CN114974936B - Preparation method of graphene supercapacitor composite electrode with high pseudo-capacitance loading capacity - Google Patents
Preparation method of graphene supercapacitor composite electrode with high pseudo-capacitance loading capacity Download PDFInfo
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
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- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a preparation method of a graphene supercapacitor composite electrode with high pseudo-capacitance loading capacity, and relates to the technical field of supercapacitors, wherein the preparation method comprises the following steps: (1) Preparing a pseudocapacitance precursor material solution, and immersing a foam polymer in the solution; (2) Taking out and drying the foam polymer absorbed with the pseudocapacitance precursor material, and then putting the foam polymer into a tablet press to press the foam polymer into a film; (3) And exposing the prepared film to laser irradiation to obtain the graphene supercapacitor composite electrode. The method overcomes the defects of insufficient doping amount, difficult doping, small precursor doping amount and the like of the existing graphene, and the prepared composite material has the advantages of high graphene quality, large pseudo-capacitance material loading amount, good cycle stability, adjustable pattern and the like; the preparation method is simple in process and low in cost, and is favorable for popularization and application as the electrode material of the super capacitor.
Description
Technical field:
the invention relates to the technical field of supercapacitors, in particular to a preparation method of a graphene supercapacitor composite electrode with high pseudo-capacitance loading capacity.
The background technology is as follows:
as the global population continues to grow, human demand for energy increases and with the growing shortage of fossil resources, the energy crisis increases, and there is an urgent need for a high power and electricity sustainable energy conversion and storage system. Intermittent renewable energy sources such as wind energy, solar energy and tidal energy have the defects of unstable power, insufficient supply quantity, non-centralized resources and the like, so the energy storage device is a key for solving the renewable energy sources. At present, the energy storage device mainly comprises: chemical energy storage devices, such as lithium batteries, fuel cells, etc., that effect charge storage by oxidation-reduction reactions; and a small portion of physical energy storage devices, such as flywheel batteries. However, they have the disadvantages of poor temperature characteristics, short service life, poor cycling stability, low energy density, environmental protection, insufficient power density, high price, poor safety and the like, and therefore, the energy storage device is always a difficulty to be solved by people. The super capacitor is also called an electric double layer capacitor, is a novel electrochemical device combining the electric energy transmission capacity and the charge storage capacity of the traditional capacitor and the battery, has the advantages of high cycle stability, long service life, high charging speed, strong large-current discharge capacity, good ultralow temperature characteristic, high power density and the like, and is an ideal energy storage device for solving the current energy crisis.
Currently, supercapacitors are largely divided into double layer capacitors and pseudocapacitance capacitors. The double-layer capacitor stores charges through an electrochemical double-layer capacitor formed by electrode materials and electrolyte, wherein the electrode materials mainly comprise activated carbon, graphene, carbon nano tubes and other carbon materials, and the double-layer capacitor has the advantages of long cycle life, high power density and the like, but has relatively low specific capacity and insufficient energy density. The pseudocapacitance capacitor takes metal oxide and conductive polymer as electrode materials, performs charge storage based on redox reaction between electrolyte and the electrode materials, has the advantages of high energy density and the like, but the metal oxide has the defects of poor conductivity, easy agglomeration and the like, so that the pseudocapacitance capacitor has lower power and thus has poor cycling stability. Therefore, researchers compound metal oxidation with conductive materials such as carbon nanotubes, activated carbon, graphene and the like to prepare the electrode material with high energy density, high power density, high cycle stability and high performance.
Graphene is considered as an ideal electrode material for supercapacitors due to its series of characteristics such as high theoretical specific surface area, excellent electron conductivity, excellent mechanical properties, and stable electrochemical properties. The main methods for preparing the graphene at present are a physical method and a chemical method, wherein the physical method generally takes graphite as a raw material, and the graphene is prepared through mechanical stripping, so that the yield is extremely low, and the large-scale production is not easy. The chemical method is a common method for preparing graphene at present, and mainly comprises a chemical vapor deposition method, a silicon carbide epitaxial growth method, a chemical oxidation-reduction method and the like. The chemical vapor deposition method and the silicon carbide epitaxial growth method sublimate carbon atoms by heating the carbon material to a relatively high temperature, deposit on the metal surface to catalyze and grow graphene, and the generated graphene has few defects and fewer oxygen-containing functional groups, but has harsh production environment and extremely high production cost of production equipment. And graphene generated by a chemical oxidation-reduction method contains a large amount of oxygen-containing functional groups and generates a large amount of pollution in the generation process. The laser-induced graphene is produced by laser-induced technology from James.M Tour subject group in 2014 through laser irradiation of polyimide film to generate local instantaneous high temperature and high pressure on the surface of the polyimide film, and the produced graphene has excellent characteristics of high crystal quality, high conductivity, few lattice defects and the like. However, when the pure graphene is used as an electrode of a supercapacitor, the energy storage capacity is poor, and the specific capacity of the supercapacitor needs to be further improved by the composite pseudo-capacitance material. On one hand, the three-dimensional porous graphene can form a conductive network in a system, so that the conductivity is improved; on the other hand, the active substances can be prevented from gathering in the preparation and growth processes, and the active substances play a role in dispersing. Thus, the defects of low energy density of the double-layer capacitor, low power density of the pseudo-capacitor and the like are overcome; the cycling stability of the capacitor is greatly improved, so that the capacitor has the advantages of high power density, high energy density and the like.
At present, related documents and patents for preparing metal oxide graphene composite materials for electrochemical capacitors mostly compound by a hydrothermal method, an electrodeposition method, a chemical vapor deposition method and the like after graphene is generated, and the defects of severe production environment, high cost, complex process and the like exist. And (3) adding a metal compound into the polymer precursor to prepare a film by a part of scholars, and generating the metal oxide graphene composite material by a high-energy beam induction technology in one step. However, the polymer precursor doping still has the challenges of low doping amount and difficult doping, and if the doping is carried out before the polymer film forming, the high-concentration doping can influence the thermo-mechanical property of the polymer after the film forming, so that the film cannot be formed; if the polymer is doped after film formation, the doping amount is very low due to the high compactness of the polymer after film formation, and the process is complex, so that the film formation quality is difficult to control. Therefore, the precursor doping preparation method which is high in concentration and content, simple and easy to operate, easy to form a film and capable of being scaled is developed, and the method has important scientific significance for realizing the development and application of the pseudocapacitance composite graphene in the energy storage field.
The invention comprises the following steps:
the invention aims to solve the technical problem of providing a preparation method of a graphene supercapacitor composite electrode with high pseudo-capacitance loading capacity.
In the invention, on one hand, foam polymerization is adopted as a substrate, so that high-concentration and high-content doping on the polymer substrate is realized, the graphene and the pseudo-capacitor are compounded at high content, and the capacitance of the electrode material is improved; on the other hand, the three-dimensional structure of the mutual penetrating connection of the grapheme enables the pseudo-capacitance material to be in contact with electrolyte ions more fully and rapidly, so that the electrochemical reaction of the pseudo-capacitance material is improved; the preparation method of the invention ensures that the pseudo-capacitance material is uniformly dispersed in the graphene bulk phase, is beneficial to improving the utilization rate of the pseudo-capacitance material, and improves the defect that the pseudo-capacitance material is easy to agglomerate, thereby improving the cycling stability of the composite material and ensuring that the composite material has more excellent electrochemical performance.
The technical problems to be solved by the invention are realized by adopting the following technical scheme:
the invention aims to provide a preparation method of a graphene supercapacitor composite electrode with high pseudo-capacitance loading capacity, which comprises the following steps:
(1) Preparing a pseudocapacitance precursor material solution, and immersing a foam polymer in the solution;
(2) Taking out and drying the foam polymer absorbed with the pseudocapacitance precursor material, and then putting the foam polymer into a tablet press to press the foam polymer into a film;
(3) And exposing the prepared film to laser irradiation to obtain the graphene supercapacitor composite electrode.
In the step (1), the pseudocapacitance precursor material is one or more of transition metal oxide, bimetallic oxide, multi-metal oxide, metal organic matter, metal inorganic matter, conductive polymer, metal hydroxide, nonmetallic compound and other compounds.
Preferably, the metal is one or more of iron, palladium, platinum, titanium, lithium, ruthenium, rubidium, silicon, manganese, zinc, magnesium, aluminum, calcium, barium, vanadium, cobalt, nickel, copper, molybdenum, zirconium, chromium and the like.
Preferably, the metal inorganic matter is one or more of chlorate, normal salt, double salt, acid salt, basic salt, borate, sulfate and the like of metal.
Preferably, the pseudocapacitance precursor material has a size of 1-10000nm.
And dissolving the pseudocapacitance precursor material in deionized water or ethanol and other solvents to prepare a pseudocapacitance precursor material solution, wherein the concentration of the pseudocapacitance precursor material solution is less than or equal to the saturation concentration.
In the step (1), the foam polymer is a composite foam polymer, a carbon single chain polymer, an aromatic-containing polymer, a semi-aromatic polymer, an aromatic heterocyclic polymer, a polyetherimide, a polyimide, a phenolic resin, a polymetallic imide, a polyethylene, a polymethacrylimideOne or more of amine, cyclic polymer, lignin and polymer with main chain containing imide ring; the density of the selected foamed polymer is 0.1-500kg/m 3 The thickness is 1-1000mm, and the length and width are any size. Preferably, the density of the selected foamed polymer is from 1 to 200kg/m 3 The thickness is 1-100mm.
In the step (2), the drying is one or more of vacuum drying, room temperature drying and freeze drying; preferably vacuum drying and room temperature drying; the drying temperature is room temperature-200 ℃, the drying time is 1min-72h, and the heating rate is 1-20 ℃/min.
In step (2), the pressure of the tablet press is 0.1-200MPa, preferably 1-25MPa; the pressing time is 0.1-30min; the thickness of the film after pressing is 0.01 to 100mm, preferably 0.1 to 5mm. In the pressing process, a flexible material can be selected as a supporting substrate, such as polyethylene terephthalate (PET) with frosting, polyvinyl chloride (PVC) with frosting, polycarbonate (PC) or other organic high polymer materials with stronger flexibility and larger friction coefficient, and can also be conductive flexible copper foil, foam nickel, foam silver, foam iron, foam zinc or other metal materials with better flexibility.
In the step (3), the adjustment parameters during laser irradiation include, but are not limited to, one or more of laser power, laser scanning speed, laser spot diameter, irradiation times, pulse frequency, foam polymer type (at least one of them), pseudocapacitance precursor material (at least one of them); the types of the laser include gas laser, solid laser, liquid laser, semiconductor laser and optical fiber laser; the laser wavelength is 10-3000nm, the scanning speed is 5-1000um/s, the laser power is 0.1-200W, the laser spot diameter is 0.5-1000um, the scanning interval is 0.1-5mm, and the pulse frequency is 2-200kHZ; the laser irradiation environment comprises an air environment and an atmosphere environment.
The second purpose of the invention is to provide a graphene supercapacitor composite electrode with high pseudo-capacitance loading prepared by the preparation method.
The graphene in the composite electrode is three-dimensional porous graphene, single-layer graphene, double-layer graphene and multi-layer stoneGraphene, platelet graphene, flocculent graphene or graphene oxide; characteristics of graphene include super hydrophilicity, high conductivity, low disorder, fewer structural defects; the specific surface area of the graphene is 5-2000m 2 /g。
The load capacity of the pseudo-capacitance material in the composite electrode is 1-80%; the shape of the pseudo-capacitance material is nanoparticle sphere, nanoparticle flower, nanoparticle block, nanowire, porous nanosphere or nanosheet, and the size is 1-200nm.
The section thickness of the composite electrode is 0.5-2000um, and the area specific capacitance is 1-10000mF.cm -2 ，10mA.cm -2 The retention rate of the capacitance is more than 94% after 6000 times of current density circulation.
The invention uses the known method to synthesize the foam polymer, soaks the pseudocapacitance precursor material decomposed by Yi Guangre in the foam polymer structure to obtain the precursor doped polymer, and presses the precursor doped polymer into a composite film in a tablet press and other equipment or presses the precursor doped polymer and the flexible substrate material into a flexible high-ductility film. And (3) carrying out laser irradiation on the polymer surface of the precursor doped polymer in an air environment or an atmosphere environment according to a scanning mode programmed by a computer, breaking down foam polymer molecular chains into single atoms or functional groups and generating graphene on the polymer film surface under a local instantaneous high-temperature and high-pressure environment generated by a laser beam, separating other heteroatom molecules from the polymer in a molecular form, and decomposing the pseudocapacitance precursor material into a pseudocapacitance material under the dual action of a photo-thermal effect. The technical scheme provided by the invention overcomes the defects of insufficient doping amount, difficult doping, small precursor doping amount and the like of the existing graphene, and the prepared composite material has the advantages of high graphene quality, large pseudo-capacitance material loading amount, good cycling stability, adjustable pattern and the like. The preparation method has the advantages of simple process, low cost and excellent electrochemical performance, and is favorable for popularization and application as an electrode material of the super capacitor.
The beneficial effects of the invention are as follows:
(1) Aiming at the defects of the existing preparation method of the pseudocapacitance composite graphene electrode material, the pseudocapacitance precursor material is doped on the graphene substrate in high concentration and high content, so that the graphene and the pseudocapacitance are compounded in high content, the type of the pseudocapacitance doping is not limited, and the pseudocapacitance composite graphene electrode material can be solid, liquid, colloid and the like.
(2) The graphene in the pseudocapacitance/graphene composite material prepared by the invention has high crystal quality, few lattice defects, and a three-dimensional porous structure, so that the ion transmission rate is greatly increased, a carrier with high specific area is provided for the pseudocapacitance material, the conductivity is high, the conductivity of the pseudocapacitance material is improved, and the electrochemical reaction is promoted.
(3) According to the invention, the pseudo-capacitance material is uniformly dispersed in the graphene, so that the pseudo-capacitance graphene composite material has ultrahigh cycling stability, and the electrochemical performance of the pseudo-capacitance graphene composite material is improved.
(4) The preparation method disclosed by the invention is simple to operate, low in cost, wide in raw materials and convenient to popularize, and can realize structure-adjustable, patternable and large-scale preparation by adjusting the process parameters, so that the preparation method is convenient to apply in multiple fields.
Description of the drawings:
FIG. 1 shows the constant current charge and discharge test results of the pseudocapacitance/graphene composite material prepared in example 1 under different laser scanning speeds;
FIG. 2 is an XRD pattern of a pseudocapacitance/graphene composite material prepared in example 2 of the present invention;
FIG. 3 is an SEM image of undoped pseudocapacitance formed in accordance with example 2;
FIG. 4 is an SEM image of a pseudocapacitance/graphene composite material made in accordance with example 2 of the present invention;
FIG. 5 is a single electrode charge-discharge cycle test result of the pseudocapacitance/graphene composite material of example 2 of the present invention;
FIG. 6 is an SEM image of pseudo-capacitor/graphene composite material prepared in example 2 under different laser powers;
FIG. 7 shows the constant current charge and discharge test results of pseudocapacitance/graphene composite materials prepared in example 2 under different laser powers;
fig. 8 shows the charge and discharge test results of the pseudocapacitance/graphene composite material prepared in example 2 of the present invention at different current densities.
The specific embodiment is as follows:
the invention is further described below with reference to specific embodiments and illustrations in order to make the technical means, the creation features, the achievement of the purpose and the effect of the implementation of the invention easy to understand.
Example 1
Step one: and (3) taking potassium permanganate as a manganese oxide precursor, weighing 6.32g of potassium permanganate powder, dissolving in 100mL of deionized water, and magnetically stirring for 30min to prepare a 0.4mol/L potassium permanganate solution.
Step two: density is 6.4kg/m 3 The polyimide foam of (2) was immersed in the above solution and the foam was extruded in the solution several times to ensure sufficient absorption of the solution, and was sonicated for 60 minutes again, and 5mL of formaldehyde solution was added to the solution and immersed for 4 hours.
Step three: the foam was removed and rinsed several times in deionized water to remove unreduced potassium permanganate and dried under vacuum at 60 ℃ for 12h.
Step four: the dried doped foam is pressed into a flexible film under the pressure of 25MPa by taking polyethylene terephthalate (PET) with frosting as a flexible substrate.
Step five: CO with a wavelength of 10.6um 2 The infrared laser emitter is set to be 0.1mm in scanning step diameter, and when the power is 6W, the influence of four different scanning speeds of 60mm/s, 80mm/s, 100mm/s and 120mm/s on the performance of the pseudo-capacitance/graphene composite material is explored.
Step six: the pseudocapacitance/graphene composite material obtained in the step five is subjected to constant current charge-discharge test in 1mol/L sodium sulfate solution at different scanning speeds, as shown in fig. 1, it can be seen that as the scanning speed is reduced, the discharge time is gradually increased, and when the scanning speed is lower than 80mm/s, the discharge time starts to be reduced, and the main reason is that the scanning speed is too low, the heat accumulation effect time is too long, the graphene structure is damaged, the manganese oxide attachment amount is reduced, and the capacitance performance is reduced.
Example 2
Step one: manganese acetate is selected as a precursor of manganese compound, 14.5g of tetrahydrate manganese acetate crystal powder is weighed and dissolved in 200mL of deionized water, and the solution is magnetically stirred for 20min to prepare 0.3mol/L manganese acetate solution.
Step two: density of 10kg/m 3 The polyimide foam of (2) is immersed in the solution and extruded several times, and the ultrasonic treatment is performed for several hours to remove redundant bubbles in the foam.
Step three: the polyimide foam absorbed with the manganese acetate solution is dried in vacuum for 12 hours at 60 ℃ with the heating rate set to 3 ℃/min.
Step four: and (3) selecting low-density metal foam nickel as a flexible substrate, stacking the dried polyimide foam on the upper surface of the foam nickel, and pressing the polyimide foam into a film under the pressure of 20 MPa.
Step five: CO with a wavelength of 10.6um 2 The infrared laser emitter has the scanning speed of 80mm/s, the scanning step diameter of 0.1mm, and compared with the influence of different laser powers of 2.4W-7.2W on the structure and electrochemical performance of the generated pseudo-capacitor/graphene composite material, as shown in fig. 6 and 7, the graphene generated when the laser power is lower than 4.8W is of a lamellar structure, and the adhered manganese oxide is more uniform. The laser power further increases the content of the adhered manganate from the lamellar structure to the crumb structure of the graphene and gradually decreases.
Under the irradiation of laser, the manganese acetate is decomposed into manganese oxide mixed by divalent manganese and trivalent manganese ions, so that the pseudocapacitance/graphene composite material is obtained. The composite material is subjected to X-ray photoelectron spectroscopy, as shown in fig. 2, and it can be seen that manganese acetate is mainly decomposed into manganous oxide under laser irradiation. The generated porous graphene is observed by using a scanning electron microscope, as shown in fig. 3, the generated graphene has a rich porous three-dimensional structure, and a rapid transmission channel is provided for rapid transmission of ions. As shown in FIG. 4, the pseudo-capacitor/graphene composite material prepared by observation of a scanning electron microscope can promote the electrolyte ions to fully react with active sites electrochemically and improve the capacitance performance by uniformly growing manganese oxide on graphene and enabling the graphene to have a richer porous structure.
Step six: manganese oxide/graphene composite electrode material is used as a working electrode, a platinum sheet is used as a counter electrode, saturated AgCl is used as a reference electrode, and Na with concentration of 1mol/L is used as a reference electrode 2 SO 4 The solution was used as an electrolyte for electrochemical performance testing on an electrochemical workstation, the area specific capacitance of which is shown in FIG. 8, having a current density of 944.17mF/cm at 1 mA -2 High capacitance performance.
Example 3
The positive and negative electrodes are both made of the manganese oxide/graphene composite electrode material obtained in the example 2, and the electrolyte is H with the concentration of 1mol/L 3 PO 4 And taking polyvinyl alcohol (PVA) as a solid gel electrolyte curing agent, and packaging to form the symmetrical flexible supercapacitor.
According to the above, the preparation method of the graphene supercapacitor composite electrode with high pseudo-capacitance loading has the advantages of simple structure, good electrochemical performance, simple preparation process, low cost and the like, can realize high-content pseudo-capacitance material doping on the polymer precursor, and can be widely used in various fields of electric energy storage.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (12)
1. The preparation method of the graphene supercapacitor composite electrode with high pseudo-capacitance loading capacity is characterized by comprising the following steps of:
(1) Preparing a pseudocapacitance precursor material solution, and immersing a foam polymer in the solution;
(2) Taking out and drying the foam polymer absorbed with the pseudo-capacitance material, and then putting the foam polymer into a tablet press to press into a film;
(3) Exposing the prepared film to laser irradiation to obtain a graphene supercapacitor composite electrode;
in the step (3), the adjustment parameters during laser irradiation comprise one or more of laser power, laser scanning speed, laser spot diameter, irradiation times, pulse frequency, foam polymer type and pseudo-capacitance material; the types of the laser include gas laser, solid laser, liquid laser, semiconductor laser and optical fiber laser; the laser wavelength is 10-3000nm, the scanning speed is 5-1000um/s, the laser power is 0.1-200W, the laser spot diameter is 0.5-1000um, the scanning interval is 0.1-5mm, and the pulse frequency is 2-200kHZ; the laser irradiation environment is an atmosphere environment.
2. The method of manufacturing according to claim 1, characterized in that: in the step (1), the pseudocapacitance material is one or more of metal organic matters, metal inorganic matters, conductive polymers and nonmetallic compounds, and the size is 1-10000nm.
3. The preparation method according to claim 2, characterized in that: in the step (1), the metal inorganic matters comprise transition metal oxides, bimetallic oxides, multi-metal oxides and metal hydroxides.
4. The preparation method according to claim 2, characterized in that: the metal is one or more of iron, palladium, platinum, titanium, lithium, ruthenium, rubidium, silicon, manganese, zinc, magnesium, aluminum, calcium, barium, vanadium, cobalt, nickel, copper, molybdenum, zirconium and chromium; the metal inorganic matter is one or more of normal salt, double salt, acid salt and basic salt of metal.
5. The method of manufacturing according to claim 4, wherein: the normal salt comprises chlorate, borate and sulfate.
6. The method of manufacturing according to claim 1, characterized in that: in the step (1), the foam polymer is a syntactic foam polymer, a carbon single chain polymer, an aromatic-containing polymer, a semi-aromatic polymer, an aromatic heterocyclic polymer, a polyetherimideOne or more of polyimide, phenolic resin, polymetallic imide, polyethylene, polymethacrylimide, cyclic polymer, lignin and polymer with main chain containing imide ring; the density of the selected foamed polymer is 0.1-500kg/m 3 The thickness is 1-1000 and mm, and the length and width are any size.
7. The method of manufacturing according to claim 1, characterized in that: in the step (2), the drying is one or more of vacuum drying, room temperature drying and freeze drying; the drying temperature is room temperature-200 ℃, the drying time is 1min-72h, and the heating rate is 1-20 ℃/min.
8. The method of manufacturing according to claim 1, characterized in that: in the step (2), the pressure of the tablet press is 0.1-200MPa, the pressing time is 0.1-30min, and the thickness of the pressed film is 0.01-100 mm; the flexible material is selected as a supporting substrate in the pressing process, and comprises polyethylene terephthalate with frosted surfaces, polyvinyl chloride with frosted surfaces, polycarbonate, conductive flexible copper foil, foam nickel, foam silver, foam iron and foam zinc.
9. The method of manufacturing according to claim 1, characterized in that: in step (3), the atmosphere comprises an air atmosphere.
10. The graphene supercapacitor composite electrode prepared by the preparation method according to any one of claims 1 to 9.
11. The graphene supercapacitor composite electrode according to claim 10, wherein: the graphene in the composite electrode is three-dimensional porous graphene, single-layer graphene, double-layer graphene, multi-layer graphene, flaky graphene, flocculent graphene or graphene oxide, and the specific surface area is 5-2000m 2 /g；
The pseudo-capacitance material in the composite electrode has the loading capacity of 1-80%, the morphology of nano-particle spheres, nano-flowers, nano-particle blocks, nanowires, porous nanospheres or nano-sheets and the size of 1-200nm.
12. The graphene supercapacitor composite electrode according to claim 10, wherein: the section thickness of the composite electrode is 0.5-2000um, and the area specific capacitance is 1-10000mF.cm -2 ， 10 mA.cm -2 The retention rate of the capacitance is 97% or more after 6000 times of current density circulation.
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