CN115188606A - Flexible self-supporting MXene quantum dot/MXene thin film electrode and preparation method and application thereof - Google Patents
Flexible self-supporting MXene quantum dot/MXene thin film electrode and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES 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
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The invention provides a flexible self-supporting MXene quantum dot/MXene thin film electrode and a preparation method and application thereof, and belongs to the technical field of flexible energy storage electrode materials. According to the invention, a hydrothermal reaction is carried out under a microwave condition, inert gas protection is not required, a molecular shearing reagent is used as a surface passivating agent and a shearing reagent of the MXene nanosheet, the antioxidation and dimension cutting of MXene are simultaneously realized, and further the 0D MXene quantum dots are derived in situ to modify the 2D MXene nanosheet by a one-step method, so that the formed same 0D MXene quantum dots and the 2D MXene are easy to form strong interaction, and the rapid transmission of electrons is facilitated; and the 2D nanosheet is used as a substrate, the 0D quantum dots are prevented from agglomerating, the 0D MXene quantum dots can provide more electrochemical active sites, and the charge storage capacity of the MXene nanosheet can be remarkably enhanced.
Description
Technical Field
The invention relates to the technical field of preparation of flexible energy storage electrode materials, in particular to a flexible self-supporting MXene quantum dot/MXene thin film electrode and a preparation method and application thereof.
Background
With the progress of science and technology and the improvement of the living standard of human beings, high-tech designs and products with advanced functions and technical innovation become the expectation of human beings and the direction of social development. Currently, some emerging flexible, bendable and foldable electronic devices, such as wearable electronics, foldable smart phones, electronic skins, and implantable medical monitoring devices, facilitate human productive life and improve the quality of life of people. In order to power these advanced electronic devices, it is necessary to develop flexible energy storage devices to ensure that these electronic devices maintain excellent and stable charge storage capabilities while undergoing deformation. Meanwhile, in order to prepare a high-performance flexible energy storage device, it is very important to develop an electrode material having excellent mechanical flexibility and high charge storage capacity.
MXene as a novel two-dimensional (2D) nano material has the characteristics of excellent conductivity, metal multivalent state, abundant surface hydrophilic functional groups, proton intercalation pseudocapacitance, high mechanical flexibility and the like. The MXene solution is subjected to vacuum filtration to prepare the flexible self-supporting MXene electrode material, and the flexible self-supporting MXene electrode material is widely researched in the field of flexible energy storage. MXene prepared usually presents a multilayer stacking morphology, and stripping multilayer nanosheets into a single layer or few layers can greatly increase the specific surface area and the electrochemically active sites of MXene. However, the MXene stripping strategy does not solve the problems of active site blockage, electrolyte transmission obstruction and the like caused by the close packing of the MXene nanosheets in the preparation process of the self-supporting electrode. Therefore, by regulating the structure or surface chemistry of MXene, a flexible self-supporting electrode material with more excellent performance can be prepared.
The 0D quantum dots have more edge active sites, shorter ion diffusion distance and larger contact area of electrolyte due to the small-size structural characteristics, and are widely applied to the fields of energy storage, catalysis, adsorption and the like. Therefore, cutting the 2D nano material into 0D quantum dots is an effective strategy for preparing high-performance electrode materials. The hydrothermal method is a common method for preparing 0D quantum dots by using a 2D material, but the MXene nanosheet is easily oxidized under the wet condition and the heating environment of the hydrothermal method, so that the excellent flexibility and conductivity of the MXene are damaged.
Disclosure of Invention
The invention aims to provide a flexible self-supporting MXene quantum dot/MXene thin film electrode and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a flexible self-supporting MXene quantum dot/MXene thin film electrode, which comprises the following steps:
mixing MXene nanosheet dispersion liquid with a molecular shearing reagent to obtain a precursor solution;
and carrying out hydrothermal reaction on the precursor solution under the microwave condition to obtain the flexible self-supporting MXene quantum dot/MXene thin film electrode.
Preferably, the preparation method of the MXene nanosheet dispersion comprises the following steps: mixing MAX raw materials and an etching solution, and etching to obtain a multilayer MXene nanosheet; and mixing the multiple layers of MXene nanosheets with water, and carrying out ultrasonic stripping to obtain MXene nanosheet dispersion liquid.
Preferably, the power of the ultrasonic stripping is 300-600W, and the time is 30-60 min.
Preferably, the MAX raw material has a chemical formula of M n+1 AX n M is Sc, ti, zr, V, nb, cr or Mo, A is Al, ga, si, TI, sn or Ge, X is C or N, and N =1 to 3.
Preferably, the concentration of the MXene nanosheet dispersion is 5 to 15 mg/mL -1 (ii) a The molecular shearing agent comprises one or more of citric acid, tannic acid, sodium alginate and polydopamine.
Preferably, the ratio of the mass of the molecular shearing reagent to the volume of the MXene nanosheet dispersion is (2-4) g (6-10) mL.
Preferably, the first and second liquid crystal materials are,mixing the MXene nanosheet dispersion liquid and a molecular shearing reagent under a stirring condition; the stirring speed is 200-400 r.min -1 The time is 8 to 12 hours.
Preferably, the temperature of the hydrothermal reaction is 160-200 ℃, the power is 600-800W, and the time is 0.5-2 h.
The invention provides a flexible self-supporting MXene quantum dot/MXene thin film electrode prepared by the preparation method in the technical scheme, which comprises a 2D MXene nanosheet and 0D MXene quantum dot modified on the surface of the 2D MXene nanosheet.
The invention provides application of the flexible self-supporting MXene quantum dot/MXene thin film electrode in a flexible energy storage device or wearable electronic equipment.
The invention provides a preparation method of a flexible self-supporting MXene quantum dot/MXene thin film electrode, which comprises the following steps: mixing MXene nanosheet dispersion liquid with a molecular shearing reagent to obtain a precursor solution; and carrying out hydrothermal reaction on the precursor solution under the microwave condition to obtain the flexible self-supporting MXene quantum dot/MXene thin film electrode. The hydrothermal reaction is carried out under the microwave condition, inert gas protection is not needed, a molecular shearing reagent is used as a surface passivating agent and a shearing reagent of the MXene nanosheets, meanwhile, the antioxidation and the dimension cutting of the MXene are realized (the 2D MXene nanosheets are sheared to form 0D MXene quantum dots), the 0D MXene quantum dots are further derivatized in situ to modify the 2D MXene nanosheets by a one-step method, the formed same 0D MXene quantum dots and the 2D MXene are easy to form strong interaction (the MXene quantum dots have more exposed Ti-OH, ti-O and C-O edge active sites, and the rich active sites can form strong hydrogen bonds and van der Waals interaction with polar functional groups on the surfaces of the MXene nanosheets), and the rapid transmission of electrons is facilitated; and the 2D nanosheet is used as a substrate, the 0D quantum dots are prevented from agglomerating, the 0D MXene quantum dots can provide more electrochemical active sites, and the charge storage capacity of the MXene nanosheet can be remarkably enhanced.
The flexible self-supporting MXene quantum dot/MXene thin film electrode prepared by the method has good mechanical flexibility and excellent charge storage capacity. FlexibilityThe symmetrical solid-state super capacitor assembled by the self-supporting 0D/2D MXene quantum dot/MXene film electrode not only has high energy density (30-100 mu Wh cm) -2 ) And power density (0.5-10 mW cm) -2 ) Stable charge storage performance is also exhibited in different bent states (0 to 180 °). Therefore, the electrode has great application potential in flexible energy storage devices (super capacitors, ion batteries, lithium sulfur batteries and the like) and wearable electronic equipment.
The preparation method is simple and controllable, has good universality, does not need a binder or a conductive reagent, greatly reduces the cost, and is easy for industrial production.
Drawings
FIG. 1 is a photomicrograph of a flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode prepared in example 1;
FIG. 2 is a high resolution TEM image (a), a 0D MXene quantum dot lattice fringe pattern (b) and a particle size distribution (c) of 0DMXene quantum dots of the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode prepared in example 1;
FIG. 3 is a high resolution TEM image (a) of the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode and the particle size distribution diagram (b) of the MXene quantum dots obtained in example 2;
FIG. 4 is a comparison graph (a) of cyclic voltammetry performance and a comparison graph (b) of constant current charge and discharge performance of the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode prepared in example 1 and the flexible self-supporting MXene thin film electrode prepared in comparative example 1;
FIG. 5 is a graph showing the specific capacitance change of the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode prepared in example 1 and the flexible self-supporting MXene thin film electrode prepared in comparative example 1 at different scanning speeds;
FIG. 6 shows the current density of 10mA cm for the device assembled by the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode prepared in example 1 -2 A cyclic stability (a) and coulombic efficiency graph (a, an embedded graph is constant current charging and discharging data of the first time and the last time of the device cycle) and a Ragon graph (b) of 10000 times of lower cycle;
FIG. 7 is a flexible charge storage capacity diagram of a flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode assembled device prepared in example 1;
FIG. 8 is a photograph of a series driven red LED from three flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode assemblies prepared in example 1.
Detailed Description
The invention provides a preparation method of a flexible self-supporting MXene quantum dot/MXene thin film electrode, which comprises the following steps:
mixing MXene nanosheet dispersion liquid with a molecular shearing reagent to obtain a precursor solution;
and carrying out hydrothermal reaction on the precursor solution under the microwave condition to obtain the flexible self-supporting MXene quantum dot/MXene thin film electrode.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The MXene nanosheet dispersion liquid and the molecular shearing reagent are mixed to obtain a precursor solution. In the present invention, the preparation method of the MXene nanosheet dispersion preferably includes the steps of: mixing MAX raw materials and an etching solution, and etching to obtain a multilayer MXene nanosheet; and mixing the multiple layers of MXene nanosheets with water, and carrying out ultrasonic stripping to obtain MXene nanosheet dispersion liquid.
In the present invention, the MAX raw material preferably has a chemical formula of M n+1 AX n M is Sc, ti, zr, V, nb, cr or Mo, A is Al, ga, si, TI, sn or Ge, X is C or N, and N = 1-3; the MAX raw material is preferably Ti 3 AlC 2 。
The invention has no special limit on the type and concentration of the etching solution, and the concentration of the corresponding etching solution known in the art can be adjusted according to the actual requirement; in the embodiment of the invention, the etching solution is LiF/HCl solution, and the LiF/HCl solution is prepared by dissolving LiF in HCl solution. The invention has no special limit on the dosage of the etching solution, and the MAX raw material can be fully etched by adjusting according to the actual requirement.
The invention is used for the MAX raw material and the etching solutionThe mixing process is not particularly limited, and the materials are uniformly mixed according to the process well known in the art; the etching is preferably carried out under stirring conditions; the rotating speed of the stirring is preferably 180 to 220rmin -1 More preferably 200rmin -1 (ii) a The etching temperature is preferably 35 ℃, and the time is preferably 48h.
After the etching is finished, the obtained etching product is preferably repeatedly centrifuged and washed until the pH is = 6-7, and the obtained lower layer is precipitated into a multilayer MXene nanosheet.
The dosage ratio of the multiple layers of MXene nanosheets to water is not specially limited, and sufficient water can be fully stripped. In the invention, the power of the ultrasonic stripping is preferably 300-600W, and the time is preferably 30-60 min.
After the ultrasonic stripping is finished, centrifuging the obtained product preferably to obtain an upper layer which is MXene nanosheet dispersion liquid; the rotation speed of the centrifugation is preferably 3000rmin -1 The centrifugation time is preferably 30 to 60min.
In the present invention, the concentration of the MXene nanosheet dispersion is preferably 5 to 15 mg/mL -1 More preferably 6 mg/mL -1 (ii) a The MXene nanosheet dispersion liquid is a few-layer 2D MXene nanosheet.
In the present invention, MXene has the chemical formula M n+1 X n T x M is Sc, ti, zr, V, nb, cr or Mo, X is C or N, T x is-OH, -O, -Cl and-F, and n =1 to 3.
In the present invention, the molecular shearing agent preferably comprises one or more of citric acid, tannic acid, sodium alginate and polydopamine; when the molecular shearing reagents are more than two of the molecular shearing reagents, the proportion of the molecular shearing reagents of different types is not particularly limited, and the molecular shearing reagents can be prepared in any proportion. The molecular shear reagent can form hydrogen bonds and coordination bonds with MXene. In the present invention, the molecular cleavage agent is preferably used in the form of an aqueous solution, and the concentration of the aqueous solution of the molecular cleavage agent is not particularly limited in the present invention, and may be adjusted depending on the specific amount of the molecular cleavage agent used.
The molecular shear reagent can prevent MXene from being oxidized in the treatment process, and can shear a 2D MXene nanosheet to form 0D MXene quantum dots, so that abundant active sites are provided, and charge storage is facilitated. The antioxidant mechanism is as follows: o is 2 And H 2 O easily attacks the exposed M atoms around the MXene nanosheets to form corresponding metal oxides, and then the oxidation gradually spreads from the edge to the center, so that the 2D nanosheet structure is damaged. Taking citric acid as an example, the citric acid is used as a surfactant and a reducing agent, and-COOH and-OH in citric acid molecules can be modified on the surface and the edge of the MXene nanosheet through chemical interaction, so that MXene is passivated to inhibit oxidation, and the reducibility of the citric acid further enhances the oxidation resistance of the MXene nanosheet. In addition, the strong coordination between-COOH in citric acid and M atoms on the surface edge of MXene and a large number of hydrogen bonds between citric acid molecules and MXene weaken C-M-C bonds in MXene, so that M-C bonds in MXene are broken. Once cracking occurs, the molecular thermal motion will continue to promote more M-C bond cleavage, shearing the 2D MXene nanoplatelets to form 0D MXene quantum dots.
In the present invention, the ratio of the mass of the molecular shearing agent to the volume of the MXene nanosheet dispersion is preferably (2 to 4) g of (6 to 10) mL, and more preferably (3 to 3.5) g of (10) mL.
In the present invention, the mixing of the MXene nanosheet dispersion and the molecular shear reagent is preferably performed under stirring conditions; the stirring speed is preferably 200-400 r.min -1 The time is preferably 8 to 12 hours, and more preferably 10 hours; the stirring is preferably carried out at room temperature.
After the precursor solution is obtained, the precursor solution is subjected to hydrothermal reaction under the microwave condition to obtain the flexible self-supporting MXene quantum dot/MXene thin film electrode.
In the present invention, the temperature of the hydrothermal reaction is preferably 160 to 200 ℃, more preferably 180 ℃; the power is preferably 600 to 800W, and the time is preferably 0.5 to 2h. In the hydrothermal reaction process, cutting the 2D MXene nanosheets into 0D MXene quantum dots; through the hydrogen bonding effect between the surface functional groups (0D MXene quantum dot and 2D MXene nanosheet, the surfaces of the 0D MXene quantum dot and the 2D MXene nanosheet are provided with the same surface functional groups, wherein the strong hydrogen bonding effect can be formed between-OH, -F and-O functional groups), and the 0D MXene quantum dot is modified on the surface of the 2D MXene nanosheet.
After the hydrothermal reaction is finished, the obtained product is preferably cooled to room temperature, and vacuum filtration, water washing and vacuum drying are sequentially carried out to obtain the flexible self-supporting MXene quantum dot/MXene film electrode.
In the present invention, the vacuum filtration preferably employs an aqueous filter membrane, and the particle size of the aqueous filter membrane is preferably 0.22 μm; the process of the water washing is not particularly limited, and the washing can be carried out according to the process well known in the field; the temperature of the vacuum drying is preferably 20-60 ℃, and the time is preferably 6-12 h.
The invention provides a flexible self-supporting MXene quantum dot/MXene thin film electrode prepared by the preparation method in the technical scheme, which comprises a 2D MXene nanosheet and 0D MXene quantum dot modified on the surface of the 2D MXene nanosheet.
The invention provides application of the flexible self-supporting MXene quantum dot/MXene thin film electrode in a flexible energy storage device or wearable electronic equipment. The method of the present invention is not particularly limited, and the method may be applied according to a method known in the art. In the present invention, the flexible energy storage device preferably comprises a supercapacitor, an ion battery or a lithium sulfur battery.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. 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 obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
At room temperature, 3.2g LiF was weighed out and dissolved in 40mL of 9mol L -1 In HCl solution; weighing 2g of MAX phase Ti 3 AlC 2 Adding the powder into the LiF/HCl mixed solution, stirring for 48h at the temperature of 35 ℃ in a water bath at the rotating speed of 200rmin -1 And then the etching is carried out to carry out the etching,repeatedly centrifuging and washing the etching product until the pH is =7, and precipitating the lower layer into a plurality of layers of MXene after centrifuging;
adding the multilayer MXene into 150mL of deionized water, performing ultrasonic treatment in an ice water bath for 1h under the condition that the ultrasonic power is 300W, and performing 3000rmin -1 Centrifuging for 1h, and collecting the upper layer solution, namely the monolayer MXene nanosheet solution with the concentration of 6mg mL -1 ；
Weighing 2g of citric acid, dissolving the citric acid in 16mL of deionized water, and measuring 10mL to 6mg mL -1 A few layers of MXene nanosheet solution, mixing the two solutions at a stirring rate of 200rmin -1 Stirring at room temperature for 10h, transferring the obtained mixed solution into a polytetrafluoroethylene microwave hydrothermal reaction kettle, and keeping the temperature at 180 ℃ for 2h under 600W; and after the mixture is completely cooled to room temperature, carrying out vacuum filtration on the obtained product by using a water system filter membrane of 0.22 mu m, washing with water, and carrying out vacuum drying for 6h at 60 ℃ to obtain the flexible self-supporting 0D/2D MXene quantum dot/MXene film electrode.
Example 2
A few-layer MXene nanosheet solution was prepared according to the procedure of example 1, at a concentration of 6mg mL -1 ；
3g of citric acid is weighed and dissolved in 16mL of deionized water, and 10mL to 6mg mL of citric acid is weighed -1 A few layers of MXene nanosheet solution, mixing the two solutions at a stirring rate of 200rmin -1 Stirring at room temperature for 12h, transferring the obtained mixed solution into a polytetrafluoroethylene microwave hydrothermal reaction kettle, and keeping the temperature at 180 ℃ for 2h under 600W; and (3) completely cooling to room temperature, carrying out vacuum filtration on the obtained product by using a 0.22-micron water system filter membrane, washing with water, and carrying out vacuum drying at 60 ℃ for 6h to obtain the flexible self-supporting 0D/2D MXene quantum dot/MXene film electrode.
Example 3
3.2g LiF was weighed out and dissolved in 40mL 9mol L at room temperature -1 In HCl solution; weighing 2g of MAX phase Ti 3 AlC 2 Slowly adding the powder into the LiF/HCl mixed solution, stirring for 48 hours in a water bath at 35 ℃ and at the rotating speed of 200rmin -1 Repeatedly centrifuging and washing the etching product until the pH is =7, and precipitating the lower layer into a plurality of layers of MXene after centrifuging;
adding the multi-layer MXene into 150mL of deionized water, and carrying out ice-water bath under the condition that the ultrasonic power is 300WAfter ultrasonic treatment for 1h, the mixture is treated by 3000rmin -1 Centrifuging for 30min, and collecting the upper layer solution, namely the layered MXene nanosheet solution with the concentration of 15mg mL -1 ；
3.5g of citric acid is weighed and dissolved in 20mL of deionized water, and 6mL of 15mg mL is weighed -1 A few layers of MXene nanosheet solution, mixing the two solutions at a stirring rate of 200rmin -1 And stirring at room temperature for 12h, transferring the obtained mixed solution into a polytetrafluoroethylene microwave hydrothermal reaction kettle, keeping the temperature at 180 ℃ for 2h under 600W, completely cooling to room temperature, carrying out vacuum filtration by using a 0.22-micron water-based filter membrane, washing with water, and carrying out vacuum drying at 60 ℃ for 6h to obtain the flexible self-supporting 0D/2D MXene quantum dot/MXene film electrode.
Comparative example 1
3.2g LiF was weighed out and dissolved in 40mL 9mol L at room temperature -1 In HCl solution; weighing 2g of MAX phase Ti 3 AlC 2 Adding the powder into the LiF/HCl mixed solution, stirring for 48 hours in a water bath at 35 ℃, and rotating at the speed of 180-220 rmin -1 Repeatedly centrifuging and washing the etching product until the pH is = 6-7, and centrifuging to obtain a lower-layer precipitate which is the multilayer MXene;
adding the multilayer MXene into 150mL of deionized water, performing ultrasonic treatment in an ice water bath for 1h under the condition that the ultrasonic power is 300W, and performing 3000rmin -1 Centrifuging for 1h, and collecting the upper layer solution, namely the layered MXene nanosheet solution with the concentration of 6mg mL -1 ；
10mL of 6mg mL was measured -1 And (3) carrying out vacuum filtration on the few-layer MXene nanosheet solution by using a 0.22-micron water-based filter membrane, and carrying out vacuum drying for 6h at 60 ℃ to obtain the flexible self-supporting MXene electrode material.
Performance testing
1) Fig. 1 shows the macro photographs of the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode prepared in example 1 in different deformation states, (a) before curling, (b) during curling, and (c) after curling, and as can be seen from fig. 1, the thin film electrode can be curled without cracking and shows excellent mechanical flexibility.
2) FIG. 2 shows a high resolution TEM image of the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode prepared in example 1 and the 0D MXene quantum dot lattice fringe pattern(b) And a particle size distribution diagram (c) of 0D MXene quantum dots; as can be seen from fig. 2 (a), dispersed 0D quantum dots are present in the 2D nanosheets). As shown in FIG. 2 (b), the lattice spacing of 0D quantum dots and MXene (Ti) 3 C 2 T x ) The (0110) crystal faces are consistent. As can be seen from fig. 2 (c), the 0D MXene quantum dots have small nano-sizes, the particle sizes are mainly concentrated in 1-4 nm, and the small-size structural characteristics endow the 0D MXene quantum dots with more redox active sites, so that the charge storage capacity of the 2D MXene nanosheet can be effectively improved.
3) FIG. 3 is a high resolution TEM image (a) of the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode and the particle size distribution diagram (b) of the MXene quantum dots obtained in example 2; as can be seen from fig. 3, increasing the amount of citric acid generates more MXene quantum dot clusters with larger particle size.
4) Cutting the thin film electrode into 1 × 1cm 2 The mass is 5mg, the three-electrode system is directly used as a working electrode, a Pt sheet and Ag/AgCl are respectively used as a counter electrode and a reference electrode, and the mass is 1mol L -1 H 2 SO 4 Cyclic voltammetry and constant current charge and discharge performance tests are carried out in the electrolyte, and the scanning speed of the cyclic voltammetry curve is 5mV s -1 The current density of the constant current charging and discharging curve is 3mA cm -2 The results are shown in FIG. 4.
FIG. 4 (a) is a comparison graph of cyclic voltammetry performances of the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode prepared in example 1 and the flexible self-supporting MXene thin film electrode prepared in comparative example 1; as shown in FIG. 4 (a), the scanning speed was 5mV s -1 Compared with the cyclic voltammetry curve, the flexible self-supporting MXene thin film electrode prepared in the comparative example 1 shows a smaller integrated area of the cyclic voltammetry curve, and shows that the flexible self-supporting MXene thin film electrode has poorer charge storage capacity than the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode.
FIG. 4 (b) is a comparison graph of constant current charging and discharging performances of the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode prepared in example 1 and the flexible self-supporting MXene thin film electrode prepared in comparative example 1; as shown in FIG. 4 (b), the passing current density was 3mA cm -2 Constant current charging and discharging curve pairCompared with the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode, the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode has longer discharge time, and the charge storage capacity of the flexible self-supporting MXene quantum dot/MXene thin film electrode is obviously better than that of the flexible self-supporting MXene thin film electrode prepared in comparative example 1.
FIG. 5 is a graph showing the specific capacitance change of the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode prepared in example 1 and the flexible self-supporting MXene thin film electrode prepared in comparative example 1 at different scanning speeds; in FIG. 5, the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode has the values of 5, 10, 20, 40, 60, 80 and 100mV s calculated by specific volume -1 The specific capacity can respectively reach 1661, 1534, 1380, 1991, 1060, 942 and 842mF cm -2 (as shown in fig. 5). While the flexible self-supporting MXene thin film electrodes prepared in comparative example 1 were at 5, 10, 20, 40, 60, 80 and 100mV s -1 The specific capacities were 1314, 1202, 1054, 868, 738, 640 and 564mF cm, respectively -2 (as shown in fig. 5), the area capacity of the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode is lower, which shows that the formation of 0D MXene quantum dot greatly improves the capacitance performance of 2D MXene.
5) Two pieces of the same size (1 cm) 2 ) The thin film electrode and PVA/H prepared in example 1 2 SO 4 Gel electrolyte (PVA was dissolved in water by heating (80 ℃ C.), and then mixed with 1mol L of PVA -1 H 2 SO 4 Prepared by stirring and mixing the solution) were assembled into a device, and the charge storage performance of the device was tested, and the results are shown in fig. 6.
FIG. 6 (a) shows the current density of a device assembled by the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode prepared in example 1 at 10 mA-cm -2 And (3) a circulation stability and coulombic efficiency chart of 10000 times of lower circulation (the embedded chart is constant current charging and discharging data of the first circulation and the last circulation of the device). As can be seen from (a) in FIG. 6, the current density of the device was 10mA cm -2 The capacity retention rate reaches 84% after 10000 times of next circulation, the coulombic efficiency is close to 100%, and the method has excellent circulation stability. FIG. 6 (b) is a Ragon graph of the device assembled by the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode prepared in example 1 and having a power density of 0.45mW cm -2 The energy density is as high as 90.33 mu Wh cm -2 . When the power density is up to 9mW cm -2 While, the device still had a higher energy density (48.28. Mu. Wh cm) -2 ). Therefore, the symmetrical solid-state supercapacitor assembled by the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode has higher energy density and power density.
FIG. 7 shows the flexible charge storage capacity of the device assembled by the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode prepared in example 1. The current density of the device is 10mA cm -2 Next, cyclic voltammograms at 0 °, 45 °, 90 ° and 180 ° bends (fig. 7 (b)) were tested, and the results are shown in fig. 7; as can be seen from fig. 7, the curves of different degrees of bending almost overlap, and the capacity retention rate approaches 100% (fig. 7 (a)), indicating that the flexible charge storage capacity is stable.
As shown in FIG. 8, three devices assembled by the flexible self-supporting 0D/2D MXene quantum dot/MXene thin film electrode prepared in example 1 were connected in series with a current density of 3mA cm based on the excellent flexible charge storage performance of the devices -2 And then, charging the serially connected devices within a voltage window of 0-2.7V, and after the charging is finished, the serially connected devices can supply power to red Light Emitting Diodes (LEDs) in a bent state.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a flexible self-supporting MXene quantum dot/MXene thin film electrode is characterized by comprising the following steps:
mixing MXene nanosheet dispersion liquid with a molecular shearing reagent to obtain a precursor solution;
and carrying out hydrothermal reaction on the precursor solution under the microwave condition to obtain the flexible self-supporting MXene quantum dot/MXene thin film electrode.
2. The production method according to claim 1, characterized in that the production method of the MXene nanosheet dispersion comprises the steps of: mixing MAX raw materials and an etching solution, and etching to obtain a multilayer MXene nanosheet; and mixing the multiple layers of MXene nanosheets with water, and carrying out ultrasonic stripping to obtain MXene nanosheet dispersion liquid.
3. The preparation method according to claim 2, wherein the power of the ultrasonic peeling is 300-600W and the time is 30-60 min.
4. The method of claim 1, wherein the MAX starting material has the formula M n+1 AX n M is Sc, ti, zr, V, nb, cr or Mo, A is Al, ga, si, TI, sn or Ge, X is C or N, and N =1 to 3.
5. The preparation method according to claim 1, wherein the concentration of the MXene nanosheet dispersion is 5 to 15 mg-mL -1 (ii) a The molecular shearing agent comprises one or more of citric acid, tannin, sodium alginate and polydopamine.
6. The preparation method according to claim 1 or 5, wherein the ratio of the mass of the molecular shearing agent to the volume of the MXene nanosheet dispersion is (2-4) g (6-10) mL.
7. The production method according to claim 1, characterized in that the mixing of the MXene nanosheet dispersion and the molecular shear reagent is performed under stirring conditions; the stirring speed is 200-400 r.min -1 The time is 8 to 12 hours.
8. The preparation method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 160-200 ℃, a power of 600-800W and a time of 0.5-2 h.
9. The flexible self-supporting MXene quantum dot/MXene thin film electrode prepared by the preparation method of any one of claims 1 to 8, comprises a 2D MXene nanosheet and 0D MXene quantum dot modified on the surface of the 2D MXene nanosheet.
10. Use of the flexible self-supporting MXene quantum dot/MXene thin film electrode of claim 9 in flexible energy storage devices or wearable electronics.
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