CN111554514A - Flexible heterogeneous nanosheet pseudocapacitance positive electrode material and preparation method thereof - Google Patents

Flexible heterogeneous nanosheet pseudocapacitance positive electrode material and preparation method thereof Download PDF

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CN111554514A
CN111554514A CN202010392366.3A CN202010392366A CN111554514A CN 111554514 A CN111554514 A CN 111554514A CN 202010392366 A CN202010392366 A CN 202010392366A CN 111554514 A CN111554514 A CN 111554514A
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tin
nanosheet
antimony
carbon cloth
array
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CN111554514B (en
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罗绍华
闫绳学
王庆
张亚辉
刘忻
冯建
李鹏伟
张琳
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Northeastern University Qinhuangdao Branch
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    • H—ELECTRICITY
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract

The invention provides a flexible heterogeneous nanosheet pseudocapacitance anode material, and relates to the field of capacitor manufacturing. The preparation steps are as follows: (1) performing hydrophilic and silver plating treatment on the carbon cloth; (2) preparing a tin-antimony precursor array of the super capacitor anode material; (3) preparing a tin-antimony alloy nanosheet array by adopting an in-situ reduction method; (4) preparing a positive electrode material of a tin-antimony alloy-tin antimony sulfide heterogeneous nanosheet. The anode material directly grows on three-dimensional carbon cloth, has a tin-antimony alloy-tin antimony sulfide heterogeneous nanosheet array structure, and has the characteristics of high purity, high density and high orientation; the anode material is neat in appearance, strict and controllable in growth conditions, simple in equipment and process, high in capacitance, good in charge and discharge stability and wide in application prospect.

Description

Flexible heterogeneous nanosheet pseudocapacitance positive electrode material and preparation method thereof
Technical Field
The invention relates to the field of capacitor manufacturing, in particular to a tin-antimony alloy-tin antimony sulfide heterogeneous nanosheet flexible pseudocapacitance material based on carbon cloth loading and a preparation method thereof.
Background
In recent years, wearable electronic devices have been developed rapidly, and conventional supercapacitors have not been able to fully meet practical requirements, and the requirements for energy storage devices have been expanding. In order to meet the energy requirements of these novel flexible electronic products, the research and development of novel flexible energy storage devices, such as flexible lithium ion batteries, flexible supercapacitors, etc., become one of the research focuses in the field of energy storage.
The all-solid-state flexible supercapacitor has a good development space and a good application prospect due to high power density, fast charge and discharge rate, wide working temperature, good stability, long service life and low later maintenance cost, and particularly due to the fact that the graphene-based all-solid-state flexible supercapacitor is rapidly developed in recent years.
However, the energy storage performance of most all-solid-state flexible supercapacitors developed at present still cannot meet daily requirements of people, such as the specific capacitance is still small, the energy density is still not high, the rate capability is relatively poor, and the like.
For example, CN108172417B provides a method for modifying the surface of carbon cloth used for flexible supercapacitor electrodes, which is an electric double layer capacitor with a current density of 1mA/cm2The specific capacitance value is 700mF/cm2Above, when the current density is increased to 20mA/cm2When the specific capacitance is kept at 600mF/cm2As described above, the capacity retention ratio is 85% or more. However, the electric double layer capacitor still shows a lower capacitance value compared with the pseudo capacitor, and cannot meet the high-end requirement.
Therefore, how to prepare the self-supporting flexible film with good conductivity by a simple and effective method and further construct the all-solid-state flexible supercapacitor with excellent electrochemical behavior becomes the key point in the field of the current supercapacitors.
CN201410137197 provides a full pseudocapacitance super capacitor, the positive electrode is made of cobaltosic oxide (Co)3O4) Attached to and grown on the multi-wall carbon nanotube/conductive carbon cloth substrate, and the negative electrode is made of iron oxide (Fe)2O3) Attached and grown on the multi-wall carbon nano tube/conductive carbon cloth substrate. At current densities of 5, 10, 15, 30, 50 and 100mA/cm, respectively2Under constant current discharge, the capacitance is 0.367, 0.338, 0.311, 0.296, 0.259 and 0.211F/cm2. The capacity retention amount is (and the current density is 5 mA/cm)2Capacitance of time) 100%, 92.1%, 84.7%, 80.7%, 70.6% and 57.5%. The current density is increased by 20 times (from 5 mA/cm)2Increased to 100mA/cm2) The specific capacity can still be maintained at 57.5 percent.
The metals Sn and Sb are high in theoretical capacity, have proper electrode potential and high electronic conductivity, and are considered to be electrode materials with great potential. In addition, alloying can mitigate the large volume change during cycling by taking advantage of the difference in the intercalation potentials of Sn and Sb. This also makes SnSb alloy a very potential negative electrode material for sodium ion batteries.
However, during the reaction process, Sn and Sb are very likely to cause electrode pulverization and structure collapse, so that the capacity is rapidly attenuated, and the practical application thereof is severely restricted. In order to solve the problem, one aspect of the present invention is to combine the substrate with a highly conductive elastic substrate, such as graphene, carbon nanotubes, carbon nanofibers, etc.; on the other hand, volume changes are damped by designing novel structures, such as hollow structures.
CN101037224 provides a preparation method of antimony doped tin oxide nanocrystals, which utilizes thermodynamic properties and kinetic properties of each component in a multi-stage combined fuel to control the whole reaction process, so that each reaction process in the combustion process presents a sequence type and a smoke-less type, i.e., hydrolysis, boiling, evaporation, concentration, melting, foaming, oxidation, doping, phase inversion and dispersion are performed orderly, the temperature rise rate does not need to be controlled manually, the combustion process is fast and stable, and a very small amount of smoke released in the reaction process can be absorbed by dilute alkali liquor. However, the preparation process of the method is complex, the obtained oxide has poor conductivity compared with a sulfide electrode, and the electrochemical performance of the oxide cannot meet the requirement of an excellent supercapacitor electrode. The transmission of electrons/ions is limited, so that the performance of the electrode is sharply reduced along with the increase of the transmission distance of the electrons/ions, thereby losing practical value.
CN103058278A provides a method for preparing tin antimony oxide nano powder, which effectively reduces the requirements on production equipment and obtains a high-performance and high-purity nano material. The preparation process of the technology is complex, the material is prepared in an ideal environment by adjusting pH, and solutes are filtered and washed out. Metal oxides, which have low surface redox activity and low electrical conductivity, have limited applications in energy storage applications.
CN107473263A provides a preparation method of superfine high-purity antimony-doped tin oxide nano-powder, and coated glass prepared from the nano-particles has high visible light transmittance, a function of blocking infrared rays and lower resistance, and can be applied to low-emissivity glass and transparent conductive glass. However, the material prepared by the method has no specific morphology, the prepared particles are easy to agglomerate, the stability of the electrochemical performance under long circulation is not facilitated, and the electrode conductivity is poor.
In addition, compared with single metal sulfide, the conductivity of the bimetallic sulfide electrode material is several times or even dozens of times of that of the single metal sulfide, and the defects of poor cycle performance and poor rate characteristic of the single metal sulfide electrode material are overcome. In addition, both components can undergo redox reactions, thereby providing greater specific capacitance. Therefore, the bimetal sulfide pseudocapacitance electrode material shows excellent electrochemical performance.
CN110223849A provides a cobalt sulfide composite electrode material, a preparation method and an application thereof, comprising the following steps: (1) placing the carbon cloth in a mixed solution containing cobalt nitrate, ammonium fluoride, urea and water for hydrothermal reaction, and growing a diamond tetraoxide on the carbon cloth to obtain a precursor; (2) and mixing the precursor with a sodium sulfide solution, and carrying out hydrothermal reaction to obtain the cobalt sulfide composite electrode material. When the scanning speed is 10mV/s, the capacitance is 0.48 and 0.51F/cm respectively2The effect is still unsatisfactory.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides a flexible heterogeneous nanosheet pseudocapacitor material and a preparation method thereof. The anode material directly grows on three-dimensional carbon cloth, has a tin-antimony alloy-tin antimony sulfide heterogeneous nanosheet array structure, and has the characteristics of high purity, high density and high orientation. The anode material is neat in appearance, strict and controllable in growth conditions, simple in equipment and process, high in capacitance, good in charge and discharge stability and wide in application prospect.
The technical scheme of the invention is as follows:
a flexible heterogeneous nanosheet pseudocapacitance anode material is prepared by the following steps:
(1) carbon cloth hydrophilicity and silver plating treatment:
cutting the carbon cloth into a shape of (0.6-1.2) cm x (1.3-1.8) cm with the mass of 0.48-0.72 g, respectively cleaning with deionized water and ethanol, drying and then carrying out strong acid etching;
then slowly adding 1.0-3.0 g of KMnO4Placing the reactant in a water bath kettle, and keeping the temperature of 30-50 ℃ for 2-4 h; finally, the treated carbon cloth is washed clean by deionized water and dried;
plating silver on the surface of the carbon cloth by using a magnetron sputtering method, wherein the plating time is 1-3 h; the thickness of the silver plating is 1-3 mu m;
(2) preparing a tin-antimony precursor array of the positive electrode material of the super capacitor:
2-4 mmol of SnCl 22 to 4mmol of SbCl3Dispersing 2-6 mmol of ammonium fluoride and 4-12 mmol of urea in 70mL of deionized water, fully stirring, transferring to a 100mL reaction kettle, adding flexible substrate carbon cloth, and sealing the reaction kettle; reacting for 6-10 h at 120-140 ℃; washing the resultant with deionized water for several times, and drying in vacuum at 40-80 ℃ for 2-4 h; obtaining a tin-antimony nanosheet precursor nano-array;
(3) preparing a tin-antimony alloy nanosheet array by adopting an in-situ reduction method:
putting the product obtained in the step (2) into a tube furnace, heating to 100-300 ℃ at a heating rate of 1-3 ℃/min, and introducing H2Reducing for 20-40 min by using/Ar airflow; in the reduction process, the tin-antimony nanosheet precursor array is converted into a tin-antimony alloy nanosheet array, and meanwhile, the nanosheet array is not damaged;
(4) preparing a positive electrode material of a tin-antimony alloy-tin-antimony sulfide heterogeneous nanosheet:
dissolving 4-6 mmol of sodium sulfide solution in 65-75 mL of deionized water, transferring the solution to a 100mL reaction kettle, placing the tin-antimony alloy nanosheet array in the reaction kettle, and sealing the reaction kettle; reacting for 6-10 h at 140-180 ℃; after cooling, washing with deionized water for several times, and vacuum drying at 40-80 ℃ for 4-8 h; and obtaining the flexible heterogeneous nanosheet pseudocapacitance anode material.
Preferably, the strong acid etching in the step (1) is to immerse the carbon cloth into 15-25 mL of concentrated H2SO4And 8-15 mL of concentrated HNO3Magnetically stirring the mixed solution for 5-15 min; said concentrated H2SO4The mass fraction of (A) is 98%; the concentrated HNO3Is 68 percent.
Preferably, H in step (3)2The volume ratio of/Ar was 10/90.
Preferably, the concentration of the sodium sulfide solution in the step (4) is 2-4 mol/L.
The beneficial technical effects of the invention are as follows:
the activated carbon cloth is activated by concentrated nitric acid, concentrated sulfuric acid and potassium permanganate and serves as a flexible carrier of the electrode material of the supercapacitor, and meanwhile, the surface of the carbon cloth is plated with silver by means of magnetron sputtering, so that the conductivity of the carbon cloth is increased, and the active sites of electrochemical reaction are increased; and then the obtained carbon cloth is put into a mixed solution of a tin source, an antimony source and a sulfur source to carry out hydrothermal reaction so as to prepare the flexible carbon cloth loading sheet tin-antimony alloy-tin-antimony sulfide supercapacitor electrode material for the supercapacitor, so that the supercapacitor electrode material with excellent comprehensive performance and high specific capacitance is constructed, and the method has a wide application prospect.
Diversification of the composition of the present invention can reduce the optical bandgap width (Eg) of the material, which helps to improve the electrical conductivity of the material. The compound formed by utilizing the coordination among the elements and the nonmetal elements has higher theoretical specific capacity. Meanwhile, the conductivity and the electrochemical activity of the bimetallic compound can be effectively improved through the interaction between the ternary compounds.
The tin-antimony alloy-tin antimony sulfide heterogeneous nanosheet prepared by the method uniformly grows on the surface of the carbon cloth, the synthetic growth condition is strictly controllable, the equipment and the process are simple, and the cost is low; the heterostructure of the formed sulfide and the tin-antimony alloy, the internal ultrahigh conductive alloy provides a quick channel for electron transfer, the external bimetallic sulfide provides pseudocapacitance performance, and the two have synergistic effect.
Tests prove that the electrolyte prepared by the invention is 3mol/L potassium hydroxide aqueous solutionThe positive electrode of the water system super capacitor is 0.5A/cm2The lower graph shows 8.61F/cm2High specific capacitance of (2).
Drawings
FIG. 1 is an SEM image and an EDS energy spectrum of the sample prepared in the step (4) before and after vulcanization.
FIG. 2 is an SEM image of the product of step (4) after sulfidation with different concentrations of sulfur source.
FIG. 3 is an SEM image of the product of the silver plating reaction without performing step (1).
FIG. 4 is an XRD pattern of the product obtained after sulfurization in step (4) with addition of sulfur sources of different concentrations.
Fig. 5 is a constant current charge and discharge curve of the three-electrode system prepared in example 1 at different current densities.
FIG. 6 is a graph of rate capability of the three-electrode system prepared in example 1 at different current densities.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
(1) carbon cloth hydrophilicity and silver plating treatment:
cutting carbon cloth into 1cm × 1.5.5 cm shape (mass is 0.62g), cleaning with deionized water and ethanol, oven drying, strongly acid etching, and slowly adding 1.0g KMnO4Placing the reactant in a water bath kettle, and keeping the temperature at 30 ℃ for 4 hours; finally, the treated carbon cloth is washed clean by deionized water and dried for standby; and (3) plating silver on the surface of the carbon cloth by using a magnetron sputtering method, wherein the plating time is 1h, and the silver plating thickness is 1 mu m.
(2) Preparing a tin-antimony precursor of a super capacitor anode material:
adding 2mmol of SnCl22mmol of SbCl32mmol of ammonium fluoride and 4mmol of urea are dispersed in a dispersion containing 70mL of deionized waterIn water, fully stirring, transferring to a 100mL sealed reaction kettle, adding a flexible substrate carbon cloth, sealing the reaction kettle, and reacting at 120 ℃ for 10 hours; washing the resultant with deionized water for several times, and vacuum drying at 40 deg.C for 4 hr;
(3) preparing a tin-antimony alloy nanosheet array by adopting an in-situ reduction method: putting the product obtained in the step (2) into a tube furnace, heating to 100 ℃ at the heating rate of 1 ℃/min, and introducing H2Ar gas flow, reducing for 40 min; in the reduction process, the tin-antimony nanosheet precursor array is converted into a tin-antimony alloy nanosheet array; meanwhile, the nano sheet array is not damaged;
(4) preparing a positive electrode material of a tin-antimony alloy-tin-antimony sulfide heterogeneous nanosheet:
dissolving 4mmol of sodium sulfide solution in 70mL of deionized water, transferring the solution into a 100mL sealed reaction kettle, placing the tin-antimony alloy nanosheet array into the reaction kettle, sealing the reaction kettle, and reacting for 10 hours at the temperature of 140 ℃; and after cooling, washing with deionized water for several times, and vacuum drying at 40 ℃ for 8h to obtain the flexible heterogeneous nanosheet pseudocapacitor positive electrode material.
The strong acid etching in the step (1) is to immerse the carbon cloth into 15mL of concentrated H2SO4And 8mL concentrated HNO3Magnetically stirring the mixed solution for 15 min; said concentrated H2SO4The mass fraction of (A) is 98%; the concentrated HNO3Is 68 percent.
H in the step (3)2The volume ratio of/Ar was 10/90. And (4) the concentration of the sodium sulfide solution in the step (4) is 2 mol/L.
The prepared flexible heterogeneous nanosheet pseudocapacitor positive electrode material is soaked in 3mol/L KOH solution for 24 hours to prepare a working electrode, then the working electrode is clamped by the working electrode clamp and an induction electrode, a platinum sheet is used as a counter electrode, and an Hg/HgO electrode is used as a reference electrode to form a three-electrode system.
Example 2:
(1) carbon cloth hydrophilicity and silver plating treatment:
cutting carbon cloth into 1cm × 1.5.5 cm shape (mass is 0.62g), cleaning with deionized water and ethanol, oven drying, performing strong acid etching, and slowly adding 2.0g KMnO4Placing the reactant in a water bath kettle, and keeping the temperature at 40 ℃ for 3 h; finally, the treated carbon cloth is washed clean by deionized water and dried for standby; plating silver on the surface of the carbon cloth by using a magnetron sputtering method, wherein the film plating time is 2 hours; the thickness of the silver plating is 2 mu m; (2) preparing a tin-antimony precursor of a super capacitor anode material:
adding 3mmol of SnCl23mmol of SbCl3Dispersing 4mmol of ammonium fluoride and 8mmol of urea in 70mL of deionized water, fully stirring, transferring to a 100mL sealed reaction kettle, adding flexible substrate carbon cloth, sealing the reaction kettle, and reacting at 130 ℃ for 8 hours; washing the resultant with deionized water for several times, and vacuum drying at 60 deg.C for 3 hr;
(3) preparing a tin-antimony alloy nanosheet array by adopting an in-situ reduction method:
putting the product obtained in the step (2) into a tube furnace, heating to 200 ℃ at a heating rate of 2 ℃/min, and introducing H2Ar gas flow, reducing for 30 min; in the reduction process, the tin-antimony nanosheet precursor array is converted into a tin-antimony alloy nanosheet array; meanwhile, the nano sheet array is not damaged;
(4) preparing a positive electrode material of a tin-antimony alloy-tin-antimony sulfide heterogeneous nanosheet:
dissolving 5mmol of sodium sulfide solution in 70mL of deionized water, transferring the solution into a 100mL sealed reaction kettle, placing the tin-antimony alloy nanosheet array into the reaction kettle, sealing the reaction kettle, and reacting for 8 hours at 160 ℃; and after cooling, washing with deionized water for several times, and vacuum drying at 60 ℃ for 6h to obtain the flexible heterogeneous nanosheet pseudocapacitor positive electrode material. The strong acid etching in the step (1) is to immerse the carbon cloth into 10mL of concentrated H2SO4And 12mL concentrated HNO3Magnetically stirring the mixed solution for 10 min; said concentrated H2SO4The mass fraction of (A) is 98%; the concentrated HNO3Is 68 percent.
H in the step (3)2The volume ratio of/Ar was 10/90. And (4) the concentration of the sodium sulfide solution in the step (4) is 3 mol/L.
The prepared flexible heterogeneous nanosheet pseudocapacitor positive electrode material is soaked in 3mol/L KOH solution for 24 hours to prepare a working electrode, then the working electrode is clamped by the working electrode clamp and an induction electrode, a platinum sheet is used as a counter electrode, and an Hg/HgO electrode is used as a reference electrode to form a three-electrode system.
Example 3:
(1) carbon cloth hydrophilicity and silver plating treatment:
cutting carbon cloth into 1cm × 1.5.5 cm shape (mass is 0.62g), cleaning with deionized water and ethanol, oven drying, performing strong acid etching, and slowly adding KMnO 3.0g4Placing the reactant in a water bath kettle, and keeping the temperature at 50 ℃ for 2 h; finally, the treated carbon cloth is washed clean by deionized water and dried for standby; plating silver on the surface of the carbon cloth by using a magnetron sputtering method, wherein the film plating time is 3 hours; the thickness of the silver plating is 3 mu m; (2) preparing a tin-antimony precursor of a super capacitor anode material:
4mmol of SnCl24mmol of SbCl36mmol of ammonium fluoride and 12mmol of urea are dispersed in deionized water containing 70mL, the mixture is transferred to a 100mL sealed reaction kettle after being fully stirred, then flexible substrate carbon cloth is added, the reaction kettle is sealed, and the reaction is carried out for 6 hours at 140 ℃; washing the resultant with deionized water for several times, and vacuum drying at 80 deg.C for 2 hr;
(3) preparing a tin-antimony alloy nanosheet array by adopting an in-situ reduction method:
putting the product obtained in the step (2) into a tube furnace, heating to 300 ℃ at a heating rate of 3 ℃/min, and introducing H2Ar gas flow, reducing for 20 min; in the reduction process, the tin-antimony nanosheet precursor array is converted into a tin-antimony alloy nanosheet array; meanwhile, the nano sheet array is not damaged;
(4) preparing a positive electrode material of a tin-antimony alloy-tin-antimony sulfide heterogeneous nanosheet:
dissolving 6mmol of sodium sulfide solution in 70mL of deionized water, transferring the solution into a 100mL sealed reaction kettle, placing the tin-antimony alloy nanosheet array into the reaction kettle, sealing the reaction kettle, and reacting for 6 hours at 180 ℃; and after cooling, washing with deionized water for several times, and vacuum drying at 80 ℃ for 4h to obtain the flexible heterogeneous nanosheet pseudocapacitor positive electrode material.
The strong acid etching in the step (1) is to immerse the carbon cloth into 25mL of concentrated H2SO4And 15mL concentrated HNO3Magnetically stirring the mixed solution for 5 min; said concentrated H2SO4The mass fraction of (A) is 98%; the concentrated HNO3Is 68 percent.
H in the step (3)2The volume ratio of/Ar was 10/90. And (4) the concentration of the sodium sulfide solution in the step (4) is 4 mol/L.
The prepared flexible heterogeneous nanosheet pseudocapacitor positive electrode material is soaked in 3mol/L KOH solution for 24 hours to prepare a working electrode, then the working electrode is clamped by the working electrode clamp and an induction electrode, a platinum sheet is used as a counter electrode, and an Hg/HgO electrode is used as a reference electrode to form a three-electrode system.
Test example:
based on example 1, referring to fig. 1, a, b in fig. 1 are SEM images of the tin antimony alloy nanosheet array sample prepared in step (3), and c, d are SEM images of the tin antimony alloy-tin antimony sulfide heteronanosheet sample prepared in step (4). The figure shows that the sample keeps the precursor morphology of the nanosheet before and after vulcanization and is not damaged. And the figure e is an EDS (EDS energy spectrum) of the tin-antimony alloy-tin-antimony sulfide heterogeneous nanosheet, the element distribution of tin-antimony sulfide in-situ growing on the carbon cloth can be observed, the main elements of the synthesized product are sulfur, tin and antimony, and the three elements can be uniformly distributed on the surface of the material.
When the sodium sulfide solution is added in the step (4), the concentration of the sodium sulfide solution is changed, and SEM images after the sodium sulfide is vulcanized at different concentrations are shown in FIG. 2. FIGS. a-d, e-h and i-l correspond to sodium sulfide concentrations of 3, 4 and 5mmol, respectively. It can be seen that when the concentration of sodium sulfide is too high (fig. i-l), the sample surface is completely covered by sulfide, and the original precursor morphology is lost.
The silver plating step was not performed in step (1), and the SEM image of the resulting final product is shown in fig. 3. It can be seen from the figure that the surface of the carbon cloth has no unevenness of in-situ growth of the silver-plated sample, and a part of the surface of the carbon cloth is exposed, as shown by the circled part in the figure.
When the sodium sulfide solution is added in the step (4), the concentration of the sodium sulfide solution is changed, and XRD patterns after different sulfur sources are vulcanized are shown in figure 4. The XRD pattern gradually shows the pattern of tin antimony sulfide along with the increase of the content of the sulfur source, and the XRD pattern only has a tin antimony alloy phase when no sulfur source is added.
FIGS. 5 and 6 are the constant current discharge curve and the rate capability plot for the three-electrode system prepared in example 1 at different current densities of 0.5, 1.0, 1.5 and 2.0A/cm, respectively2Under the condition of constant current discharge, the capacitance of the capacitor is respectively 8.61, 8.23, 7.64 and 7.12F/cm2. The capacity retention amount is (and the current density is 0.5A/cm)2Capacitance comparison) 95.6%, 88.7% and 82.7%.
While the embodiments of the present invention have been disclosed above, it is not limited to the applications listed in the description and embodiments, but is fully applicable to various fields suitable for the present invention, and it will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in the embodiments without departing from the principle and spirit of the present invention, and therefore the present invention is not limited to the specific details without departing from the general concept defined in the claims and the scope of equivalents thereof.

Claims (4)

1. A flexible heterogeneous nanosheet pseudocapacitance anode material is characterized by comprising the following preparation steps:
(1) carbon cloth hydrophilicity and silver plating treatment:
cutting the carbon cloth into a shape of (0.6-1.2) cm x (1.3-1.8) cm with the mass of 0.48-0.72 g, respectively cleaning with deionized water and ethanol, drying and then carrying out strong acid etching;
then slowly adding 1.0-3.0 g of KMnO4Placing the reactant in a water bath kettle, and keeping the temperature of 30-50 ℃ for 2-4 h; finally, the treated carbon cloth is washed clean by deionized water and dried;
plating silver on the surface of the carbon cloth by using a magnetron sputtering method, wherein the plating time is 1-3 h; the thickness of the silver plating is 1-3 mu m;
(2) preparing a tin-antimony precursor array of the positive electrode material of the super capacitor:
2-4 mmol of SnCl22 to 4mmol of SbCl3Dispersing 2-6 mmol of ammonium fluoride and 4-12 mmol of urea in 70mL of deionized water, fully stirring, transferring to a 100mL reaction kettle, adding flexible substrate carbon cloth, and sealing the reaction kettle; reacting for 6-10 h at 120-140 ℃; washing the resultant with deionized water for several times, and drying in vacuum at 40-80 ℃ for 2-4 h; obtaining a tin-antimony nanosheet precursor nano-array;
(3) preparing a tin-antimony alloy nanosheet array by adopting an in-situ reduction method:
putting the product obtained in the step (2) into a tube furnace, heating to 100-300 ℃ at a heating rate of 1-3 ℃/min, and introducing H2Reducing for 20-40 min by using/Ar airflow; in the reduction process, the tin-antimony nanosheet precursor array is converted into a tin-antimony alloy nanosheet array, and meanwhile, the nanosheet array is not damaged;
(4) preparing a positive electrode material of a tin-antimony alloy-tin-antimony sulfide heterogeneous nanosheet:
dissolving 4-6 mmol of sodium sulfide solution in 65-75 mL of deionized water, transferring the solution to a 100mL reaction kettle, placing the tin-antimony alloy nanosheet array in the reaction kettle, and sealing the reaction kettle; reacting for 6-10 h at 140-180 ℃; after cooling, washing with deionized water for several times, and vacuum drying at 40-80 ℃ for 4-8 h; and obtaining the flexible heterogeneous nanosheet pseudocapacitance anode material.
2. The flexible heterogeneous nanosheet pseudocapacitor material of claim 1, wherein the strong acid etching in step (1) is carried out by immersing carbon cloth in 15-25 mL of concentrated H2SO4And 8-15 mL of concentrated HNO3Magnetically stirring the mixed solution for 5-15 min; said concentrated H2SO4The mass fraction of (A) is 98%; the concentrated HNO3Is 68 percent.
3. The flexible heteronanosheet pseudocapacitive positive electrode material of claim 1, wherein the H of step (3) is2The volume ratio of/Ar was 10/90.
4. The flexible heterogeneous nanosheet pseudocapacitor cathode material of claim 1, wherein the sodium sulfide solution of step (4) has a concentration of 2-4 mol/L.
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