CN111128561A - Flexible asymmetric solid-state supercapacitor with nanostructure and preparation method thereof - Google Patents
Flexible asymmetric solid-state supercapacitor with nanostructure and preparation method thereof Download PDFInfo
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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
- H01G11/22—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 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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- 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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- 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
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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
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- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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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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Abstract
The invention relates to the technical field of asymmetric super capacitors, in particular to a flexible asymmetric solid-state super capacitor with a nano structure and a preparation method thereof. The flexible asymmetric solid-state supercapacitor comprises a positive electrode, a negative electrode, a diaphragm and an electrolyte, wherein the positive electrode is made of carbon foam/cobalt nickel sulfide materials, the negative electrode is made of carbon foam/bismuth trioxide materials, and the electrolyte is made of polyvinyl alcohol/potassium hydroxide gel. The method of the invention selects the electrode material,The design of a micro-nano structure, the assembly of a macroscopic device, the multilayer compounding and the synergy ensure that the prepared flexible solid-state supercapacitor has good electrochemical performance, the voltage window is expanded to 1.5V, and the current density is 1 mA/cm2When the capacitance of the area reaches 475 mF/cm2At 3.73 mW/cm3Has a power density of 0.74mWh/cm3High energy density. The method is simple and easy to implement, green and environment-friendly, and has excellent performance, so that effective technical support can be provided for the design of the next-generation high-performance flexible super capacitor.
Description
Technical Field
The invention relates to the technical field of asymmetric super capacitors, in particular to a flexible asymmetric solid-state super capacitor with a nano structure and a preparation method thereof.
Background
With the development of flexible electronics, wearable electronic devices are rapidly entering the lives of people. In order to realize the commercialization of wearable devices, the energy supply components of the wearable devices also need to be flexible and have high performance, and therefore, the high-performance flexible energy storage devices will increasingly show potential market values. In recent years, asymmetric supercapacitors are widely applied to flexible energy storage devices due to wide working voltage, ultrahigh power density, fast charging rate and long cycle life, and development of flexible positive and negative electrode materials with both mechanical properties and energy storage properties is a key point for realizing efficient energy storage of the flexible positive and negative electrode materials.
The currently commonly used positive electrode active material is transition metal oxide, wherein nickel-cobalt bimetallic oxide (nickel cobaltate, NiCo)2O4) Have recently been studied extensively. Nickel cobaltates, which have twice the conductivity of single metal oxides, are considered to be more effective electrode materials, however, have poor charging capacity and sustained cycle life, limiting their use in the energy storage field. Nickel cobalt bimetallic sulfide (cobalt nickel sulfide, NiCo)2S4) Compared with nickel-cobalt bimetallic oxide, the nickel-cobalt bimetallic oxide has smaller energy band gap, so that the conductivity of the nickel-cobalt sulfide is at least two times higher than that of the nickel cobaltate; cobalt nickel sulfide, on the other hand, has a higher electrochemical activity and higher capacity than other single metal oxides or sulfides due to its inherent redox reactive sites. Although cobalt nickel sulfide has achieved an improvement in the energy storage performance of nickel cobalt based systems, it has not yet met with large power sourcesThe development of electronic devices, hybrid vehicles and smart grids, and therefore, the increase of the specific area capacity, rate capability and cycling stability of these materials is still a major challenge. An effective method for improving the multiplying power of the cobalt nickel sulfide material is to design a multi-three-dimensional multi-level structure to provide a larger specific surface area and a higher surface loading capacity, so as to promote effective charge and mass exchange in the Faraday redox reaction process.
Bismuth trioxide is widely used as a negative active material due to the advantages of innocuity, easy synthesis, wide band gap, good oxide ion conductivity, proper negative working window, high electrochemical stability, high redox reversibility and the like, but the capacitance of the bismuth trioxide is severely limited due to low conductivity of the bismuth trioxide in the preparation process. Therefore, in order to obtain high energy, the electrode material needs to be selected and optimized, and the micro-nano structure of the material is designed to ensure that the performance of the material is optimal.
In order to improve the mechanical properties of the electrode material, the positive and negative electrode active materials are required to be loaded on a flexible substrate to form a flexible electrode. The melamine foam has flexibility and is rich in three-dimensional structure pore channels, and after carbonization, the pore structure can still keep good mechanical properties and can be used as an ideal carrier of a flexible device. How to optimize the components of the electrode material and construct a functional interface, and realize the effective load of the active electrode material on a flexible substrate, the preparation of the flexible asymmetric supercapacitor with both mechanical properties and energy storage properties still faces huge challenges.
Disclosure of Invention
The invention aims to solve the problems and provides a flexible asymmetric solid-state supercapacitor with a nano structure and a preparation method thereof.
The technical scheme for solving the problems is to provide a flexible asymmetric solid-state supercapacitor with a nano structure, which comprises a positive electrode, a negative electrode, a diaphragm and an electrolyte, wherein the positive electrode is selected from a carbon foam/cobalt nickel sulfide material for growing cobalt nickel sulfide on a porous carbon substrate, the negative electrode is selected from a carbon foam/bismuth trioxide material for growing bismuth trioxide on the porous carbon substrate, and the electrolyte is selected from polyvinyl alcohol/potassium hydroxide gel.
Preferably, the carbon foam/bismuth trioxide material is prepared by growing bismuth trioxide on a porous carbon substrate from a bismuth precursor solution through a hydrothermal method.
Preferably, the carbon foam/bismuth trioxide material is prepared by the following steps: dissolving bismuth nitrate in a solvent with the volume ratio of 2:1, obtaining a precursor solution of bismuth in the ethanol-ethylene glycol mixed solution; and (3) immersing the porous carbon substrate into a bismuth precursor solution, reacting for 3-8h at the temperature of 150-200 ℃, cooling, cleaning and drying to obtain the carbon foam/bismuth trioxide material.
Preferably, the carbon foam/cobalt nickel sulfide material is prepared by growing a cobalt nickel precursor on a porous carbon substrate by a hydrothermal method through a mixed solution of cobalt salt, nickel salt and a pH regulator, and then immersing the cobalt nickel precursor into a vulcanizing agent.
Preferably, the pH regulator is urea.
Preferably, the carbon foam/cobalt nickel sulphide material is prepared by: preparing a mixed solution of nickel salt, cobalt salt and urea; immersing the porous carbon substrate into the mixed solution, reacting for 8-12h at 100-200 ℃, cooling, cleaning and drying to obtain a precursor material; and (3) immersing the precursor material into a vulcanizing agent solution, reacting for 10-15h at the temperature of 80-120 ℃, cooling, cleaning and drying to obtain the carbon foam/cobalt nickel sulfide material.
Preferably, the nickel salt is NiCl2。
Preferably, CoCl is selected as the cobalt salt2。
Preferably, the vulcanizing agent is 0.1-0.5mol/L thioacetamide solution.
Preferably, the polyvinyl alcohol/potassium hydroxide gel is a gel obtained by dissolving PVA in KOH solution and stirring at 90-100 ℃ until the PVA is transparent.
Preferably, the polyvinyl alcohol/potassium hydroxide gel is prepared by: 4-8 g of PVA is dissolved in 40-60 mL of 1-5 mol/L KOH solution and stirred at 90-100 ℃ until the solution is transparent, thus obtaining polyvinyl alcohol/potassium hydroxide gel.
Preferably, the porous carbon substrate is nitrogen-doped porous carbon foam obtained by carbonizing melamine sponge.
Preferably, the carbonization treatment comprises the steps of: the melamine sponge is placed in a high-temperature tube furnace, argon is introduced for 15-40 min at room temperature before pyrolysis, the flow of the argon is 500-1500 standard cubic centimeters per minute, and air in the tube is exhausted. Then keeping the flow rate of the argon gas, raising the temperature to 600-900 ℃ at the speed of 5-20 ℃/min, pyrolyzing for 1-3h, and then slowly cooling to the room temperature.
Preferably, the separator is cellulose paper.
The invention also aims to provide a preparation method of the flexible asymmetric solid-state supercapacitor with the nano structure, which comprises the following steps: and assembling the anode, the cathode, the diaphragm and the electrolyte into a solid capacitor, and then packaging by PET.
Preferably, the assembling comprises the steps of: and soaking the anode and the cathode in an electrolyte, taking out after wetting, assembling the anode, the electrolyte, the diaphragm, the electrolyte and the cathode in sequence, and curing at room temperature for 2-6h to obtain the flexible asymmetric solid supercapacitor.
Preferably, the PET package comprises the steps of: and (4) wrapping the assembled solid capacitor in a PET film, and heating and plasticizing.
The invention has the beneficial effects that:
1. the carbon foam with the three-dimensional interconnection network structure is used as an electrode substrate, and has the advantages of good chemical stability, rich porous structure, open pore channel, large specific surface area, good conductivity and the like, thereby being beneficial to the migration of electrolyte and the uniform growth of transition metal oxide on a carbon foam framework.
2. The positive electrode and the negative electrode respectively adopt cobalt nickel sulfide and bismuth trioxide, and the working voltage window of the super capacitor can be greatly expanded by superposing the absolute complementary voltage windows of the positive electrode and the negative electrode, so that the super capacitor can provide high energy density capability.
3. The high-conductivity nitrogen-doped carbon foam is combined with cobalt nickel sulfide and bismuth trioxide active electrode materials, and the double-layer capacitance of the carbon foam is combined with the Faraday capacitance of metal oxide, so that the super-capacitance is improved, the optimized synergistic effect of the structure and the composition of the nano mixed electrode material is improved, and the performance of the asymmetric solid supercapacitor is greatly improved.
4. The method is simple, practicable, environment-friendly and low in cost, and avoids the use of adhesives and conductive additives, and meanwhile, the flexible asymmetric solid super capacitor device has the advantages of working voltage expansion, large capacitance, high energy density and good rate capability.
Drawings
FIG. 1 is an SEM image of a carbon foam produced in example 1 of the present application;
FIG. 2 is an SEM image of a carbon foam/cobalt nickel sulfide material prepared in example 1 of the present application;
FIG. 3 is an SEM image of a carbon foam/bismuth trioxide material made in example 1 of the present application;
FIG. 4 is an XRD pattern of carbon foam/cobalt nickel sulfide and carbon foam/bismuth trioxide produced in example 1 of the present application;
FIG. 5 is a cyclic voltammogram of a flexible asymmetric solid-state supercapacitor made in example 1 of the present application;
FIG. 6 is a graph showing the charging and discharging curves of the flexible asymmetric solid-state supercapacitor made in example 1 of the present application;
FIG. 7 is a graph of rate capability of a flexible asymmetric solid-state supercapacitor made in example 1 of the present application;
FIG. 8 is a Ragon plot and comparison to a comparative example of a flexible asymmetric solid-state supercapacitor made in example 1 of the present application;
fig. 9 is a structural diagram of a flexible asymmetric solid-state supercapacitor manufactured in example 1 of the present application.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the accompanying drawings, but the present invention is not limited to these embodiments.
Example 1
A flexible asymmetric solid-state supercapacitor of a nanostructure is prepared by the following steps:
(1) preparing a porous carbon substrate: placing melamine sponge in a high-temperature tube furnace, firstly introducing argon at room temperature for 25min, wherein the flow of the argon is 1000cm3And/min, exhausting air in the pipe. Then keeping the flow rate of argon gas, raising the temperature to 800 ℃ at the speed of 5 ℃/min, pyrolyzing for 1h, and slowly cooling to room temperature to obtain the carbon foam.
(2) Preparation of the positive electrode: mixing NiCl2，CoCl2And urea were dissolved in deionized water and continuously stirred to form a homogeneous pink solution. And (2) immersing the carbon foam obtained in the step (1) into the solution, transferring the carbon foam into a polytetrafluoroethylene hydrothermal reaction kettle, placing the polytetrafluoroethylene hydrothermal reaction kettle in an air-blowing drying oven, preserving the heat at 100 ℃ for 12 hours, and cooling to room temperature. Then washed with deionized water and dried to obtain the carbon foam/cobalt nickel hydroxide material. And soaking the obtained carbon foam/cobalt nickel hydroxide in 0.2 mol/L thioacetamide solution, carrying out hydrothermal treatment at 95 ℃ for 12 hours, cooling to room temperature, washing with deionized water, and drying to obtain the carbon foam/cobalt nickel sulfide material.
(3) Preparation of a negative electrode: 0.97g of bismuth nitrate pentahydrate is dissolved in a mixed solution of ethanol and ethylene glycol in a volume ratio of 2:1, and the solution is stirred and dissolved to obtain a dispersion liquid. And (2) immersing the carbon foam obtained in the step (1) into the dispersion, transferring the carbon foam into a polytetrafluoroethylene hydrothermal reaction kettle, placing the polytetrafluoroethylene hydrothermal reaction kettle in an air-blowing drying oven, preserving the heat at 160 ℃ for 5 hours, and cooling to room temperature. Then washing with deionized water and drying. And (3) putting the dried sample into a high-temperature tube furnace, and annealing in an argon atmosphere to obtain the carbon foam/bismuth trioxide material.
(4) Preparing an electrolyte: 6 g of PVA was dissolved in 60 mL of a 2mol/L KOH solution and stirred at 95 ℃ until it was transparent, to obtain a polyvinyl alcohol/potassium hydroxide gel.
(5) Cellulose paper is selected as the diaphragm.
(6) And soaking the anode and the cathode in an electrolyte, taking out after wetting, assembling the anode, the electrolyte, the diaphragm, the electrolyte and the cathode in sequence, and curing at room temperature for 5 hours to obtain the flexible asymmetric solid-state supercapacitor.
(7) And (4) wrapping the assembled solid capacitor in a PET film, and heating and plasticizing.
(8) The electrode materials were characterized and the results are shown in fig. 1-4.
Fig. 1 shows the microscopic morphology of the carbon foam material, and it is seen that the carbon foam has a three-dimensional interconnected network structure with a smooth and flat surface, and the interconnected structure is favorable for the migration of electrolyte and the uniform growth of cobalt nickel sulfide nanorods and bismuth trioxide nanosheets on the carbon foam skeleton.
Fig. 2 is a microscopic topography of a carbon foam/cobalt nickel sulfide material, with cobalt nickel sulfide growing uniformly and vertically on the carbon foam skeleton, without significant aggregation, forming a typical pine-twig like structure.
Fig. 3 shows a carbon foam/bismuth trioxide material, and it can be seen from fig. 3 that bismuth nitrate is decomposed into bismuth trioxide nanosheets after simple solvent heat treatment, and under a higher magnification, the bismuth trioxide nanosheets can be observed to densely grow on a carbon foam skeleton, and are assembled into a structure similar to agaric.
FIG. 4 is a phase diagram of carbon foam/cobalt nickel sulfide and carbon foam/bismuth trioxide measured by X-ray diffraction (XRD). By searching JCPDS card database, it can be found that the prepared carbon foam/cobalt nickel sulfide material can easily index to cubic phase of cobalt nickel sulfide (JCPDS, No. 00-020-. In the carbon foam/bismuth trioxide phase, in addition to one diffraction peak from carbon foam, four diffraction peaks at 2 θ values of 28 °, 32.4 °, 46.5 °, and 55.1 ° corresponding to the (111), (200), (220), and (311) crystal planes of carbon foam/bismuth trioxide are well oriented to the cubic phase of carbon foam/bismuth trioxide (JCPDS, No. 27-0052).
And (3) carrying out electrochemical performance test on the prepared flexible asymmetric solid-state supercapacitor: the flexible asymmetric solid-state supercapacitor is connected to an electrochemical workstation, the performance of the flexible asymmetric solid-state supercapacitor is tested through cyclic voltammetry and constant current charging and discharging, and the area capacitance, the power density and the energy density are calculated. The detection results are shown in fig. 5-8.
Fig. 5 is a cyclic voltammogram of a flexible asymmetric solid-state supercapacitor, which is prepared by using carbon foam/cobalt nickel sulfide as a positive electrode, carbon foam/bismuth trioxide as a negative electrode, and polyvinyl alcohol/potassium hydroxide as a gel electrolyte. The operating voltage window of the flexible asymmetric solid-state supercapacitor device can be expanded to 1.5V by superimposing the absolute complementary voltage windows of the positive and negative electrodes, demonstrating its ability to provide high energy density.
FIG. 6 is a graph of the charge and discharge curves of the flexible asymmetric solid-state supercapacitor, and from the GCD curve of FIG. 6, the values of the asymmetric supercapacitor at 1, 2, 4, 6, 8 and 10 mA/cm can be calculated2The area capacitance is 475.5, 340.2, 284.2, 223.4, 207.6 and 152.8 mF/cm2。
Fig. 7 is a graph of rate performance of the flexible asymmetric solid-state supercapacitor, and it can be seen from fig. 7 that the prepared flexible asymmetric solid-state supercapacitor device shows good rate performance.
FIG. 8 is a Ragon graph of a flexible asymmetric solid-state supercapacitor, in FIG. 8, square dots represent asymmetric supercapacitors in the present embodiment, and it can be seen from FIG. 8 that at a power density of 3.73 mW/cm3When the energy density is 0.74mWh/cm3。
Fig. 9 is a construction diagram of a flexible asymmetric solid-state supercapacitor demonstrating the feasibility of the present application.
Example 2
A flexible asymmetric solid-state supercapacitor of a nanostructure is prepared by the following steps:
(1) preparing a porous carbon substrate: placing melamine sponge in a high-temperature tube furnace, firstly introducing argon for 15min at room temperature, wherein the flow of the argon is 500cm3And/min, exhausting air in the pipe. Then keeping the flow rate of argon gas, raising the temperature to 600 ℃ at the speed of 5 ℃/min, pyrolyzing for 1h, and slowly cooling to room temperature to obtain the carbon foam.
(2) Preparation of the positive electrode: mixing NiCl2，CoCl2And urea were dissolved in deionized water and continuously stirred to form a homogeneous pink solution. And (2) immersing the carbon foam obtained in the step (1) into the solution, transferring the carbon foam into a polytetrafluoroethylene hydrothermal reaction kettle, placing the polytetrafluoroethylene hydrothermal reaction kettle into an air-blowing drying oven, preserving the heat at 200 ℃ for 8 hours, and cooling to room temperature. Then washed with deionized water and dried to obtain the carbon foam/cobalt nickel hydroxide material. And soaking the obtained carbon foam/cobalt nickel hydroxide in 0.1 mol/L thioacetamide solution, carrying out hydrothermal treatment at 80 ℃ for 10 hours, cooling to room temperature, washing with deionized water, and drying to obtain the carbon foam/cobalt nickel sulfide material.
(3) Preparation of a negative electrode: 0.9g of bismuth nitrate pentahydrate is dissolved in a mixed solution of ethanol and ethylene glycol in a volume ratio of 2:1, and the mixed solution is stirred and dissolved to obtain a dispersion liquid. And (2) immersing the carbon foam obtained in the step (1) into the dispersion, transferring the carbon foam into a polytetrafluoroethylene hydrothermal reaction kettle, placing the polytetrafluoroethylene hydrothermal reaction kettle in an air-blowing drying oven, preserving the heat at 150 ℃ for 3 hours, and cooling to room temperature. Then washing with deionized water and drying. And (3) putting the dried sample into a high-temperature tube furnace, and annealing in an argon atmosphere to obtain the carbon foam/bismuth trioxide material.
(4) Preparing an electrolyte: 4g of PVA was dissolved in 40 mL of a 1mol/L KOH solution and stirred at 90 ℃ until it was clear, to give a polyvinyl alcohol/potassium hydroxide gel.
(5) Cellulose paper is selected as the diaphragm.
(6) And soaking the anode and the cathode in an electrolyte, taking out after wetting, assembling the anode, the electrolyte, the diaphragm, the electrolyte and the cathode in sequence, and curing at room temperature for 2 hours to obtain the flexible asymmetric solid-state supercapacitor.
(7) And (4) wrapping the assembled solid capacitor in a PET film, and heating and plasticizing.
Example 3
A flexible asymmetric solid-state supercapacitor of a nanostructure is prepared by the following steps:
(1) preparing a porous carbon substrate: placing melamine sponge in a high-temperature tube furnace, firstly introducing the melamine sponge at room temperatureArgon gas flow of 1500cm for 40 min3And/min, exhausting air in the pipe. Then keeping the flow rate of argon gas, raising the temperature to 900 ℃ at the rate of 20 ℃/min, pyrolyzing for 3h, and slowly cooling to room temperature to obtain the carbon foam.
(2) Preparation of the positive electrode: mixing NiCl2，CoCl2And urea were dissolved in deionized water and continuously stirred to form a homogeneous pink solution. And (2) immersing the carbon foam obtained in the step (1) into the solution, transferring the carbon foam into a polytetrafluoroethylene hydrothermal reaction kettle, placing the polytetrafluoroethylene hydrothermal reaction kettle in an air-blowing drying oven, preserving the heat at 150 ℃ for 10 hours, and cooling to room temperature. Then washed with deionized water and dried to obtain the carbon foam/cobalt nickel hydroxide material. And soaking the obtained carbon foam/cobalt nickel hydroxide in 0.5mol/L thioacetamide solution, carrying out hydrothermal treatment at 120 ℃ for 15 hours, cooling to room temperature, washing with deionized water, and drying to obtain the carbon foam/cobalt nickel sulfide material.
(3) Preparation of a negative electrode: dissolving 1.2g of bismuth nitrate pentahydrate in a mixed solution of ethanol and ethylene glycol in a volume ratio of 2:1, and stirring and dissolving to obtain a dispersion liquid. And (2) immersing the carbon foam obtained in the step (1) into the dispersion, transferring the carbon foam into a polytetrafluoroethylene hydrothermal reaction kettle, placing the polytetrafluoroethylene hydrothermal reaction kettle in an air-blowing drying oven, preserving the heat at 200 ℃ for 8 hours, and cooling to room temperature. Then washing with deionized water and drying. And (3) putting the dried sample into a high-temperature tube furnace, and annealing in an argon atmosphere to obtain the carbon foam/bismuth trioxide material.
(4) Preparing an electrolyte: 8 g of PVA was dissolved in 50 mL of a 5mol/L KOH solution and stirred at 100 ℃ until it was transparent, to obtain a polyvinyl alcohol/potassium hydroxide gel.
(5) Cellulose paper is selected as the diaphragm.
(6) And soaking the anode and the cathode in an electrolyte, taking out after wetting, assembling the anode, the electrolyte, the diaphragm, the electrolyte and the cathode in sequence, and curing at room temperature for 6 hours to obtain the flexible asymmetric solid-state supercapacitor.
(7) And (4) wrapping the assembled solid capacitor in a PET film, and heating and plasticizing.
Comparative examples 1 to 4
A flexible asymmetric solid-state supercapacitor was prepared according to the prior art and has the structure shown in table 1 below.
The performance ratio of the supercapacitor of comparative example to the supercapacitor of example 1 is shown in fig. 8, in which a dot with a circle number of 2 indicates the performance result of comparative example 1, a dot with a regular triangle number of 3 indicates the performance result of comparative example 2, a dot with an inverted triangle number of 4 indicates the performance result of comparative example 3, and a dot with a diamond shape number of 5 indicates the performance result of comparative example 4. Fig. 8 shows that the flexible asymmetric solid supercapacitor obtained by the method has better performance than the conventional supercapacitor through reasonable matching between the anode and cathode materials and the substrate.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. The utility model provides a flexible asymmetric solid-state ultracapacitor system of nanostructure, includes positive pole, negative pole, diaphragm and electrolyte, its characterized in that: the anode is selected from a carbon foam/cobalt nickel sulfide material for growing cobalt nickel sulfide on a porous carbon substrate, the cathode is selected from a carbon foam/bismuth trioxide material for growing bismuth trioxide on the porous carbon substrate, and the electrolyte is selected from polyvinyl alcohol/potassium hydroxide gel.
2. The nanostructured flexible asymmetric solid-state supercapacitor according to claim 1, wherein: the carbon foam/bismuth trioxide material is prepared by growing bismuth trioxide on a porous carbon substrate by a hydrothermal method from a bismuth precursor solution.
3. The nanostructured flexible asymmetric solid-state supercapacitor according to claim 1, wherein: the carbon foam/cobalt nickel sulfide material is prepared by growing a cobalt nickel precursor on a porous carbon substrate by a hydrothermal method through a mixed solution of cobalt salt, nickel salt and a pH regulator, and then immersing the cobalt nickel precursor into a vulcanizing agent.
4. The nanostructured flexible asymmetric solid-state supercapacitor according to claim 3, wherein: the vulcanizing agent is thioacetamide solution.
5. The nanostructured flexible asymmetric solid-state supercapacitor according to claim 1, wherein: the porous carbon substrate is nitrogen-doped porous carbon foam obtained by carbonizing melamine sponge.
6. The nanostructured flexible asymmetric solid-state supercapacitor according to claim 1, wherein: the polyvinyl alcohol/potassium hydroxide gel is obtained by dissolving PVA in KOH solution and then stirring at 90-100 ℃ until the PVA is transparent.
7. The nanostructured flexible asymmetric solid-state supercapacitor according to claim 1, wherein: the diaphragm is made of cellulose paper.
8. A method for preparing a nano-structured flexible asymmetric solid-state supercapacitor according to any one of claims 1 to 7, wherein: the method comprises the following steps: and assembling the anode, the cathode, the diaphragm and the electrolyte into a solid capacitor, and then packaging by PET.
9. The method for preparing the flexible asymmetric solid-state supercapacitor with the nano structure according to claim 8, wherein the flexible asymmetric solid-state supercapacitor with the nano structure comprises the following steps: the assembly comprises the following steps: and soaking the anode and the cathode in an electrolyte, taking out after wetting, assembling the anode, the electrolyte, the diaphragm, the electrolyte and the cathode in sequence, and curing at room temperature for 2-6h to obtain the flexible asymmetric solid supercapacitor.
10. The method for preparing the flexible asymmetric solid-state supercapacitor with the nano structure according to claim 8, wherein the flexible asymmetric solid-state supercapacitor with the nano structure comprises the following steps: the PET package comprises the following steps: and (4) wrapping the assembled solid capacitor in a PET film, and heating and plasticizing.
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