CN110993359B - Flexible solid-state asymmetric supercapacitor device and preparation method and application thereof - Google Patents
Flexible solid-state asymmetric supercapacitor device and preparation method and application thereof Download PDFInfo
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- 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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Abstract
The invention provides a flexible solid-state asymmetric supercapacitor device and a preparation method and application thereof. The positive electrode material of the super capacitor device is oxygen-deficient NiCo taking flexible carbon cloth as a substrate2O4A nanowire array material; the negative electrode material is a three-dimensional mesoporous graphene nano material; the solid electrolyte is polyvinyl alcohol/lithium chloride gel. The method of the invention sets the temperature and time of the hydrothermal reaction, thereby growing uniform NCO nanowire arrays on the flexible carbon cloth substrate; and introducing oxygen vacancies on the surface of the NCO nano material by setting the temperature and time of thermal reduction. On the other hand, the cathode material of the flexible solid asymmetric supercapacitor device is prepared by controlling the growth factor of the 3DPG nano material. The super capacitor device has the advantages of high energy density, high power density, long service life and the like, and has a great application prospect in the aspect of energy storage.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a flexible solid asymmetric supercapacitor device and a preparation method and application thereof.
Background
Energy is an important basic resource for the development of human society. However, as the world energy resource production place is far away from the energy consumption center, especially along with the development of the world economy, the dramatic increase of the world population and the continuous improvement of the living standard of people, the world energy demand is continuously increased, thereby causing the competition of energy resources to be violent, the environmental pollution to be aggravated and the environmental protection pressure to be increased. Therefore, the deep development and the efficient utilization of new energy are realized, and the development of a high-specific-energy, clean and safe chemical power system becomes an important requirement for social development.
Supercapacitors are considered to be efficient, practical energy storage devices with performance that is intermediate between conventional capacitors and batteries. In addition, the super capacitor has the advantages of rapid charge and discharge, super-long service life, environmental protection, capability of working in a wider temperature range and the like, and has great application prospect. Because of the increasing shortage of petroleum resources and the increasing pollution of the exhaust gas of petroleum-burning internal combustion engines to the environment, especially in large and medium cities, the increase of solid particles in the air has a great influence on human bodies, and people are researching new energy devices for replacing internal combustion engines. Research and development of hybrid power, fuel cell, chemical cell products and applications have been carried out with certain success. But they have not been well solved because of their inherent fatal weaknesses such as short service life, poor temperature characteristics, environmental pollution of chemical batteries, complex system, high cost, etc. The super capacitor has excellent characteristics, benefits and avoids disadvantages, can partially or completely replace the traditional chemical battery to be used as a traction power supply and a starting energy source of a vehicle, and has wider application range than the traditional chemical battery. Therefore, the research and development of super capacitors are not performed in all countries in the world, especially in the developed countries in the western world, but how to prepare super capacitors with good capacitance performance and stable cycle performance on a large scale at low cost becomes a main reason for limiting the development of super capacitors.
NiCo in contrast to other materials2O4The (NCO) material not only has higher theoretical capacitance, but also has rich resources, low price and environmental protection, thereby being high in development potentialAn electrode material. However, due to its weak electrical conductivity, its rate capability, energy density and power density are low and stability is poor, which severely restricts its wide application in high performance super capacitor. In order to improve the characteristic, in recent years, a great deal of research is carried out on the morphology and structure of the material. Such as sheet, nanoflower, granule, etc. Although the capacitance performance of the electrode material is greatly improved after long-term exploration, the intrinsic weak conductivity of the electrode material is not fundamentally solved. Therefore, it is of great significance to develop a simple, high-efficiency and low-energy-consumption preparation method of the NCO nano material and to substantially improve the conductive capability and the energy storage performance of the NCO nano material. In addition, the existing flexible and bendable capacitor has low energy density and complicated manufacturing process, which limits its practical application. Therefore, how to increase the energy density of the existing super capacitor while simplifying its manufacturing process is a current key task.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a flexible solid asymmetric supercapacitor device.
The invention also aims to provide a preparation method of the flexible solid asymmetric supercapacitor device.
The invention further aims to provide application of the flexible solid asymmetric supercapacitor device.
The purpose of the invention is realized by the following technical scheme:
a flexible solid asymmetric supercapacitor device comprises a positive electrode material, a negative electrode material and a solid electrolyte; the anode material is oxygen-deficient NiCo taking flexible carbon cloth as a substrate2O4(NCOx) A nanowire array material; the negative electrode material is a three-dimensional mesoporous graphene (3DPG) nano material taking flexible carbon cloth as a substrate; the solid electrolyte is polyvinyl alcohol/lithium chloride (PVA/LiCl) gel.
NCO taking flexible carbon cloth as substratexThe nanowire array material is prepared by the following method:
A. preparing an NCO nanowire array material: will be provided withNickel nitrate hexahydrate (Ni (NO)3)2·6H2O), cobalt nitrate hexahydrate (Co (NO)3)2·6H2O), thiourea (CH)4N2S) and ammonium fluoride (NH)4F) Dissolving in deionized water, ultrasonically dispersing uniformly, adding cleaned flexible carbon cloth, and carrying out hydrothermal reaction; washing and drying the reaction product to obtain an NCO nanowire array material growing on the flexible carbon cloth substrate;
B. preparation of NCOxNanowire array materials: placing the NCO nanowire array material obtained in the step A in a vacuum environment, and carrying out thermal reduction reaction in a nitrogen atmosphere to obtain NCOxA nanowire array material.
In step A, said Ni (NO)3)2·6H2O、Co(NO3)2·6H2O、CH4N2S、NH4F. The proportion of deionized water is preferably 0.5-2.5 g: 1-4 g: 1-5 g: 0.5-2.5 g: calculating the proportion of 50-300 mL; more preferably, the amount of the compound is 1 g: 2 g: 1 g: 1 g: the proportion of 100 mL.
In the step a, the preparation method of the cleaned flexible carbon cloth comprises the following steps: and (3) placing the flexible carbon cloth in absolute ethyl alcohol for ultrasonic treatment to obtain the cleaned flexible carbon cloth.
In step a, the dissolution conditions are preferably dissolution at room temperature.
The room temperature is preferably 10-30 ℃; more preferably 24 to 26 ℃.
In the step A, the temperature of the hydrothermal reaction is preferably 80-200 ℃; more preferably 120 deg.c.
In the step A, the time of the hydrothermal reaction is preferably 2-36 h; more preferably 2-12 h; more preferably 12 h.
In step a, the specific operation of washing is as follows: and washing with deionized water after the reaction product is naturally cooled.
In step a, the drying is preferably natural drying.
In the step B, the pressure of the vacuum environment is preferably 10-30 mTorr; more preferably 20 mTorr.
In the step B, the injection speed of the nitrogen is preferably 50-150 mL/min-1(ii) a More preferably 100 mL/min-1。
In the step B, the temperature of the thermal reduction reaction is preferably 100-500 ℃; more preferably 100-300 ℃; most preferably 300 deg.c.
In the step B, the time of the thermal reduction reaction is preferably 0.5-3 h; more preferably 3 h.
In the step B, the heating rate of the thermal reduction reaction is preferably 5 ℃ min-1。
The 3DPG nano material with the flexible carbon cloth as the substrate is prepared by the following method: and uniformly mixing the graphene oxide suspension with a potassium hydroxide (KOH) solution, adding the cleaned flexible carbon cloth, reacting to obtain graphene gel growing on the flexible carbon cloth substrate, and drying to obtain the 3DPG nano material.
The graphene oxide suspension is prepared by the following method: oxidizing graphite powder by a Hummers method to prepare graphene oxide, and ultrasonically dispersing in deionized water to obtain a graphene oxide suspension.
The Hummers method for preparing graphene oxide preferably refers to paragraph 12 of patent CN 108395578A.
In a system obtained by uniformly mixing the graphene oxide suspension and a potassium hydroxide solution: the mass molar ratio of the graphene oxide to the potassium hydroxide is preferably 1-5 g: 0.05-0.25 mol; more preferably 1 to 3 g: 0.05-0.25 mol; most preferably 3 g: 0.132 mol.
The concentration of the graphene oxide suspension is preferably 1-5 mg/mL-1(ii) a More preferably 1 to 3 mg/mL-1(ii) a Most preferably 3 mg/mL-1。
The concentration of the KOH solution is preferably 0.05-0.25 mol.L-1(ii) a More preferably 0.132 mol. L-1。
The volume ratio of the graphene oxide suspension to the KOH solution is preferably 1: 1.
the reaction temperature is preferably 60-220 ℃; more preferably 160-190 ℃; most preferably 180 deg.c.
The reaction time is preferably 3-8 h; more preferably 5 h.
The drying is preferably freeze drying.
The freeze drying time is preferably 1-4 days; more preferably 2 days.
The positive electrode material and the negative electrode material may be cut into appropriate sizes before assembly, and are preferably cut into 2 × 3cm2Is rectangular.
A preparation method of a flexible solid asymmetric supercapacitor device comprises the following steps:
(1) preparation of flexible carbon cloth substrate:
placing the flexible carbon cloth in absolute ethyl alcohol for ultrasonic treatment to obtain a cleaned flexible carbon cloth substrate;
(2)NCOxpreparing a nanowire array material:
A. preparing an NCO nanowire array material: 1g of Ni (NO)3)2·6H2O，2g Co(NO3)2·6H2O, 1g Thiourea and 1g NH4Dissolving the F in 100mL of deionized water at room temperature, adding the flexible carbon cloth substrate obtained in the step (1), ultrasonically dispersing uniformly, transferring the mixture into a reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 12h, naturally cooling, washing with deionized water, and airing to obtain an NCO nanowire array material growing on the flexible carbon cloth substrate;
B. preparation of NCOxNanowire array materials:
the first step is as follows: placing the NCO nanowire array material obtained in the step A into a quartz tube, and vacuumizing the quartz tube to 20 mTorr;
the second step is that: injecting N into the evacuated quartz tube2Is a reaction of N2The injection rate of (2) is controlled to be 100mL min-1Heating the quartz tube to reaction temperature of 300 deg.C for 3 hr, naturally cooling, and stopping injecting N2To obtain NCOxA nanowire array material;
(3) preparation of 3DPG nano material:
A. preparation of graphite oxideAlkene suspension: oxidizing graphite powder to prepare graphene oxide by a Hummers method, and ultrasonically dispersing in deionized water to obtain the graphene oxide with the concentration of 3 mg/mL-1A graphene oxide suspension;
B. preparing 3DPG nano material: 20mL of 3 mg/mL-1Graphene oxide suspension and 20mL of 0.132 mol.L-1Uniformly mixing KOH solution, adding the flexible carbon cloth substrate obtained in the step (1), uniformly dispersing by ultrasonic, transferring the mixture into a reaction kettle, reacting for 5 hours at 180 ℃ to obtain graphene gel growing on the flexible carbon cloth substrate, and freeze-drying the obtained graphene gel for 2 days to obtain a 3DPG nano material;
(4) assembling the flexible solid asymmetric supercapacitor device:
NCO prepared in step (2)xAnd (3) packaging the nano material serving as the anode material, the 3DPG nano material prepared in the step (3) serving as the cathode material and PVA/LiCl gel serving as solid electrolyte to obtain the flexible solid asymmetric supercapacitor device.
A flexible solid asymmetric supercapacitor device is prepared by the method.
The flexible solid asymmetric supercapacitor device is applied to the technical field of electrochemical energy storage.
Compared with the prior art, the invention has the following advantages and effects:
(1) the invention provides a preparation method of a flexible solid asymmetric supercapacitor device, which comprises the steps of setting the temperature and time of a hydrothermal reaction, and growing a uniform NCO nanowire array on a flexible carbon cloth substrate; by setting the temperature and time of thermal reduction, oxygen vacancies are introduced on the surface of the NCO nano material, and the active sites and the conductivity of the NCO nano material are increased, so that the capacity, the rate capability and the cycling stability of the flexible solid asymmetric supercapacitor device are greatly improved. On the other hand, the cathode material of the flexible solid asymmetric supercapacitor device is prepared by controlling the growth factor of the 3DPG nano material.
(2) According to the flexible solid asymmetric supercapacitor device provided by the invention, the NCOx nano electrode material and the 3DPG nano electrode material are directly prepared on the flexible carbon cloth carrier, so that the specific surface area of the electrode material is increased, the performance of the flexible solid asymmetric supercapacitor device is effectively improved, and the flexible solid asymmetric supercapacitor device can be applied to assembly of the flexible solid asymmetric supercapacitor device. In addition, oxygen vacancies introduced into the surface of the NCO nano material can further increase the active sites and the conductivity of the NCO nano material, so that the reversible capacity, the rate capability and the cycling stability of the flexible solid-state asymmetric supercapacitor device are greatly improved.
(3) The invention provides application of a flexible solid-state asymmetric supercapacitor in the technical field of electrochemical energy storage, can provide a flexible solid-state asymmetric supercapacitor with high capacity, high multiplying power and long service life, and also has the advantages of high energy density, good flexibility and the like, and the requirements on the flexible solid-state supercapacitor can be met by the total power density, the energy density and the cycle life.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) result of the 3DPG nano-material in example 1, wherein the scale is 50 μm.
FIG. 2 is a graph of the Raman spectrum and the high resolution XPS characterization results of the 3DPG nanomaterial in example 1; wherein a is a Raman spectrum result chart of the 3DPG nano material; b is a high-resolution XPS result graph of the 3DPG nano material C1 s.
FIG. 3 is the NCO in example 1xScanning Electron Microscope (SEM) result images of the nanowire array materials are 2 microns in scale.
FIG. 4 is the NCO and NCO in example 1xAn X-ray powder diffraction (XRD) and electron paramagnetic resonance spectrum characterization result diagram of the nanowire array material; wherein a is NCO and NCOxX-ray powder diffraction (XRD) result pattern of (a); b is NCO and NCOxElectron paramagnetic resonance spectroscopy results.
FIG. 5 is the NCO in example 1xConstant current charge and discharge curve diagram of the nanowire array material electrode.
FIG. 6 is the NCO in example 1xAnd (3) a long cycle performance result graph of the nanowire array material electrode.
FIG. 7 is the NCO in example 1x//3DPG Flexible solid asymmetric SupergradeConstant current charge and discharge curve diagram of capacitor device.
FIG. 8 is the NCO in example 1xCV curve graphs of the flexible solid-state asymmetric supercapacitor device of the/3 DPG in different bending states.
FIG. 9 is the NCO in example 1xThe energy density and the power density of the flexible solid asymmetric supercapacitor device of the DPG are shown in the figure.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and the detailed description, and it should be noted that any combination of the embodiments or technical features described below can be used to form a new embodiment without conflict.
Example 1
A flexible solid asymmetric supercapacitor device comprises a positive electrode material, a negative electrode material and a solid electrolyte; oxygen-deficient NCO with positive electrode material taking flexible carbon cloth as substratexA nanowire array material; the cathode material is a 3DPG nano material taking flexible carbon cloth as a substrate, and the solid electrolyte is PVA/LiCl gel. The preparation method of the flexible solid asymmetric supercapacitor device comprises the following steps:
(1) preparation of flexible carbon cloth substrate:
placing the flexible carbon cloth in absolute ethyl alcohol for ultrasonic treatment to obtain a cleaned flexible carbon cloth substrate;
(2)NCOxpreparing a nanowire array material:
A. preparing an NCO nanowire array material: 1.0g of Ni (NO)3)2·6H2O，2.0g Co(NO3)2·6H2O, 1.0g Thiourea and 1.0g NH4Dissolving the F in 100mL of deionized water at room temperature, performing ultrasonic dispersion uniformly, adding the flexible carbon cloth substrate obtained in the step (1), transferring the mixture into a reaction kettle, performing hydrothermal reaction at 120 ℃ for 12h, naturally cooling, washing with deionized water, and drying to obtain an NCO nanowire material growing on the flexible carbon cloth substrate;
B. preparation of NCOxNanowire array materials:
the first step is as follows: placing the NCO nanowire array material obtained in the step A into a quartz tube, and vacuumizing the quartz tube to 20 mTorr;
the second step is that: injecting N into the evacuated quartz tube2Is a reaction of N2The injection rate of (2) is controlled to be 100mL min-1During the heating, the quartz tube is heated to a reaction temperature of 300 ℃ (the heating speed is controlled to be 5 ℃ and min-1) Heating for 3h, naturally cooling, and stopping injecting N2To obtain NCOxA nanowire array material;
(3) preparation of 3DPG nano material:
A. preparing a graphene oxide suspension: oxidizing graphite powder to prepare graphene oxide by a Hummers method, and ultrasonically dispersing in deionized water to obtain the graphene oxide with the concentration of 3 mg/mL-1Graphene oxide suspension (see paragraph 12 of patent CN108395578A for a specific preparation method);
B. preparing 3DPG rice material: 20mL of 3 mg/mL-1Graphene oxide suspension and 20mL of 0.132 mol.L- 1KOH solution is mixed evenly, and the mixture is added into the flexible carbon cloth substrate (2 multiplied by 3 cm) obtained in the step (1)2) Transferring the mixture into a reaction kettle, and reacting for 5 hours at 180 ℃ to obtain graphene gel growing on the flexible carbon cloth substrate; freeze-drying the obtained graphene gel for 2 days to obtain a 3DPG nano material;
(4) assembling the flexible solid asymmetric supercapacitor device:
NCO prepared in step (2)xTaking the nano material as a positive electrode material, taking the 3DPG nano material prepared in the step (3) as a negative electrode material, and taking PVA/LiCl gel as solid electrolyte; cutting the anode material and the cathode material into rectangles of 0.5cm multiplied by 2cm before assembly, and packaging the rectangles by using a packaging machine to obtain the flexible solid asymmetric super capacitor device.
Examples 2 to 4
Examples 2 to 4 were prepared in the same manner as in example 1, except for the temperature used for the thermal reduction. The specific temperature control in the preparation of examples 2-4 is shown in Table 1. NCO was investigated by referring to the same constant current charge/discharge test as in the above-mentioned Effect example 1xElectrochemical properties of the nanomaterial. NCO from example 1xNano materialAt 2mA · cm-2Specific capacity corresponding to 2.97F cm-2NCO from examples 2 to 4 was testedxThe nano material is 2mA cm-2The corresponding area is specific to capacity.
TABLE 1 temperature regulation of thermal reduction
Examples 6 to 9
Examples 6 to 9 were prepared in the same manner as in example 1 except for the atmosphere used for the thermal reduction. Specific O in the preparation of examples 6-92The temperature control of the atmosphere is shown in Table 2. NCO was investigated by referring to the same constant current charge/discharge test as in the above-mentioned Effect example 1xElectrochemical properties of the nanomaterial. NCO from examples 1 to 5xThe nano material is 2mA cm-2The specific capacity corresponding to the specific time is 1.92F cm-2、2.03F·cm-2、2.97F·cm-2、1.47F·cm-2、1.43F·cm-2NCO from examples 6 to 9 was testedxThe nano material is 2mA cm-2The corresponding area is specific to capacity.
TABLE 2 at O2Temperature regulation under atmosphere
Examples 11 to 14
Examples 11 to 14 were prepared in the same manner as in example 1, except for the time required for the hydrothermal reaction. Specific timing of the preparation of examples 11-14 is shown in Table 3. NCO was investigated by referring to the same constant current charge/discharge test as in the above-mentioned Effect example 1xElectrochemical properties of the nanomaterial. NCO from example 1xThe nano material is 2mA cm-2Specific capacity corresponding to 2.97F cm-2NCO from examples 11 to 14 was testedxThe nano material is 2mA cm-2The corresponding area is specific to capacity.
TABLE 3 time control of hydrothermal reaction
Examples 15 to 18
Examples 15 to 18 were prepared in the same manner as in example 1, except for the concentration of graphene oxide. Specific concentration control in the preparation processes of examples 15-18 is shown in Table 4. The electrochemical performance of the 3DPG nano material is researched by referring to the constant current charge and discharge test method which is the same as that of the effect example 1. The 3DPG nano material prepared in the example 1 is at 1.5mA cm-2Specific capacity corresponding to time is 0.556F cm-23DPG nanomaterials prepared in examples 15-18 were tested at 2mA cm-2The corresponding area is specific to capacity.
Table 4 concentration regulation of graphene oxide
Examples 19 to 22
Examples 19 to 22 were prepared in the same manner as in example 1, except that the hydrothermal reaction temperature for 3DPG preparation was changed. The specific temperature control in the preparation of examples 19-22 is shown in Table 5. The electrochemical performance of the 3DPG nano material is researched by referring to the constant current charge and discharge test method which is the same as that of the effect example 1. The 3DPG nano material prepared in the example 1 is at 1.5mA cm-2Specific capacity corresponding to time is 0.556F cm-23DPG nanomaterials prepared in examples 19-22 were tested at 2mA cm-2The corresponding area is specific to capacity.
TABLE 53 temperature control of DPG hydrothermal reaction
Effect example 1
The 3DPG nano material prepared by the method is subjected to a field emission Scanning Electron Microscopy (SEM) test, and the result is shown in figure 1, which shows that the 3DPG nano material is in a three-dimensional mesoporous shape.
The 3DPG nano material prepared in the above way is characterized by Raman spectrum and high resolution XPS, and the result is shown in figure 2, and the ratio I of the two peak intensities of the 3DPG nano materialD：IG0.93 was reached, indicating that 3DPG has very abundant defects in the edges and planes of graphite lamellae. In addition, the C1s peak was fit into four peaks, corresponding to C — C bond, C — OH bond, C ═ O bond, and C ═ O — OH bond, respectively, which occupy the major components.
For NCO prepared as described abovexThe nanowire array material was subjected to field emission scanning electron microscopy, and the results are shown in fig. 3, in which uniform nanowire arrays were grown on the flexible carbon cloth fibers.
For NCO prepared as described abovexThe nanowire array material is subjected to X-ray powder diffraction (XRD) and electron paramagnetic resonance spectrum characterization, and FIG. 4a shows that the crystal structures of the NCO nanowire material before and after thermal reduction treatment are consistent, and the crystal strength of the NCO nanowire material after thermal reduction treatment is reduced; fig. 4b shows that after the thermal reduction treatment, a strong signal peak appears at g ═ 2.27 in the NCO nanomaterial, indicating that the NCO nanomaterial has introduced oxygen vacancies.
Effect example 2
For NCO prepared as described abovexThe electrochemical performance of the nano material is researched by adopting a constant current charge-discharge test method, and NCOxThe constant current charge and discharge test of the nanomaterial is completed at room temperature by the electrochemical workstation CHI 760D in Shanghai Huachen, and the voltage window of the test is 0-5V, and the results are shown in FIG. 5 and FIG. 6.
As can be seen from FIG. 5, NCO prepared as described abovexThe capacity of the nano material ranges from 2mA cm-22.96 F.cm-3Changing to 40mA cm-21.77 F.cm-3The result shows that the material has good reversibility and rate capability.
As can be seen from FIG. 6, the NCO isxThe nano material is at 10mA cm-2The current density of the positive electrode material still has a capacity retention rate of 96.5 percent after 20000 times of continuous charging and discharging, which shows that the NCOxThe nano material has good circulation stability.
Effect example 3
The prepared flexible solid asymmetric supercapacitor device is subjected to constant current charge and discharge test to study the energy storage performance, the constant current charge and discharge test of the flexible solid asymmetric supercapacitor is completed by the test of a CHI 760D electrochemical workstation in Shanghai at room temperature, the voltage window of the test is 0-1.6V, and the result is shown in figure 7.
As can be seen from FIG. 7, the capacity of the flexible solid asymmetric supercapacitor device prepared as described above ranges from 2mA cm-28.76 F.cm-3Change to 20mA cm-26.49 F.cm-3The result shows that the material has good reversibility and rate capability.
The flexibility of the flexible solid-state asymmetric supercapacitor device is tested, and as a result, as shown in fig. 8, no matter the flexible solid-state asymmetric supercapacitor is in an unbent state, a state of being bent by 90 degrees, or a state of being bent by 135 degrees, the capacitance and the CV curve of the flexible solid-state asymmetric supercapacitor do not change obviously, which indicates that the flexible solid-state asymmetric supercapacitor can be used in any bending state without damaging the CV curve and the capacitance. Therefore, the flexible solid asymmetric supercapacitor device can be arbitrarily bent or twisted without damaging the CV curve and the capacity.
Finally, the energy density and the power density of the flexible solid-state asymmetric supercapacitor device are calculated, and as shown in fig. 9, the current density of the flexible solid-state asymmetric supercapacitor device is 2 mA-cm-2The maximum energy density can reach 3.12mW h cm-3And the energy density of the super capacitor is larger than that of some asymmetric super capacitor devices and batteries published recently.
In conclusion, the super capacitor device has the characteristics of large capacity, high multiplying power and long service life, has the advantages of high energy density, good flexibility and the like, and has a great application prospect in the technical field of electrochemical energy storage.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (3)
1. A preparation method of a flexible solid asymmetric supercapacitor device comprises the following steps:
(1) preparation of flexible carbon cloth substrate:
placing the flexible carbon cloth in absolute ethyl alcohol for ultrasonic treatment to obtain a cleaned flexible carbon cloth substrate;
(2) oxygen deficient NiCo2O4Preparing a nanowire array material:
A. preparation of NiCo2O4Nanowire array materials: dissolving 1g of nickel nitrate hexahydrate, 2g of cobalt nitrate hexahydrate, 1g of thiourea and 1g of ammonium fluoride in 100mL of deionized water at room temperature, ultrasonically dispersing uniformly, adding the flexible carbon cloth obtained in the step (1), transferring the mixture into a reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 12h, naturally cooling, washing with deionized water, and airing to obtain NiCo growing on a flexible carbon cloth substrate2O4A nanowire array material;
B. preparation of oxygen-deficient NiCo2O4Nanowire array materials:
the first step is as follows: b, mixing the NiCo obtained in the step A2O4The nanowire array material is placed in a quartz tube, and the quartz tube is vacuumized to 20 mTorr;
the second step is that: injecting N into the evacuated quartz tube2Is a reaction of N2The flow rate of (2) was controlled to 100mL min−1Heating the quartz tube to reaction temperature of 300 deg.C for 3 hr, naturally cooling, and stopping injecting N2Obtaining oxygen-deficient NiCo2O4A nanowire array material;
(3) preparing a three-dimensional mesoporous graphene nano material:
A. preparing a graphene oxide suspension: oxidizing graphite powder to prepare graphene oxide by a Hummers method, and ultrasonically dispersing in deionized water to obtain the graphene oxide with the concentration of 3mg mL−1A graphene oxide suspension;
B. preparing a three-dimensional mesoporous graphene nano material: 20mL of 3mg mL−1Graphene oxide suspension and 20mL of 0.132mol L−1Uniformly mixing a potassium hydroxide solution, adding the flexible carbon cloth substrate obtained in the step (1), transferring the mixture into a reaction kettle, reacting at 180 ℃ for 5 hours to obtain graphene gel growing on the flexible carbon cloth substrate, and freeze-drying for 2 days to obtain a three-dimensional mesoporous graphene nano material;
(4) assembling the flexible solid asymmetric supercapacitor device:
the oxygen-deficient NiCo prepared in the step (2) is added2O4And (3) packaging the nanowire array material serving as a positive electrode material, the three-dimensional mesoporous graphene nanomaterial prepared in the step (3) serving as a negative electrode material and polyvinyl alcohol/lithium chloride gel serving as a solid electrolyte to obtain the flexible solid asymmetric supercapacitor device.
2. A flexible solid-state asymmetric supercapacitor device, comprising: obtained by the production method according to claim 1.
3. Use of the flexible solid-state asymmetric supercapacitor device of claim 2 in the field of electrochemical energy storage technology.
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