CN110628056B - Graphene/polypyrrole particle composite gel film and preparation method thereof - Google Patents
Graphene/polypyrrole particle composite gel film and preparation method thereof Download PDFInfo
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- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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Abstract
The invention discloses a graphene/polypyrrole particle composite gel film and a preparation method thereof, wherein the preparation method comprises the following steps: s1, mixing pyrrole with hydrochloric acid solution to form gel pool solution; s2, uniformly mixing the graphene oxide and the high oxidation state metal oxide particle dispersion liquid to form a graphene oxide/high oxidation state metal oxide mixed dispersion liquid; s3, extruding the mixed dispersion liquid into a gel pool solution through a nozzle to generate a graphene oxide/polypyrrole particle composite hydrogel film; s4, adding the graphene oxide/polypyrrole particle composite hydrogel film into a reducing solution to generate a graphene/polypyrrole particle composite hydrogel film; and S5, drying the graphene/polypyrrole particle composite hydrogel film to obtain the graphene/polypyrrole particle composite hydrogel film. The polypyrrole particles in the graphene/polypyrrole particle composite film prepared by the method are uniformly distributed.
Description
Technical Field
The invention relates to the field of graphene material preparation, and particularly relates to a graphene/polypyrrole particle composite gel film and a preparation method thereof.
Background
Graphene is a six-membered ring two-dimensional material formed by hybridization of carbon atoms SP2, has excellent mechanical properties, electrical properties and thermal properties, and is widely concerned in research.
The polypyrrole has higher specific capacity and higher conductivity, is an ideal electrode component material, is introduced into a graphene material, modifies the graphene, and can effectively improve the energy density of the graphene material. However, because polypyrrole has poor water dispersibility, when polypyrrole is introduced into a graphene material by a conventional preparation method, it is difficult to prepare a graphene/polypyrrole particle composite film in which polypyrrole is uniformly distributed.
In view of the above-mentioned drawbacks, the inventors of the present invention have finally obtained the present invention through a long period of research and practice.
Disclosure of Invention
In order to solve the technical defects, the technical scheme adopted by the invention is to provide a preparation method of a graphene/polypyrrole particle composite gel film, which is characterized by comprising the following steps:
s1, mixing the pyrrole and the hydrochloric acid solution in a gel pool to form a gel pool solution;
s2, uniformly mixing graphene oxide and the dispersion liquid of the metal oxide particles with the high oxidation state number to form graphene oxide/metal oxide with the high oxidation state number, and adding the graphene oxide/metal oxide with the high oxidation state number into a feeding container;
s3, squeezing the graphene oxide/metal oxide with high oxidation state into a gel pool through a nozzle connected with the fluid conveying machine by utilizing the fluid conveying machine, and contacting the graphene oxide/metal oxide with high oxidation state with the gel pool solution to generate the graphene oxide/polypyrrole particle composite hydrogel film;
s4, adding the graphene oxide/polypyrrole particle composite hydrogel film into a reducing solution through a conveying wheel to generate a graphene/polypyrrole particle composite hydrogel film;
and S5, drying the graphene/polypyrrole particle composite hydrogel film to obtain the graphene/polypyrrole particle composite hydrogel film.
Preferably, the drying method in step S5 includes air drying and vacuum drying.
Preferably, the drying method in step S5 further includes freeze drying and supercritical drying.
Preferably, the metal oxide with a high oxidation state comprises manganese oxide, iron oxide, cobalt dioxide, tin oxide and chromium oxide.
Preferably, the particle size of the metal oxide with high oxidation state is 10-500 nm.
Preferably, the fluid delivery mechanism in step S3 includes an injection pump and a turbo-pressurizing pump.
Preferably, the reducing solution in step S4 includes a hydroiodic acid solution and a vitamin C solution.
Preferably, the concentration of pyrrole in the gel pool solution is 0.1-5 vol%.
Preferably, the cross-sectional width of the nozzle at step S3 is in the range of 0.1mm-12mm, and the cross-sectional length of the nozzle is adjustable in the range of 0.1mm-1 m.
The invention provides a graphene/polypyrrole particle composite gel film.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a preparation method of a graphene/polypyrrole particle composite gel film, which takes a graphene oxide dispersion liquid and a high oxidation state metal oxide particle dispersion liquid as precursors, utilizes the characteristics that the high oxidation state metal oxide particles have oxidability, good water dispersibility and easy uniform distribution in the graphene oxide dispersion liquid, and uses the high oxidation state metal oxide particles as a template in a polypyrrole generation process, so that the polypyrrole particles in the graphene/polypyrrole particle composite film prepared by the method are uniformly distributed;
2. according to the preparation method of the graphene/polypyrrole particle composite gel film, a wet spinning method is adopted in a film forming process, the width and the thickness of the prepared graphene oxide/polypyrrole particle composite hydrogel film can be controlled by adjusting the injection speed of the graphene oxide/high oxidation state metal oxide mixed dispersion liquid and the size of a nozzle, and further the size of the graphene/polypyrrole particle composite gel film prepared by the method is controllable;
3. according to the preparation method of the graphene/polypyrrole particle composite gel film, the mixed dispersion liquid is conveyed by using a fluid conveying machine, and the prepared graphene oxide/polypyrrole particle composite hydrogel film can be automatically conveyed to a reducing solution in a reduction pool through a conveying wheel to perform a reduction reaction to generate the graphene/polypyrrole particle composite gel film, so that the preparation method of the graphene/polypyrrole particle composite gel film has the advantages of simple and reliable process method and easiness in batch production;
4. according to the preparation method of the graphene/polypyrrole particle composite hydrogel film, provided by the invention, by utilizing the characteristics of good water dispersibility and high oxidizability of the high oxidation state metal oxide, the prepared polypyrrole particles are uniformly distributed in the generated graphene oxide/polypyrrole particle composite hydrogel film, the generated graphene/polypyrrole particle composite hydrogel film does not contain the high oxidation state metal oxide, other impurities influencing the performance of the graphene/polypyrrole particle composite hydrogel film cannot be introduced in the reaction process, and the step of removing small balls in the traditional graphene material modification is omitted while the product performance is improved;
5. the invention provides a graphene/polypyrrole particle composite gel film, wherein polypyrrole particles in the graphene/polypyrrole particle composite gel film are uniformly distributed, and the uniformly distributed polypyrrole particles prop apart adjacent graphene sheet layers, so that the graphene/polypyrrole particle composite gel film has a porous structure, and the porous structure can increase the contact area with an electrolyte when the graphene/polypyrrole particle composite gel film is used as an electrode material, and can effectively prevent aggregation between the graphene sheet layers.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below.
Fig. 1 is a schematic flow chart of a process for preparing a graphene/polypyrrole particle composite gel thin film according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a graphene/polypyrrole particle composite hydrogel thin film according to the second embodiment of the present invention;
fig. 3 is a scanning electron microscope image of the surface of the graphene/polypyrrole particle composite gel thin film in the second embodiment of the present invention;
fig. 4 is a carbon distribution diagram of the surface of the graphene/polypyrrole particle composite gel thin film in the second embodiment of the present invention;
fig. 5 is a nitrogen distribution diagram of the surface of the graphene/polypyrrole particle composite gel thin film in the second embodiment of the present invention;
fig. 6 is a distribution diagram of oxygen on the surface of the graphene/polypyrrole particle composite gel thin film in the second embodiment of the present invention;
fig. 7 is a scanning electron microscope image of a cross section of the graphene/polypyrrole particle composite gel thin film in the second embodiment of the present invention.
The figures in the drawings represent:
1-a fluid transfer machine; 2-a transfer wheel; 3-a gel pool; 4-reduction pool.
Detailed Description
The above and further features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.
Example one
Referring to fig. 1, fig. 1 is a schematic view of a process flow of preparing a graphene/polypyrrole particle composite gel film in this embodiment.
The preparation method of the graphene/polypyrrole particle composite gel film provided by the embodiment comprises the following steps:
s1, mixing pyrrole and hydrochloric acid solution in a gel pool 3 to form gel pool solution;
s2, uniformly mixing the graphene oxide with the dispersion liquid of the metal oxide particles with the high oxidation state to form a graphene oxide/metal oxide with the high oxidation state, and adding the graphene oxide/metal oxide with the high oxidation state into a feeding container;
s3, squeezing the graphene oxide/metal oxide with high oxidation state number mixed dispersion liquid in the step S2 into a gel pool 3 through a nozzle connected with the fluid conveying machine 1 by using the fluid conveying machine 1, and contacting the graphene oxide/metal oxide with high oxidation state number mixed dispersion liquid with a gel pool solution to generate a graphene oxide/polypyrrole particle composite hydrogel film;
s4, adding the graphene oxide/polypyrrole particle composite hydrogel film generated in the step S3 into a reducing solution through a conveying wheel 2 to generate a graphene/polypyrrole particle composite hydrogel film;
and S5, drying the graphene/polypyrrole particle composite hydrogel film generated in the step S4 to obtain the graphene/polypyrrole particle composite gel film.
Wherein the concentration of pyrrole in the solution of the gel pool is 0.1-5 vol%, and the concentration of hydrochloric acid is 0.1-10 mol/L; the graphene oxide is prepared by a hummers method, and the size of a sheet layer of the graphene oxide is 10-500 mu m; taking the graphene oxide dispersion liquid and the high oxidation state metal oxide particle dispersion liquid as precursors, and firstly obtaining the graphene oxide/high oxidation state metal oxide mixed dispersion liquid with uniformly dispersed high oxidation state metal oxide particles by utilizing the characteristic of better water dispersibility of the high oxidation state metal oxide; the concentration of the preferable graphene oxide dispersion liquid is 5-30 mg/mL, the concentration of the preferable high oxidation state metal oxide mixed dispersion liquid is 1-80 mg/mL, and the volume ratio of the preferable graphene oxide dispersion liquid to the high oxidation state metal oxide mixed dispersion liquid is 5-0.5; adding the prepared graphene oxide/metal oxide mixed dispersion liquid with high oxidation state into a gel pool solution containing pyrrole, contacting the pyrrole with metal oxide particles with high oxidation state, taking the metal oxide particles with high oxidation state as a template, oxidizing the pyrrole to generate polypyrrole under the oxidation action of the metal oxide with high oxidation state, gradually increasing the amount of the generated polypyrrole along with the progress of oxidation reaction, gradually reducing the metal oxide particles with high oxidation state along with the progress of reaction until the metal oxide particles with high oxidation state are completely consumed, finishing the oxidation reaction, gradually replacing the original metal oxide particles with newly generated polypyrrole to form polypyrrole particles with the same shape, size and position as the metal oxide particles with high oxidation state as the template, namely replacing the metal oxide particles with high oxidation state as the template with the generated polypyrrole particles, dispersed in graphene oxide; because the high oxidation state metal oxide has the characteristic of good water dispersibility, the high oxidation state metal oxide particles are uniformly dispersed in the graphene oxide/high oxidation state metal oxide mixed dispersion liquid, and the newly generated polypyrrole particles replace the positions of the high oxidation state metal oxide particles, therefore, the prepared polypyrrole particles are uniformly distributed in the generated graphene oxide/polypyrrole particle composite hydrogel film, and because the high oxidation state metal oxide is completely consumed in the reaction, the generated graphene oxide/polypyrrole particle composite hydrogel film does not contain the high oxidation state metal oxide, and other impurities influencing the performance of the graphene/polypyrrole particle composite hydrogel film cannot be introduced in the reaction process, so that the product performance is improved, and the small ball removing step required in the traditional graphene material modification is omitted, the reaction process is simplified.
In the reaction, the high oxidation state metal oxide particles simultaneously play the roles of an oxidant, a sacrificial template and a polypyrrole particle dispersing agent, so that the performance of the product is improved, and the reaction steps are simplified.
The particle size of the high oxidation state metal oxide particles is 10-500 nm, so that the particle size of polypyrrole particles in the generated graphene/polypyrrole particle composite gel film is controlled to be 10-500 nm.
The generated polypyrrole particles are interacted with functional groups on adjacent graphene oxide sheet layers, so that the acting force between the graphene oxide sheet layers is enhanced, a gel is formed, the conversion from sol to the gel is realized, the polypyrrole particles generated by taking the metal oxide particles with high oxidation state as a template are uniformly dispersed in the formed gel, the distance between the adjacent graphene oxide sheet layers is expanded due to the existence of the polypyrrole particles, and the formed graphene oxide/polypyrrole particle composite gel film has a uniform porous structure; because the shape and the size of the generated polypyrrole particles are the same as those of the high oxidation state metal oxide particles serving as the template, the shape and the size of the generated polypyrrole particles can be controlled by controlling the shape and the size of the high oxidation state metal oxide particles, and further the pore structure and the pore size of the generated graphene oxide/polypyrrole particle composite gel film are controlled, so that the structure of the generated graphene/polypyrrole particle composite gel film can be controlled.
In the film forming process, by a method similar to wet spinning, a fluid conveying machine 1 is utilized, graphene oxide/metal oxide mixed dispersion liquid with high oxidation state is extruded into a gel pool 3 through a nozzle connected with the fluid conveying machine 1 at a certain injection speed, the graphene oxide/metal oxide mixed dispersion liquid with high oxidation state is contacted with a gel pool solution, and pyrrole in the gel pool solution is oxidized by the metal oxide with high oxidation state to generate polypyrrole particles and interacts with adjacent graphene oxide through functional groups, so that the acting force between graphene oxide sheet layers is enhanced, the conversion from sol to gel is realized, and the graphene oxide/polypyrrole particle composite hydrogel film is generated; wherein, the injection speed refers to the ratio of the injection volume of the fluid conveying machine 1 in unit propelling time to the corresponding cross-sectional area of the nozzle; the preferred injection speed of the invention is 0.1-20 mm/s; according to the technical process, the width and the thickness of the prepared graphene oxide/polypyrrole particle composite hydrogel film can be controlled by adjusting the injection speed of the graphene oxide/high oxidation state metal oxide mixed dispersion liquid and the size of a nozzle according to requirements, the preferred width of the cross section of the nozzle is 0.1-12 mm, the preferred length of the cross section of the nozzle is 0.1-1 m, namely the thickness and the width of the prepared graphene oxide/polypyrrole particle composite hydrogel film are 0.1-12 mm and 0.1-1 m respectively; the length of the prepared graphene oxide/polypyrrole particle composite hydrogel film can be set randomly according to requirements; because the fluid conveying machine 1 is used for conveying the mixed dispersion liquid, the prepared graphene oxide/polypyrrole particle composite hydrogel film can be automatically conveyed to the reducing solution in the reduction tank 4 through the conveying wheel 2 for reduction reaction to generate the graphene/polypyrrole particle composite gel film, so that the preparation method of the graphene/polypyrrole particle composite gel film has the advantages of controllable film size, simple and reliable process method and easiness in batch production, and can be applied to preparation of electrode materials of supercapacitors in a large scale.
When the technical scheme is used for reduction reaction, the preferable reducing solution is a vitamin C solution and a hydriodic acid solution; wherein the optimal concentration of the vitamin C solution is 0.1-100 g/L, the temperature during reduction is preferably 0-100 ℃, and the reduction time is preferably 1-600 min; the preferable concentration of the hydriodic acid solution is 1-55%, the temperature during reduction is preferably 0-100 ℃, and the reduction time is preferably 1-600 min.
Drying the prepared graphene/polypyrrole particle composite hydrogel film to obtain a graphene/polypyrrole particle composite hydrogel film; the drying method can be air drying or vacuum drying, or freeze drying or supercritical drying. The dried graphene/polypyrrole particle composite gel film can be used as an electrode material of a water-system electrolyte super capacitor and an electrode material of an organic electrolyte system super capacitor, and even if the mobility and ionic conductivity of the organic electrolyte are low and the specific capacity of the super capacitor is reduced, the organic electrolyte has higher decomposition voltage, so that the working voltage of the super capacitor is remarkably improved, and the energy density is higher.
When the method of drying in air or vacuum drying is selected, the drying temperature is selected to be 20-100 ℃, and the drying time is 2-10 hours; after drying in the air or vacuum drying, the water in the graphene/polypyrrole particle composite hydrogel film is evaporated, the graphene sheet layers are stacked more densely, and the sheet layers are separated by uniformly distributed polypyrrole particles to form the graphene/polypyrrole particle composite hydrogel film.
When freeze drying or supercritical drying is selected, the drying temperature is-60 ℃ to 0 ℃, and the drying time is 2 to 10 hours; after freeze drying or supercritical drying, the graphene sheets in the product have larger interlayer spacing and a looser structure, and the graphene/polypyrrole particle composite xerogel film with uniformly distributed polypyrrole particles among the layers is formed. The graphene/polypyrrole particle composite xerogel film is used for a super capacitor, and the specific capacity of the super capacitor can be effectively improved.
Example two
The preparation method of the graphene/polypyrrole particle composite gel film provided by the embodiment comprises the following steps:
s1, mixing pyrrole with a hydrochloric acid solution in a gel pool 3 to form a gel pool solution, wherein the volume of the gel pool solution is 200mL, the content of pyrrole in the gel pool solution is 0.1 vol%, and the concentration of hydrochloric acid is 1 mol/L;
s2, violently stirring or shaking 2mL of graphene oxide with the concentration of 5mg/mL and 1mL of manganese oxide particle dispersion liquid with the concentration of 5mg/mL for 2min to uniformly mix the graphene oxide and the manganese oxide particles to form graphene oxide/manganese oxide mixed dispersion liquid, and adding the graphene oxide/manganese oxide mixed dispersion liquid into a feeding container, wherein the particle size of manganese oxide particles in the step is 20 nm;
s3, extruding the graphene oxide/manganese oxide mixed dispersion liquid into a gel pool through a nozzle connected with an injection pump, wherein the injection speed of the injection pump is 5mm/S, and the size of the nozzle is 0.4mm multiplied by 12 mm; contacting the graphene oxide/manganese oxide mixed dispersion liquid with a gel pool solution, and standing for 30min to generate a graphene oxide/polypyrrole particle composite hydrogel film;
and S4, adding the graphene oxide/polypyrrole particle composite hydrogel film obtained in the step S3 into a 22.5% hydriodic acid solution through a conveying wheel, and reducing at 80 ℃ for 6 hours to obtain the graphene/polypyrrole particle composite hydrogel film.
Because a large number of water molecules exist in the graphene/polypyrrole particle composite hydrogel film, electrolyte ions in aqueous electrolyte can be favorably diffused into the electrode, so that the graphene/polypyrrole particle composite hydrogel film can be directly soaked in the aqueous electrolyte to be used as an aqueous supercapacitor electrode material; the graphene/polypyrrole particle composite hydrogel film prepared in the embodiment is used as a supercapacitor material, a potassium chloride solution with the concentration of 1mol/L is used as an electrolyte to assemble a supercapacitor, and the specific capacity of the supercapacitor can reach 165F/g.
The thickness of the graphene/polypyrrole particle composite hydrogel film prepared by the embodiment is 0.4mm, the width is 12mm, and the length can be selected according to needs; the particle size of polypyrrole particles in the graphene/polypyrrole particle composite hydrogel film is 20nm, and the polypyrrole particles are uniformly distributed in the graphene/polypyrrole particle composite hydrogel film.
Referring to fig. 2, fig. 2 is a schematic diagram of the graphene/polypyrrole particle composite hydrogel film prepared in this embodiment, and the graphene/polypyrrole particle composite hydrogel film prepared by this method has a regular shape and a controllable size, and is suitable for mass production.
And S5, freeze-drying the graphene/polypyrrole particle composite hydrogel film generated in the step S4 for 10 hours at the temperature of 50 ℃ below zero in vacuum to obtain the graphene/polypyrrole particle composite hydrogel film.
Referring to fig. 3, fig. 3 is a scanning electron microscope image of the surface of the graphene/polypyrrole particle composite gel thin film prepared in this embodiment. EDS element content analysis is carried out on the graphene/polypyrrole particle composite gel film, and the element content is shown in a table 1:
TABLE 1
| Element | Weight％ | Atomic％ |
| CK | 61.85 | 66.84 |
| NK | 19.07 | 17.67 |
| OK | 19.09 | 15.49 |
| Totals | 100.00 |
As can be seen from table 1, the surface of the graphene/polypyrrole particle composite gel thin film prepared by the present invention mainly comprises carbon and nitrogen elements, which indicates that particles in the prepared graphene/polypyrrole particle composite gel thin film are polypyrrole particles, that is, manganese oxide particles are completely consumed as a template in the reaction, and the polypyrrole particles substitute for the manganese oxide particles and are distributed in the graphene/polypyrrole particle composite gel thin film.
Referring to fig. 4, 5, and 6, fig. 4, 5, and 6 are respectively a carbon element distribution diagram, a nitrogen element distribution diagram, and an oxygen element distribution diagram of the surface of the graphene/polypyrrole particle composite gel thin film prepared in this embodiment, and it can be seen from the diagrams that nitrogen elements, carbon elements, and oxygen elements are uniformly distributed in the graphene/polypyrrole particle composite gel thin film, and since nitrogen elements are elements in the polypyrrole particles and the distribution of nitrogen elements represents the distribution of the polypyrrole particles, nitrogen elements are uniformly distributed, which indicates that the polypyrrole particles are uniformly distributed in the graphene/polypyrrole particle composite gel thin film.
Referring to fig. 7, fig. 7 is an electron mirror image of a cross section of the graphene/polypyrrole particle composite gel thin film prepared in this embodiment, and it can be seen from the image that the cross section of the graphene/polypyrrole particle composite gel thin film is a uniform porous structure, and these porous structures can increase the structural area with the electrolyte and can effectively prevent aggregation between graphene sheets when the graphene/polypyrrole particle composite gel thin film is used as an electrode material.
EXAMPLE III
The preparation method of the graphene/polypyrrole particle composite gel film provided by the embodiment comprises the following steps:
s1, mixing pyrrole with a hydrochloric acid solution in a gel pool 3 to form a gel pool solution, wherein the volume of the gel pool solution is 200mL, the content of pyrrole in the gel pool solution is 1 vol%, and the concentration of hydrochloric acid is 1 mol/L;
s2, violently stirring or shaking 2mL of graphene oxide with the concentration of 10mg/mL and 1mL of iron oxide particle dispersion liquid with the concentration of 20mg/mL for 2min to uniformly mix the graphene oxide and the iron oxide particles to form graphene oxide/iron oxide mixed dispersion liquid, and adding the graphene oxide/iron oxide mixed dispersion liquid into a feeding container, wherein the particle size of the iron oxide particles in the step is 200 nm;
s3, extruding the graphene oxide/ferric oxide mixed dispersion liquid into a gel pool through a nozzle connected with a turbine pressure pump, wherein the injection speed of the turbine pressure pump is 10mm/S, and the size of the nozzle is 0.2mm multiplied by 2 mm; contacting the graphene oxide/ferric oxide mixed dispersion liquid with a gel pool solution, and standing for 30min to generate a graphene oxide/polypyrrole particle composite hydrogel film;
s4, adding the graphene oxide/polypyrrole particle composite hydrogel film obtained in the step S3 into a 0.1g/L vitamin C solution through a conveying wheel 2, and reducing the mixture at 100 ℃ for 600min to obtain the graphene oxide/polypyrrole particle composite hydrogel film.
And S5, freeze-drying the graphene/polypyrrole particle composite hydrogel film generated in the step S4 at-60 ℃ for 10 hours to obtain the graphene/polypyrrole particle composite xerogel film.
The graphene/polypyrrole particle composite xerogel film prepared by the embodiment has the thickness of 0.2mm, the width of 2mm and the length which can be selected according to the needs; the particle size of polypyrrole particles in the graphene/polypyrrole particle composite hydrogel film is 200nm, and the polypyrrole particles are uniformly distributed in the graphene/polypyrrole particle composite xerogel film.
Example four
The preparation method of the graphene/polypyrrole particle composite gel film provided by the embodiment comprises the following steps:
s1, mixing pyrrole and hydrochloric acid solution in a gel pool 3 to form gel pool solution, wherein the volume of the gel pool solution is 200mL, the content of pyrrole in the gel pool solution is 2 vol%, and the concentration of hydrochloric acid is 5 mol/L;
s2, violently stirring or shaking 2mL of graphene oxide with the concentration of 15mg/mL and 1mL of tin oxide particle dispersion liquid with the concentration of 40mg/mL for 2min to uniformly mix the graphene oxide and the tin oxide particles to form graphene oxide/tin oxide mixed dispersion liquid, and adding the graphene oxide/tin oxide mixed dispersion liquid into a feeding container, wherein the particle size of iron oxide particles in the step is 300 nm;
s3, extruding the graphene oxide/tin oxide mixed dispersion liquid into a gel pool through a nozzle connected with a turbine pressure pump, wherein the injection speed of the turbine pressure pump is 16mm/S, and the size of the nozzle is 0.4mm multiplied by 12 mm; contacting the graphene oxide/tin oxide mixed dispersion liquid with a gel pool solution, and standing for 30min to generate a graphene oxide/polypyrrole particle composite hydrogel film;
s4, adding the graphene oxide/polypyrrole particle composite hydrogel film obtained in the step S3 into a vitamin C solution with the concentration of 50g/L through a conveying wheel 2, and reducing the solution at 50 ℃ for 1 hour to obtain the graphene/polypyrrole particle composite hydrogel film.
And S5, drying the graphene/polypyrrole particle composite hydrogel film generated in the step S4 in the air at 100 ℃ for 2 hours to obtain the graphene/polypyrrole particle composite xerogel film.
The graphene/polypyrrole particle composite xerogel film prepared by the embodiment has the thickness of 0.4mm, the width of 12mm and the length which can be selected according to the needs; the particle size of polypyrrole particles in the graphene/polypyrrole particle composite hydrogel film is 300nm, and the polypyrrole particles are uniformly distributed in the graphene/polypyrrole particle composite xerogel film.
EXAMPLE five
The preparation method of the graphene/polypyrrole particle composite gel film provided by the embodiment comprises the following steps:
s1, mixing pyrrole and hydrochloric acid solution in a gel pool 3 to form gel pool solution, wherein the volume of the gel pool solution is 200mL, the content of pyrrole in the gel pool solution is 3 vol%, and the concentration of hydrochloric acid is 6 mol/L;
s2, violently stirring or shaking 2mL of graphene oxide with the concentration of 20mg/mL and 1mL of cobalt dioxide particle dispersion liquid with the concentration of 60mg/mL for 2min to uniformly mix the graphene oxide and the cobalt dioxide particles to form graphene oxide/cobalt dioxide mixed dispersion liquid, and adding the graphene oxide/cobalt dioxide mixed dispersion liquid into a feeding container, wherein the particle size of the cobalt dioxide particles in the step is 400 nm;
s3, extruding the graphene oxide/cobalt dioxide mixed dispersion liquid into a gel pool through a nozzle connected with a turbine pressure pump, wherein the injection speed of the turbine pressure pump is 16mm/S, and the size of the nozzle is 0.4mm multiplied by 12 mm; contacting the graphene oxide/cobalt dioxide mixed dispersion liquid with a gel pool solution, and standing for 30min to generate a graphene oxide/polypyrrole particle composite hydrogel film;
and S4, adding the graphene oxide/polypyrrole particle composite hydrogel film obtained in the step S3 into a vitamin C solution with the concentration of 100g/L through a conveying wheel 2, and reducing the mixture at 10 ℃ for 3 hours to obtain the graphene/polypyrrole particle composite hydrogel film.
And S5, carrying out carbon dioxide supercritical drying on the graphene/polypyrrole particle composite hydrogel film generated in the step S4 for 24 hours to obtain the graphene/polypyrrole particle composite xerogel film.
The graphene/polypyrrole particle composite xerogel film prepared by the embodiment has the thickness of 0.4mm, the width of 12mm and the length which can be selected according to the needs; the particle size of polypyrrole particles in the graphene/polypyrrole particle composite hydrogel film is 400nm, and the polypyrrole particles are uniformly distributed in the graphene/polypyrrole particle composite xerogel film.
EXAMPLE six
The preparation method of the graphene/polypyrrole particle composite gel film provided by the embodiment comprises the following steps:
s1, mixing pyrrole and hydrochloric acid solution in a gel pool 3 to form gel pool solution, wherein the volume of the gel pool solution is 200mL, the content of pyrrole in the gel pool solution is 5 vol%, and the concentration of hydrochloric acid is 10 mol/L;
s2, violently stirring or shaking 2mL of graphene oxide with the concentration of 30mg/mL and 1mL of chromium oxide particle dispersion liquid with the concentration of 80mg/mL for 2min to uniformly mix the graphene oxide and the chromium oxide particles to form graphene oxide/chromium oxide mixed dispersion liquid, and adding the graphene oxide/chromium oxide mixed dispersion liquid into a feeding container, wherein the particle size of the chromium oxide particles in the step is 500 nm;
s3, extruding the graphene oxide/chromium oxide mixed dispersion liquid into a gel pool through a nozzle connected with a turbine pressure pump, wherein the injection speed of the turbine pressure pump is 20mm/S, and the size of the nozzle is 0.4mm multiplied by 12 mm; contacting the graphene oxide and chromium oxide mixed dispersion liquid with a gel pool solution, and standing for 30min to generate a graphene oxide/polypyrrole particle composite hydrogel film;
and S4, adding the graphene oxide/polypyrrole particle composite hydrogel film obtained in the step S3 into a 55% hydriodic acid solution through a conveying wheel 2, and reducing at 80 ℃ for 6 hours to obtain the graphene/polypyrrole particle composite hydrogel film.
And S5, carrying out carbon dioxide supercritical drying on the graphene/polypyrrole particle composite hydrogel film generated in the step S4 for 10 hours to obtain the graphene/polypyrrole particle composite xerogel film.
The graphene/polypyrrole particle composite xerogel film prepared by the embodiment has the thickness of 0.4mm, the width of 12mm and the length which can be selected according to the needs; the particle size of polypyrrole granules in the graphene/polypyrrole granule composite hydrogel film is 500nm, and the polypyrrole granules are uniformly distributed in the graphene/polypyrrole granule composite xerogel film.
EXAMPLE seven
According to the graphene/polypyrrole particle composite gel film prepared by the preparation method in the embodiment, polypyrrole particles in the graphene/polypyrrole particle composite gel film are uniformly distributed, and the polypyrrole particles are used as an active substance and an intercalation substance to construct a porous structure and simultaneously introduce a high specific volume phase, so that the graphene/polypyrrole particle composite gel film can be used as an electrode material of a supercapacitor of an organic electrolyte system, and even if the mobility and the ionic conductivity of the organic electrolyte are low and the specific volume of the supercapacitor is reduced, the organic electrolyte has higher decomposition voltage, so that the working voltage of the supercapacitor is remarkably improved, and the supercapacitor has higher energy density.
The graphene/polypyrrole particle composite gel film provided by the invention has the thickness of 1-2000 um, the width of 0.1-1 m, and the length of the film can be infinitely prolonged according to the actual volume of injection slurry. Polypyrrole granules are uniformly distributed among graphene sheet layers, so that graphene is prevented from agglomerating or stacking to form a microscopic porous structure.
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. A preparation method of a graphene/polypyrrole particle composite gel film is characterized by comprising the following steps:
s1, mixing the pyrrole and the hydrochloric acid solution in a gel pool to form a gel pool solution;
s2, uniformly mixing graphene oxide and the dispersion liquid of the metal oxide particles with high oxidation state numbers to form graphene oxide/metal oxide with high oxidation state numbers, and adding the graphene oxide/metal oxide with high oxidation state numbers into a feeding container; wherein, the metal oxide with high oxidation valence state comprises manganese oxide, ferric oxide, cobalt dioxide, tin oxide and chromium oxide; the particle size of the high oxidation valence metal oxide is 10-500 nm;
s3, squeezing the graphene oxide/metal oxide mixed dispersion liquid with high oxidation state into a gel pool through a nozzle connected with the fluid conveying machinery by utilizing a fluid conveying machinery, and contacting the graphene oxide/metal oxide mixed dispersion liquid with high oxidation state with the gel pool solution to generate a graphene oxide/polypyrrole particle composite hydrogel film;
s4, adding the graphene oxide/polypyrrole particle composite hydrogel film into a reducing solution through a conveying wheel to generate a graphene/polypyrrole particle composite hydrogel film;
and S5, drying the graphene/polypyrrole particle composite hydrogel film to obtain the graphene/polypyrrole particle composite hydrogel film.
2. The method for preparing a graphene/polypyrrole particle composite gel thin film according to claim 1, wherein the drying treatment method in step S5 includes drying in air and vacuum drying.
3. The method for preparing a graphene/polypyrrole particle composite gel thin film according to claim 1, wherein the drying treatment method in step S5 further includes freeze drying and supercritical drying.
4. The method for preparing a graphene/polypyrrole particle composite gel thin film according to claim 1, wherein the fluid transfer mechanism in step S3 includes a syringe pump and a turbo-pump.
5. The method of preparing a graphene/polypyrrole particle composite gel thin film according to claim 4, wherein the reducing solution in step S4 includes a hydriodic acid solution and a vitamin C solution.
6. The method for preparing the graphene/polypyrrole particle composite gel thin film according to claim 5, wherein the concentration of pyrrole in the gel pool solution is 0.1-5 vol%.
7. The method for preparing a graphene/polypyrrole granule composite gel thin film according to claim 6, wherein the cross-sectional width of the nozzle in step S3 is in a range of 0.1mm to 12mm, and the cross-sectional length of the nozzle is adjustable in a range of 0.1mm to 1 m.
8. A graphene/polypyrrole particle composite gel thin film prepared by the preparation method of the graphene/polypyrrole particle composite gel thin film according to any one of claims 1 to 7.
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