CN109192550B - Self-supporting film and preparation method and application thereof - Google Patents
Self-supporting film and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 36
- 239000007864 aqueous solution Substances 0.000 claims abstract description 35
- 239000012528 membrane Substances 0.000 claims abstract description 31
- 150000002505 iron Chemical class 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
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- 239000000243 solution Substances 0.000 claims description 35
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000010408 film Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
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- 238000005303 weighing Methods 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 229940071870 hydroiodic acid Drugs 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims 1
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 67
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 67
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 16
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for 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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses an inorganic nanoparticle loaded reduced graphene oxide self-supporting film, a preparation method and application. The invention stirs the polyvinyl alcohol PVA aqueous solution and the GO aqueous solution containing inorganic iron salt at constant temperature until the mixture is uniform, and obtains PVA/Fe through vacuum filtration2O3the/GO membrane is reduced to prepare PVA/Fe under the action of a reducing agent2O3a/rGO membrane. The preparation method of the invention has the advantages of simple operation, mild reaction conditions and easy large-scale production, and the prepared PVA/Fe2O3the/rGO membrane composite material has excellent electrochemical performance, and the specific capacitance of the composite material as a positive electrode material and a negative electrode material of a super capacitor respectively reaches 534F/g and 838.2F/g under the current density of 10A/g.
Description
Technical Field
The invention relates to the technical field of chemical materials and energy storage materials, in particular to a reduced graphene oxide self-supporting film loaded by inorganic nanoparticles, a preparation method and application.
Background
The super capacitor is an electrochemical energy storage device and has the advantages of high charge-discharge rate, high power density, long service life, safety, environmental protection and the like. The supercapacitor has a higher specific capacitance than other secondary batteries. The specific capacitance of the super capacitor is mainly provided by substances with redox reaction, and the redox substances applied to the super capacitor material at present comprise metal oxides, metal hydroxides, conductive polymers and the like. Among them, iron element is abundant in the earth, and the mining conditions are mature, so it is a very important place in national economy. Therefore, the application of the iron oxide with low cost to the super capacitor can greatly reduce the production cost.
Graphene (Graphene), a single atomic layer with close-packed carbon atoms, was commonly found by two scientists at the university of manchester, uk in 2004, and has received much attention both at home and abroad due to its good light transmission, electrical conductivity and extremely high mechanical strength. To date, graphene has been developed and applied in electronic components, optoelectronic materials, and energy applications. Graphene-based carbon-based supercapacitors are ideal flexible supercapacitors. However, the capacitor specific capacitance of graphene is low, so that the preparation of the organic-inorganic composite supercapacitor by taking graphene as a support material has extremely important practical significance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an inorganic nanoparticle-supported reduced graphene oxide self-supporting film, a preparation method and application. The invention combines the high conductivity, Fe, of the rGO material2O3The high specific capacitance capability and the adhesive PVA safety, thereby preparing the self-supporting film to be applied to the field of solid-state supercapacitors. The preparation method of the invention has simple operation, mild reaction conditions and easy large-scale production.
According to the invention, the reduced graphene material is obtained by reducing graphene oxide with a reducing agent, iron oxide is loaded on the surface of graphene in the reduction process, and the iron oxide, the graphene oxide and the iron oxide are stably combined together by utilizing the cross-linking effect of polyvinyl alcohol (PVA), so that the performance of the supercapacitor is effectively improved, and the recycling stability of the material is enhanced. The technical scheme of the invention is specifically introduced as follows.
A preparation method of an inorganic nanoparticle loaded reduced graphene oxide self-supporting film comprises the following specific steps:
(1) weighing PVA in deionized water, heating to 80-90 ℃, and continuously stirring until the solution is clear and transparent to obtain a PVA aqueous solution;
(2) taking inorganic iron salt, and carrying out ultrasonic treatment on the inorganic iron salt in 1.5-2.5 mg/ml graphene oxide GO solution for 25-35 min to obtain a uniformly mixed GO aqueous solution containing the inorganic iron salt;
(3)dripping GO aqueous solution containing inorganic iron salt into PVA aqueous solution, stirring until the inorganic iron salt and the PVA aqueous solution are uniformly mixed, and obtaining PVA/FeCl through a vacuum filtration mode3a/GO membrane;
(4) mixing PVA/FeCl3the/GO membrane is placed in a reducing agent solution, reacts for 0.5-3 hours at the temperature of 60-100 ℃, and is subjected to post-treatment to obtain the reduced graphene oxide self-supporting film loaded with inorganic nano particles, namely PVA/Fe2O3a/rGO membrane.
In the invention, in the step (1), the mass volume concentration of the PVA aqueous solution is between 1 and 20 mg/mL.
In the invention, in the step (2), the inorganic ferric salt is anhydrous ferric trichloride, ferric trichloride hexahydrate, ferric nitrate or ferric sulfate; the graphene oxide GO is prepared by a Hummer method.
In the invention, in the step (2), the mass ratio of the inorganic iron salt to the graphene oxide is 20: 1-80: 1.
In the invention, in the step (3), the volume ratio of the GO aqueous solution containing the inorganic iron salt to the PVA aqueous solution is 1: 3-1: 6.
In the present invention, in the step (4), the reducing agent is selected from any one of hydrazine hydrate, hydroiodic acid, ascorbic acid, and sodium borohydride.
In the invention, in the step (4), the temperature is 90-100 ℃, and the reaction time is 1.5-3 h.
In the invention, in the step (4), the post-treatment comprises the steps of soaking the raw materials in deionized water for 12-72 hours, and then naturally drying the raw materials at the temperature of 20-40 ℃ for 12-72 hours.
The invention also provides the reduced graphene oxide self-supporting film loaded by the inorganic nano particles prepared by the preparation method.
The invention further provides an application of the reduced graphene oxide self-supporting film loaded with the inorganic nanoparticles in a supercapacitor, and the application method comprises the following steps: soaking the reduced graphene oxide self-supporting film loaded with inorganic nano particles in H2SO4Taking out the PVA solution for 1.5 to 2.5 hours, naturally drying the PVA solution at the temperature of between 20 and 40 ℃, and taking carbon cloth as a current collector to prepare the solid-state supercapacitorA material.
Above H2SO4The preparation method of the PVA aqueous solution comprises the steps of respectively taking deionized water, concentrated sulfuric acid and polyvinyl alcohol (PVA) with the mass ratio of 10:1:1, violently stirring the mixture of the deionized water, the concentrated sulfuric acid and the polyvinyl alcohol (PVA) at the temperature of 85 ℃ until the whole system is clear and transparent, and obtaining a mixed solution which is H2SO4An aqueous PVA solution.
Compared with the prior art, the beneficial effects of the invention are mainly embodied in the following aspects:
based on the physical and chemical properties of the graphene material, the redox capability of the Fe oxide is combined, and the polyvinyl alcohol PVA is used as a main binder, so that the electrochemical property of the graphene supercapacitor is further improved, and the recycling stability of the graphene supercapacitor is enhanced.
PVA/Fe by reducing agent method2O3Reduction of/GO membrane into inorganic nanoparticle-supported reduced graphene oxide self-supporting thin film (PVA/Fe)2O3rGO membrane), simple operation, mature synthesis process, easy control of reaction process and realization of mass production.
The specific capacitance of the reduced graphene oxide self-supporting film loaded by the inorganic nanoparticles as the anode material and the cathode material of the super capacitor respectively reaches 534F/g and 838.2F/g under the current density of 10A/g.
Drawings
FIG. 1 is PVA/Fe in example 12O3SEM picture of/GO membrane.
FIG. 2 is PVA/Fe in example 12O3SEM image of/rGO membrane.
FIG. 3 is a cyclic voltammetry graph in example 1.
Fig. 4 is a constant current charge and discharge curve diagram in example 1.
FIG. 5 is a cyclic voltammetry graph in example 2.
Fig. 6 is a constant current charge and discharge curve diagram in example 2.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples, but the present invention is not limited to the following examples.
The preparation method of the invention mainly adjusts PVA to Fe2O3Quality ratio of rGO to control the final product PVA/Fe2O3Electrochemical performance of/rGO membrane, inorganic iron (including FeCl) is adopted as iron source3，Fe(NO3)3Etc.), the reducing agent employs an organic reducing agent (including hydrazine hydrate, hydroiodic acid, etc.). In Fe2O3Under the condition of a certain mass proportion of rGO, the electric conductivity of the film is weakened along with the increase of the mass of PVA, the specific capacitance is reduced, but the mechanical property of the film is improved, and the tensile and anti-bending properties are enhanced.
Example 1
Weighing 0.5g of PVA in 50ml of deionized water, heating the solution to 85 ℃ in an oil bath heating mode, and continuously stirring until the solution is clear and transparent to obtain a PVA aqueous solution; 0.5g of FeCl was taken3Carrying out ultrasonic treatment for 30min in GO solution with the mass of 15mg and the concentration of 2mg/ml to obtain FeCl-containing solution which is uniformly mixed3In aqueous GO solution. Will contain FeCl3The GO aqueous solution is dripped into the PVA aqueous solution and stirred until the mixture is uniform. Obtaining PVA/FeCl under the condition of vacuum filtration3the/GO membrane (the electron microscope scanning is shown in figure 1) is placed in hydrazine hydrate solution and kept for 2 hours at 95 ℃ to obtain the electrode material PVA/Fe2O3a/rGO membrane.
Mixing PVA/Fe2O3Standing the/rGO membrane in deionized water for 6 hours, changing water for 2-4 times, and then protecting the surface structure of the material by adopting a natural drying mode to obtain self-supporting PVA/Fe2O3a/rGO membrane. Re-infiltrating in H2SO4After 2 hours, the PVA aqueous solution was taken out and dried naturally, and electrochemical performance tests (including specific capacitance, rate capability, and the like) were performed using carbon cloth as a current collector.
An electron scanning microscope (SEM, as shown in figure 2) is used for representing the surface microstructure of the material, and the material is shown to be in a three-dimensional porous structure, graphene is in a two-dimensional lamellar structure, a large number of metal oxide nanoparticles exist between lamellae, and the PVA coats the graphene and the nanoparticles, so that sufficient adhesive capacity is provided, a compact three-dimensional network structure is formed, and a foundation is provided for the high specific surface area of the super-electric material. The electrochemical performance of the Chenhua CHI760e electrochemical workstation detector is tested by the cyclic voltammetry shown in figure 3, the scanning rates are respectively 10 mV/g, 20 mV/g, 30 mV/g, 50 mV/g, 80 mV/g and 100mV/g, the voltage window is in the range of 0-0.45V, and the oxidation-reduction peak in the figure shows that the material has excellent oxidation-reduction capability. As shown in the constant current charging and discharging test of FIG. 4, the specific capacitance reaches 720, 698.9, 611 and 534F/g respectively when the test is carried out under the conditions that the current density is 1, 2, 5 and 10A/g respectively and the voltage window is 0-0.35V.
Example 2
Weighing 1g of PVA in 50ml of deionized water, heating the solution to 85 ℃ in an oil bath heating mode, and continuously stirring until the solution is clear and transparent to obtain a PVA aqueous solution; 0.5g of FeCl was taken3Carrying out ultrasonic treatment for 30min in GO solution with the mass of 15mg and the concentration of 2mg/ml to obtain FeCl-containing solution which is uniformly mixed3In aqueous GO solution. Will contain FeCl3The GO aqueous solution is dripped into the PVA aqueous solution and stirred until the mixture is uniform. Obtaining PVA/FeCl under the condition of vacuum filtration3Placing the/GO membrane in a hydrazine hydrate solution, and keeping the solution at 95 ℃ for 2 hours to obtain an electrode material PVA/Fe2O3a/rGO membrane.
Mixing PVA/Fe2O3Standing the/rGO membrane in deionized water for 6 hours, changing water for 2-4 times, and then protecting the surface structure of the material by adopting a natural drying mode to obtain self-supporting PVA/Fe2O3a/rGO membrane. Re-infiltrating in H2SO4After 2 hours, the PVA aqueous solution was taken out and dried naturally, and electrochemical performance tests (including specific capacitance, rate capability, and the like) were performed using carbon cloth as a current collector.
As shown in the test of cyclic voltammetry of FIG. 5, the scanning rates are respectively 10, 20, 30, 50, 80 and 100mV/g, the voltage window is in the range of-1.5-0V, and a pair of redox peaks in the graph shows that the material has excellent redox capability. As shown in the constant current charge and discharge test of FIG. 6, the specific capacitance respectively reaches 838.2F/g and 606.5F/g when the test is carried out under the conditions that the current density is 10A/g and 20A/g respectively and the voltage window is-1.23-0V.
Example 3
Weighing 1g of PVA in 50ml of deionized water, heating the solution to 85 ℃ in an oil bath heating mode, and continuously stirring until the solution is clear and transparent to obtain a PVA aqueous solution; taking 1g of FeCl3Carrying out ultrasonic treatment for 30min in GO solution with the mass of 15mg and the concentration of 2mg/ml to obtain FeCl-containing solution which is uniformly mixed3In aqueous GO solution. Will contain FeCl3The GO aqueous solution is dripped into the PVA aqueous solution and stirred until the mixture is uniform. Obtaining PVA/FeCl by vacuum filtration3Placing the/GO membrane in hydriodic acid solution, and keeping the membrane at 95 ℃ for 2 hours to obtain an electrode material PVA/Fe2O3a/rGO membrane.
Mixing PVA/Fe2O3Standing the/rGO membrane in deionized water for 6 hours, changing water for 2-4 times, then adopting a natural drying mode to protect the surface structure of the material, drying and obtaining PVA/Fe2O3a/rGO membrane. Re-infiltrating in H2SO4After 2 hours, the PVA aqueous solution was taken out and dried naturally, and electrochemical performance tests (including specific capacitance, rate capability, and the like) were performed using carbon cloth as a current collector.
Example 4
Weighing 0.5g of PVA in 50ml of deionized water, heating the solution to 85 ℃ in an oil bath heating mode, and continuously stirring until the solution is clear and transparent to obtain a PVA aqueous solution; 0.5g of Fe (NO) was taken3)3Performing ultrasonic treatment for 30min in GO solution with mass of 20mg and concentration of 2mg/ml to obtain Fe (NO) with uniform mixing3)3In aqueous GO solution. And (3) dropwise adding the GO aqueous solution containing ferric nitrate into the PVA aqueous solution, and stirring until the mixture is uniformly mixed. Obtaining PVA/Fe (NO) by vacuum filtration3)3Placing the/GO membrane in hydriodic acid solution, and keeping the membrane at 95 ℃ for 2 hours to obtain an electrode material PVA/Fe2O3a/rGO membrane.
Mixing PVA/Fe2O3Standing the/rGO membrane in deionized water for 6 hours, changing water for 2-4 times, then adopting a natural drying mode to protect the surface structure of the material, drying and obtaining PVA/Fe2O3a/rGO membrane. Re-infiltrating in H2SO4After 2 hours, the PVA solution was taken out and dried naturally, and then coated with carbon clothAnd (3) carrying out electrochemical performance tests (including specific capacitance, rate capability and the like) on the current collector.
The above are exemplary embodiments of the present invention, which describe the main features of the present invention, and do not limit the scope of the present invention, and all the changes and modifications of the experimental conditions according to the idea of the present invention are within the scope of the present invention.
Claims (3)
1. A preparation method of an inorganic nanoparticle-loaded reduced graphene oxide self-supporting film is characterized by comprising the following specific steps:
(1) weighing PVA in deionized water, heating to 80-90 ℃, and continuously stirring until the solution is clear and transparent to obtain a PVA aqueous solution;
(2) taking inorganic iron salt, and carrying out ultrasonic treatment on the inorganic iron salt in 1.5-2.5 mg/ml graphene oxide GO solution for 25-35 min to obtain a uniformly mixed GO aqueous solution containing the inorganic iron salt;
(3) dripping GO aqueous solution containing inorganic iron salt into PVA aqueous solution, stirring until the inorganic iron salt and the PVA aqueous solution are uniformly mixed, and obtaining PVA/FeCl through a vacuum filtration mode3a/GO membrane;
(4) mixing PVA/FeCl3Placing the GO membrane in a reducing agent solution, reacting for 0.5-3 hours at the temperature of 60-100 ℃, and performing post-treatment to obtain a reduced graphene oxide self-supporting film loaded with inorganic nanoparticles;
in the step (1), the mass volume concentration of the PVA aqueous solution is 1-20 mg/mL;
in the step (2), the inorganic ferric salt is anhydrous ferric trichloride, ferric trichloride hexahydrate, ferric nitrate or ferric sulfate; the graphene oxide GO is prepared by a Hummer method;
in the step (2), the mass ratio of the inorganic ferric salt to the graphene oxide is 20: 1-80: 1;
in the step (3), the volume ratio of the GO aqueous solution containing the inorganic iron salt to the PVA aqueous solution is 1: 3-1: 6;
in the step (4), the reducing agent is selected from any one of hydrazine hydrate, hydroiodic acid, ascorbic acid or sodium borohydride;
in the step (4), the temperature is 90-100 ℃, and the reaction time is 1.5-3 h;
in the step (4), the post-treatment comprises the steps of soaking the raw materials in deionized water for 12-72 hours, and then naturally drying the raw materials at the temperature of 20-40 ℃ for 12-72 hours.
2. An inorganic nanoparticle-supported reduced graphene oxide self-supporting thin film prepared according to the preparation method of claim 1.
3. The application of the inorganic nanoparticle-supported reduced graphene oxide self-supporting thin film in the aspect of the supercapacitor is characterized in that the application method comprises the following steps: soaking the reduced graphene oxide self-supporting film loaded with inorganic nano particles in H2SO4And after 1.5-2.5 hours in the PVA aqueous solution, taking out and naturally drying at the temperature of 20-40 ℃, and taking carbon cloth as a current collector to prepare the solid supercapacitor material.
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