantly developing towards flexibility, lightweight direction. The flexible substrate electrode is prepared by preparing an electrode material on a flexible, stretchable or compressible flexible substrate, and the substrate is used as a deformation carrier, but the substrate material often influences the performance of the electrode material. The self-supporting flexible electrode does not need to be additionally provided with an additional substrate material, the influence of other materials on the electrode material can be greatly reduced, the advantages of the electrode material can be fully exerted, and the quality of the flexible electrode is improved, so that the overall performance of the device is improved. The invention provides a self-supporting flexible composite film for overcoming the defects in the prior art.
Example 1
In an embodiment of the present invention, a method for preparing a self-supporting flexible composite film includes:
(1)α-MoO3the preparation of (1): uniformly stirring molybdenum powder and hydrogen peroxide solution according to a certain proportion, transferring the mixture into a reaction kettle, putting the reaction kettle into an oven, reacting for 3 days at the reaction temperature of 180 ℃, filtering a reaction product after the reaction is finished, thoroughly cleaning the reaction product by using deionized water and absolute ethyl alcohol, and drying the reaction product for 12 hours in vacuum at the temperature of 70 ℃.
(2)MoO3Preparing a/GO composite film: taking a proper amount of alpha-MoO3Dissolving the nanowires in deionized water, and dropwise adding 0.5ml polydiene dimethyl ammonium chloride (PDDA) solution in the process of continuous stirring after uniformly stirring to ensure that the alpha-MoO3The surface of the nanowire is positively charged. Excess PDDA was removed by centrifugation, washing and redispersion. And then weighing a certain amount of GO powder, adding the GO powder into the aqueous solution, and performing ultrasonic dispersion by using a probe ultrasonic instrument to obtain a 1mg/mL uniformly dispersed GO aqueous solution. Then, the previously prepared positively charged MoO3The nanowire aqueous solution is dropwise added into the 1mg/mL GO aqueous solution with negative charges under the ultrasonic condition, and self-assembled MoO is formed due to electrostatic interaction3aqueous/GO nanocomposite solution. After further sonication, the MoO obtained above was subjected to3Vacuum filtering the/GO nano compound water solution through a filter membrane with the aperture of 220nm, washing with deionized water for several times, freezing the filtered film in a freeze dryer for 15min, and finally freezing the MoO3the/GO film is taken off from the filter membrane and dried in vacuum at 60 ℃. FIG. 1(b) is MoO3The material graph of the/GO composite film is about 4cm in diameter.
(3) Preparation of MoNO/rGO film: the obtained MoO3Placing the GO film into a tubular furnace to carry out 550 ℃ heat treatment in an ammonia atmosphere, wherein the heating rate is 5 ℃/min; and (3) heat preservation time: and (4) after the heat treatment is finished for 120 minutes, naturally cooling the tube furnace, and taking out the sample.
Example 2
Referring to fig. 1, a flow of an embodiment of a method for manufacturing a self-supporting flexible composite film according to the present invention is different from that of embodiment 1 in that: in this embodiment, the procedure of setting the tube furnace in the preparation of the MoNO/rGO film in step (3) is as follows: and (3) carrying out heat treatment at 600 ℃ in an ammonia atmosphere, wherein the heating rate is 3 ℃/min, and the heat preservation time is 80 min.
Example 3
In an embodiment of the method for preparing a self-supporting flexible composite film of the present invention, the method for preparing a self-supporting flexible composite film described in this embodiment is different from that of embodiment 1 in that: in the embodiment, the procedure of arranging the tube furnace in the preparation of the MoNO/rGO film in the step (3) is to perform 650 ℃ heat treatment in an ammonia atmosphere, wherein the heating rate is 2 ℃/min, and the heat preservation time is 30 min.
Referring to FIG. 2, FIG. 2 shows α -MoO3SEM image of nanowire, from which alpha-MoO can be seen3alpha-MoO with nano-wire length up to dozens of microns and super-long3The nano-wire provides a precondition for the preparation of the flexible self-supporting film and is pumped by vacuumFilter, alpha-MoO3The nanowires will be firmly intertwined to form a flexible film with good mechanical properties.
Referring to FIG. 3, FIG. 3 shows α -MoO3XRD pattern of nano wire, XRD spectral line obtained by scanning and alpha-MoO3The PDF cards are well matched, which shows that the nanowire material prepared by the method is alpha-MoO3。
Please refer to FIG. 4, FIG. 4 is a MoO3Characterization of GO after heat treatment in ammonia. After high-temperature annealing, the graphene oxide is fully reduced, the original structural morphology of the nanowire is still maintained after heat treatment, the reduced graphene oxide is uniformly dispersed on the surface of the nanowire to form a good conductive network, the transmission rate of electrons in the electrode material is greatly increased, and the rate capability of the electrode material is favorably improved. Fig. 4(f) is a TEM image of the MoNO/rGO composite film, from which it can be seen that although the composite film was ultrasonically dispersed before TEM analysis, the MoNO nanowires and rGO were well combined and rGO was uniformly dispersed on the surface of the MoNO nanowires, which is consistent with previous SEM image analysis. FIG. 4(e) is an EDS energy spectrum of a MoNO/rGO composite film, which shows that the composite film prepared by us contains Mo, N, O and C elements, wherein the Cu element is from a copper mesh for TEM test.
Referring to fig. 5, fig. 5 shows the electrochemical performance of the obtained thin film material. The CV curve of (a) proves that the MoNO/rGO material has good electrochemical performance, and when the scanning speed is increased from 5mV/s to 200mV/s, the CV curve keeps a very complete rectangle without distortion and deformation, which indicates that the electrode material has good electrochemical reversibility. Fig. 5(b) is a constant current charge and discharge (GCD) curve of the MoNO/rGO self-supporting flexible composite thin film electrode at different current densities, and it can be seen from the figure that the GCD curve has a symmetrical triangular characteristic, and the voltage is almost in a linear relationship with the charge and discharge time, which indicates that the electrode material has good rate capability. While no significant IR drop was observed on the discharge curve, indicating that the transfer of electrons and the migration of electrolyte ions was very rapid. FIG. 5(c) is a calculated area ratio of the electrode materialThe change of the capacitance with the current density is 2mA/cm2The specific capacitance of the area of the discharge current under the density is up to 303mF/cm2. The main reason why the area specific capacitance is reduced with the further increase of the current density is that the redox reaction occurring on the electrode surface consumes a large amount of ions with the increase of the current density, resulting in the reduction of the ion concentration in the electrolyte near the electrode surface, while the ion diffusion rate in the electrolyte is limited, and the ion concentration near the electrode surface cannot be balanced in time, thereby generating concentration polarization. To further understand the kinetics of electrolyte ions and electrons during the electrochemical reaction, we tested the electrochemical impedance spectrum of the electrode material (fig. 5 (d)). From the measured electrochemical impedance spectroscopy results, the analysis can be performed from the following 3 angles, respectively:
(1) the intercept of the intersection of the X-axis and the high frequency region represents that the total Equivalent Series Resistance (ESR) of the whole circuit is relatively small, about 0.1 omega cm2；
(2) The smaller radius of the semi-arc at the middle and high frequency region indicates that there is a smaller interfacial charge transfer resistance (R) between the electrode material and the electrolytect)；
(3) In a low-frequency area, the real part and the imaginary part of the alternating-current impedance curve are almost in a vertical relation, and the fact that the electrode material has good capacitance performance is shown.
Referring to table 1, the area specific capacitance of the prepared MoNO/rGO electrode material was compared to some other electrode materials reported so far.
TABLE 1 comparison of MoNO/rGO electrode material area specific capacitance with some other electrode materials reported so far
As shown in Table 1, under the condition of higher current density than other composite materials, the MoNO/rGO electrode material prepared by the method still can keep larger area specific capacitance, which shows that the composite thin film material prepared by the method has obvious advantages in performance.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. A self-supporting flexible composite film and a preparation method thereof are characterized by comprising the following steps:
(1) mixing the pseudocapacitance material and the carbon material in a physical mode to obtain a mixed solution;
(2) carrying out vacuum filtration on a solution obtained by mixing the pseudocapacitance material and the carbon material to obtain a pseudocapacitance material/carbon material composite material;
(3) and carrying out heat treatment on the obtained pseudo-capacitance material/carbon material composite material at 550-650 ℃ in a tubular furnace under the atmosphere of ammonia gas for nitrogen doping, and reducing the carbon material at 550-650 ℃ under the heat treatment to finally obtain the self-supporting flexible composite film.
2. The method of claim 1, wherein the pseudocapacitive material is a metal oxide material.
3. The method of claim 2, wherein the metal oxide material is α -MoO with a layered structure3。
4. The method of claim 3, wherein the α -MoO is in the form of a film3Is a nanowire material.
5. The self supporting flexible composite sheet of claim 4Method for producing a membrane, characterized in that the alpha-MoO3Is prepared by a hydrothermal method.
6. The method of claim 1, wherein the carbon material is graphene oxide powder.
7. The preparation method of the self-supporting flexible composite film according to claim 1, wherein the physical mixing is to disperse the pseudocapacitance material in deionized water and then add polydienedimethylammonium chloride solution to make the surface of the pseudocapacitance material positively charged; and adding the carbon material dispersion liquid into the pseudocapacitance material dispersion liquid, adsorbing the pseudocapacitance material and the carbon material through electrostatic interaction, and performing ultrasonic homogenization.
8. The method for preparing the self-supporting flexible composite film according to claim 1, wherein the nitrogen doping conditions are as follows: carrying out heat treatment at 550-650 ℃ in ammonia atmosphere, wherein the heating rate is 2-5 ℃/min, the heat preservation time is 30-120 min, and naturally cooling to room temperature after the heat treatment is finished.
9. A self-supporting flexible composite film prepared by the method of any one of claims 1 to 8.
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