CN111252768A - Preparation method and application of titanium carbide MXene functionalized graphene nanocomposite film - Google Patents
Preparation method and application of titanium carbide MXene functionalized graphene nanocomposite film Download PDFInfo
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Abstract
The invention relates to a preparation method and application of a titanium carbide MXene functionalized graphene nanocomposite film.However, it has been a challenge to prepare graphene nanocomposite thin films with high strength and high conductivity. In order to solve the problem, a hydrophilic and high-conductivity MXene nanosheet is adopted, Ti-O-C covalent bonds are used for removing functionalized graphene oxide, and chemical crosslinking is carried out through organic molecules, so that the super-toughness MXene functionalized graphene nanocomposite film is prepared. The introduced MXene nanosheets and organic molecules not only reduce the porosity of the graphene film, but also improve the orientation degree of the graphene nanosheets. Therefore, due to the interface synergistic effect, the prepared graphene nanocomposite film has the ultrahigh toughness of 42.7MJ m‑3And high conductivity 1329.0S cm‑1. And a flexible super capacitor assembled based on the super-tough and high-conductivity MXene functionalized graphene nanocomposite film shows high volume energy density and excellent flexibility.
Description
Technical Field
The invention relates to a preparation method of a titanium carbide MXene functionalized graphene nanocomposite film and application of the titanium carbide MXene functionalized graphene nanocomposite film in a flexible supercapacitor, and belongs to the field of nanocomposite preparation.
Background
Due to the rapid development of flexible energy storage devices and portable, portable electronic devices, flexible reduced graphene oxide films have gradually been applied to these fields. However, since the poor mechanical properties and low conductivity of the flexible reduced graphene oxide thin film have been a bottleneck to be solved, the wide application of the material in many mobile devices is limited. For example, researchers have introduced inorganic materials including double-walled nanotubes (adv. mater.2012,24, 1838-. Although high tensile strength is achieved in the prepared nanocomposite, the toughness of the resulting composite is still at a lower level. In addition, researchers are inspired by natural shells, and the interfacial strength between GO layers of the nanocomposite is improved by chemical crosslinking and by using oxygen-containing functional groups on the surface of graphene oxide. For example, covalent bonds such as borate (adv.mater.2011,23, 3842-; ca2+(Adv.Mater.2016,28,2834-2839)、Zn2 +(Chem.Commun.2015,51,2671-2674.)、 Mg2+(ACSNano 2008,2,572-578) plasma bonding; the mechanical property improvement of the graphene-based nanocomposite is promoted by pi-pi conjugate stacking effects of Thermoplastic Polyurethane (TPU) (ACSNano 2015,9,708-714), dopamine (PDA) (ACSNano 2014,8,9511-9517) and the like and hydrogen bond-titanium carbide or valence bond interface synergistic effects of polyvinyl alcohol (PVA) (Adv. Mater.2012,24,3426-3431), cellulose, polymethyl methacrylate (PMMA) (Adv. Funct. Mater.2010,20,3322-3329) and the like. Although these methods significantly improve the mechanical strength of the nanocomposite, the reduced graphene oxide nanocomposites prepared tend to be accompanied by a reduction in toughness and electrical conductivity. Therefore, the method for preparing graphene nanocomposite film with high mechanical properties and high conductivity has been a great challenge!
Two-dimensional material titanium carbide transition metal nanosheet MXene (Ti)3C2Tx) Due to its high conductivity, high specific surface area, excellent electrochemical properties and good mechanical properties, it is gradually receiving much attention and research. The MXene nanosheet has a large number of functional groups T on the surfacexSuch as hydrogen group (OH), oxygen-containing group (O) and fluorine-containing group (F). Thus, the presence of these functional groups facilitates that MXene can be used to functionalize graphene oxide nanoplatelets (GO) to prepare corresponding nanocomposite films.
At present, relevant patents related to the reduced graphene oxide/MXene nanocomposite material include: a preparation method of titanium carbide MXene/graphene/polyvinyl alcohol composite gel (CN20190000791118), a preparation method of a proton exchange membrane fuel cell cathode catalyst of titanium carbide based on an MXene/rGO composite carrier (CN102019000627612), a preparation method of a titanium carbide graphene oxide/MXene composite membrane and application (CN 10201900045350). Papers on reduced graphene oxide/MXene are: a) adv, Energy Mater.2017,7, 1601847-; b) ACS Nano 2019,13, 14319-14328; c) ACS Nano 2019,13, 14308-14318; d) J.mater.chem.A2017,5, 17442-17451; e) the patents and the papers only discuss MXene as an active substance for electrical energy storage, electrocatalysis and electromagnetic shielding, and relevant reports are provided for the mechanical properties and the mechanism research of the relevant interface action of the MXene functionalized reduced graphene oxide nanocomposite film.
Disclosure of Invention
The technical problem of the invention is solved: the defects of the prior art are overcome, the preparation method of the titanium carbide MXene functionalized graphene nanocomposite film and the application of the titanium carbide MXene functionalized graphene nanocomposite film in the flexible supercapacitor are provided, and the graphene nanocomposite film with super toughness and high conductivity can be successfully prepared.
The invention provides a method for preparing an MXene functionalized graphene oxide nanocomposite film MrGO-AD by forming a covalent bond through MXene functionalized graphene oxide and the synergistic effect of a pi-pi conjugated stacking interface between the graphene oxide and a 1-aminopyrene-suberic acid bis (N-hydroxysuccinimide ester) molecule (AD). The MXene functionalized graphene oxide nanocomposite film has the toughness of 2.8-42.7MJ m-3The tensile strength is 266.9-699.1MPa and the high conductivity is 412.7-1329.0S cm-1. The MXene functionalized graphene nanocomposite material has ultrahigh toughness, which is caused by the interfacial synergistic effect of Ti-O-C covalent bonds between reduced graphene oxide and MXene, slippage between MXene nanosheet layers and pi-pi conjugated stacking effect between the reduced graphene oxide and AD molecules. Meanwhile, the formation of Ti-O-C common bonds accelerates the electron transmission rate of the graphene nanocomposite film and improves the conductivity of the nanocomposite film. The small-angle scattering and the wide-angle scattering prove that the MXene nanosheets and the AD molecules can reduce the porosity of the graphene film and improve the orientation degree of the graphene nanosheets, and the interface synergistic effect among the components is revealed by in-situ Raman spectroscopy and molecular dynamics simulation. Based on the super toughness and high conductivity, the flexible supercapacitor assembled by the MXene functionalized graphene oxide nanocomposite film also shows high volume energy density. Therefore, a titanium carbide potential is provided for preparing the graphene nanocomposite film with super toughness, high strength and high conductivity through an interface cooperation strategy, and the graphene nanocomposite film is promoted to have wide application scenarios in aerospace and flexible devices.
The invention is realized by the following technical scheme: firstly, a single-layer MXene nanosheet solution is obtained through chemical etching and ultrasonic stripping methods, and the proportion range of the MXene nanosheets is regulated. Preparing a series of MXene functionalized graphene oxide nanocomposite films with different MXene contents by using a suction filtration and self-assembly method; reducing by hydriodic acid (HI) to obtain an MXene functionalized reduced graphene oxide nanocomposite film; soaking the MXene functionalized reduced graphene oxide nanocomposite film in an N, N-dimethylformamide solution of AD molecules, washing and drying to obtain the MXene functionalized graphene nanocomposite film.
The invention specifically realizes the following steps:
(1) mixing raw material Ti3AlC2Stirring and etching by adopting a chemical etching method and taking lithium fluoride (LiF) and hydrochloric acid (HCl) as etching agents to obtain an organ-shaped MXene phase; then preparing a single-layer MXene nanosheet uniform aqueous solution by means of ultrasonic stripping and centrifugal separation;
(2) adding a uniform aqueous solution of single-layer MXene nanosheets prepared by means of ultrasonic stripping and centrifugal separation into an aqueous solution of Graphene Oxide (GO), and performing ultrasonic treatment to form a uniform dispersion liquid of the single-layer MXene nanosheets and the graphene oxide;
(3) stirring and chemically reacting the single-layer MXene nanosheet and the graphene oxide uniform dispersion liquid in the step (2), and reacting to obtain an MXene nanosheet and graphene oxide uniform dispersion liquid;
(4) carrying out vacuum filtration on the MXene nanosheet and the graphene oxide uniform dispersion liquid obtained in the step (3), wherein the MXene nanosheet and the graphene oxide nanosheet in the uniform dispersion liquid are subjected to self-assembly to prepare an MXene functionalized graphene oxide nanocomposite film MGO, and the thickness of the prepared film is 2-10 microns;
(5) regulating the quality of the single-layer MXene nanosheets, repeating the steps (2), (3) and (4) to prepare MXene functionalized graphene oxide nanocomposite films with different MXene nanosheet contents;
(6) reducing the MXene functionalized graphene oxide nanocomposite film obtained in the step (5) by adopting hydroiodic acid (HI) to prepare an MXene functionalized reduced graphene oxide nanocomposite film MrGO, wherein the thickness of the prepared film is 2-10 μm;
(7) and (3) placing the MXene functionalized reduced graphene oxide nano composite material film in the step (6) into an N, N-dimethylformamide solution of 1-aminopyrene-suberic acid bis (N-hydroxysuccinimide ester) (AD) molecules to be soaked for 2-24h, wherein 20-24h is the preferred time, so that the MXene functionalized graphene nano composite material film MrGO-AD is obtained, and the thickness of the prepared film is 2-10 μm.
The step (2) adopts ultrasonic stripping and centrifugal separation to prepare a uniform aqueous solution of a single-layer MXene nanosheet, and comprises the following steps: dispersing organ-shaped MXene phase in water, performing closed ultrasonic treatment for 0.5-1h, and performing centrifugal separation to obtain MXene nanosheet dispersion liquid; then the mass ratio of the MXene nanosheet solution to the added graphene oxide is controlled to be 5-50%, wherein 15-20% is the preferred mass ratio, and the high toughness (14.2-42.7MJ m) is prepared through the preferred ratio in the range-3) And high conductivity (412.7-1329.0S cm-1) The graphene nanocomposite film of (1).
In the step (3), the ultrasonic time is 5-10 minutes, the stirring reaction is carried out for 6-8 hours, and the monolayer MXene nanosheets and the GO nanosheets can be fully reacted at the time without generating precipitates.
In the step (4), the process of preparing the MXene functionalized graphene oxide nanocomposite film MGO by self-assembly is as follows: firstly, adding MXene nanosheet and graphene oxide uniform dispersion liquid into a suction filtration funnel, and enabling the vacuum degree of a suction filtration device to reach 0.09-0.1 MPa; and after the filtration is finished, obtaining the MXene functionalized graphene oxide nanocomposite film with the thickness of 2-10 mu m, and obtaining the graphene oxide nanocomposite film with obvious and compact layer shape by a filtration mode.
In the step (5), the mass fraction of the MXene nanosheets is regulated to be 5-50%, wherein 15-20% is a preferred mass ratio, namely the mass of the added graphene oxide accounts for 95-50% of the total mass, and 85-80% is the preferred mass ratio. The mass fraction of the MXene nanosheet solution with the optimal mechanical property is determined by representing the mechanical property of MXene functionalized graphene oxide nanocomposite films with different mass fractions.
The MXene nanosheet mass fraction is preferably controlled to be 15-20%, so that the toughness and the conductivity of the prepared graphene oxide nanocomposite film can be improved.
In the step (6), the MXene functionalized reduced graphene oxide nanocomposite film is treated by using a HI solution with the concentration of 37.0-38.0% for 6-12h, then washed by using ethanol, soaked for 12-24h, and dried in vacuum at the temperature of 50-60 ℃ to obtain the MXene functionalized reduced graphene oxide nanocomposite film.
Wherein, the HI is used for soaking for 6-12h for fully reducing the MXene functionalized graphene oxide nanocomposite film; the ethanol is soaked for a long time to remove residual HI in the MXene functionalized reduced graphene oxide nanocomposite film; the drying at 50-60 ℃ is to prevent the oxidation of the film.
The step (7) is specifically as follows: the method comprises the steps of soaking a reduced graphene oxide-MXene nanocomposite in a N, N-Dimethylformamide (DMF) solution of 12mM AD molecules for 2-24h, wherein 20-24h is the preferred time, washing with the DMF solution for 4-5 times, continuing washing with ethanol for 5-6 times, and then drying in vacuum at 50-60 ℃ to obtain an MXene functionalized graphene nanocomposite film.
Wherein, the soaking for 20-24h is to ensure that AD molecules and graphene are fully reacted; the DMF solution is washed for 4-5 times to remove the redundant AD molecules on the surface of the film; the drying at 50-60 ℃ is to prevent the oxidation of the film.
And (5) assembling the MXene functionalized graphene nanocomposite film obtained in the step (7) into a flexible supercapacitor.
Measuring the volume energy density of the flexible super capacitor up to 13.0mWh cm-3And the assembled flexible super capacitor keeps excellent flexibility, and the capacity retention rate is still 87-98% after the flexible super capacitor is bent for 17000 times at 180 degrees.
The preparation method of the flexible supercapacitor comprises the following steps: mixing PVA and water in the mass ratio of 1:10, heating to 90 deg.c until all PVA and phosphoric acid are dissolved, adding PVA and phosphoric acidH3PO4) The mass ratio of the components is 1:1, stirring is carried out for 12 hours, and then the prepared MrGO-AD graphene nano composite material film is soaked in PVA/H3PO4And (3) reserving blank positions with the width of 0.5cm at two ends in gel electrolysis for 4 hours, taking out the soaked MrGO-AD thin film electrode from the gel electrolyte, assembling the electrode face to form a flexible supercapacitor, connecting the blank positions at the two ends with copper leads by using silver adhesive, and then testing related electrochemical performances, wherein all tests are tested by using an electrochemical workstation at room temperature. The electrochemical performance and the flexibility stability of the flexible supercapacitor prepared by the steps are kept stable and unchanged after 20000 cycles, and can reach 98% after 17000 cycles in a 180-degree bent state.
Electrochemical capacity, cycling stability, volumetric energy density, volumetric power density, and bending stability tests.
The principle of the invention is as follows: the MXene functionalized graphene nanocomposite film is constructed by adopting graphene oxide, MXene nanosheets and AD molecules. MXene nanosheets and AD molecules are introduced, so that the pores among the reduced graphene oxide layers can be reduced, and the orientation of the reduced graphene oxide is improved. Meanwhile, compared with the existing technology for preparing the high-toughness nano composite material, the invention has the characteristics that:
(1) MXene is firstly used for functionalizing and reducing graphene oxide, and a Ti-O-C covalent bond is formed between the MXene and the graphene oxide, so that the mechanical strength and the conductivity of the reduced graphene oxide nano composite material are improved;
(2) due to the slippage effect existing between the MXene nanosheets and the covalent bond formed between the MXene nanosheets and the reduced graphene oxide, the toughness of the reduced graphene oxide nanocomposite can be improved;
(3) except the covalent bond formed between MXene nano-sheets and GO and the sliding action formed between MXene nano-sheets, AD molecules are continuously introduced through the pi-pi conjugated stacking action, so that the ultrahigh toughness of the MrGO-AD nano composite material film is 2.8-42.7MJ m-3And high conductivity 412.7-1329.0S cm-1；
(4) In addition, the covalent bond formed between the graphene oxide and the MXene nanosheets and the interface synergistic effect of the pi-pi conjugated stacking effect formed between the graphene oxide and the AD molecules not only reduce the porosity between graphene layers, but also improve the orientation of the reduced graphene oxide. The invention designs a preparation method of a titanium carbide MXene functionalized graphene nanocomposite film and application of the titanium carbide MXene functionalized graphene nanocomposite film in a flexible supercapacitor through an interface synergistic effect.
Drawings
Fig. 1 is a schematic diagram of a preparation method of a titanium carbide MXene functionalized graphene nanocomposite film and an application of the titanium carbide MXene functionalized graphene nanocomposite film in a flexible supercapacitor. Firstly, preparing a single-layer MXene nanosheet aqueous solution and a graphene oxide aqueous solution, adding the single-layer MXene nanosheet aqueous solution into the graphene oxide aqueous solution under the stirring condition, and carrying out ultrasonic dispersion and full reaction under stirring to obtain a uniform dispersion liquid; and then obtaining the MXene functionalized graphene oxide nanocomposite film by vacuum filtration and self-assembly technology. And preparing the MXene functionalized reduced graphene oxide nanocomposite film by chemical reduction (hydroiodic acid reduction). And then soaking the MXene functionalized reduced graphene oxide nanocomposite film in an N, N-dimethylformamide solution of AD molecules, and preparing the MXene functionalized reduced graphene oxide nanocomposite film MrGO-AD through pi-pi conjugated accumulation.
FIG. 2 is an evidence of the interfacial synergy of Ti-O-C covalent bond and pi-pi conjugate stacking effect occurring in the preparation method of a titanium carbide MXene functionalized graphene nanocomposite film and the application thereof in a flexible supercapacitor, according to the present invention: a, XRD spectrogram; b, infrared spectrogram; c, Raman spectrum; d, a Ti 2p spectrogram of the film; e, C1s spectrum of film; f, UV-vis spectrum of the film.
Fig. 3 shows the mechanical properties of a titanium carbide MXene functionalized graphene nanocomposite film and its application in a flexible supercapacitor. a-d, wide-angle scattering characterization; e-f, small angle scattering spectrogram; g, corresponding small angle scattering intensity map; h, porosity comparison graph; i, a stress-strain diagram; j, tensile strength and toughness comparison plots; k, tensile strength, electrical conductivity, and toughness comparison plots.
Fig. 4 is a mechanism explanation about the mechanical property improvement of the preparation method of the titanium carbide MXene functionalized graphene nanocomposite film and the application thereof in the flexible supercapacitor. a-d, in situ Raman plots; e, a molecular dynamics simulation diagram; f-i, tensile failure side SEM image.
FIG. 5 shows the performance of a titanium carbide MXene functionalized graphene composite film in preparing a flexible supercapacitor. a, assembling a flexible super capacitor; b, cyclic voltammograms; c, a charge-discharge diagram; d, a rate performance graph; e, a circulation stability chart; f, energy density and power density comparison.
FIG. 6 shows flexibility tests and demonstration of the aspect of preparing a titanium carbide MXene functionalized graphene composite material film into a flexible supercapacitor. a, a bending stability diagram; b, bending circulation stable diagram; c, bending a cyclic impedance diagram; d, a flexible super capacitor parallel assembly diagram; e-f, stability diagrams of parallel and series connection of different bending states; g-i, demonstration diagrams of the lighted LED lamps in different bending states.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The following examples are only for explaining the present invention, the scope of the present invention shall include the full contents of the claims, and the full contents of the claims of the present invention can be fully realized by those skilled in the art through the following examples.
The method of the invention is realized as follows: obtaining a single-layer MXene dispersion liquid by a chemical etching and ultrasonic stripping method; stirring and reacting MXene nanosheet dispersion liquid and GO nanosheet dispersion liquid; after the reaction, a series of different MXene functionalized graphene oxide nanocomposite films are prepared by a vacuum filtration and self-assembly method. And carrying out chemical reduction (HI) to obtain the MXene functionalized reduced graphene oxide nanocomposite film. And finally, soaking the MXene functionalized reduced graphene nanocomposite film in an N, N-dimethylformamide solution of AD molecules, and washing and drying to obtain the MXene functionalized graphene nanocomposite film.
The single-layer MXene nanosheet is a 2D layered material with titanium carbide Ti and C alternately existing, the surface of the single-layer MXene nanosheet contains a large number of oxygen-containing functional groups, the single-layer MXene nanosheet has good conductivity, large specific surface area, mechanical property and electrochemical energy storage performance, and graphene oxide is easy to reduce and forms a Ti-O-C covalent bond with the graphene oxide; the graphene oxide nanosheet is used as an oxygen-containing derivative of graphene, the surface of the graphene oxide nanosheet contains rich active groups such as hydroxyl groups, epoxy groups and carboxyl groups, and the graphene oxide nanosheet is easily soluble in water; the AD molecules contain benzene ring functional groups such as benzene rings and the like, so that a stable pi-pi conjugated accumulation effect is easily formed between the AD molecules and the rGO.
The thickness of the prepared MXene functionalized graphene nanocomposite film is 2-10 microns.
Example 1
According to the XRD spectrum (a in figure 2) of the prepared material, the pure MXene film has a characteristic peak with 6 degrees and the interlayer spacing of
This indicates that MXene nanoplatelets were successfully formed from Ti3AlC2The peeling was successful. When MXene nanosheets were added, the interlayer spacing of the MGO film was from that of pure GO
Rise to
Demonstrating successful incorporation of MXene nanoplatelets between GO layers. After HI reduction, the interlayer spacing of MrGO decreases to
This indicates that a significant amount of oxygen-containing functional groups on the GO nanosheet surface were removed. After introduction of the AD molecule, MInterlayer spacing of rGO-AD films up to
Infrared spectroscopy (FTIR) measurement shows that the wavelength of MGO, MrGO and MrGO-AD thin films is 837cm-1A new characteristic peak appears, which indicates the formation of Ti-O-C covalent bonds between MXene nanosheets and GO nanosheets. Moreover, compared with the MrGO film, the MrGO-AD film has an infrared spectrum of 1253cm-1、～1538cm-1And 1658cm-1Corresponding to-NH-and-C ═ O of the AD molecule, respectively, demonstrates that the AD molecule successfully cross-links with rGO nanoplates through pi-pi conjugate stacking. Raman Spectroscopy (Raman) testing indicated I for MGO filmsD:IGThe ratio of (A) is increased from-0.9 to-1.2 of the GO film, which shows that a valence bond effect is formed between the GO and MXene nano-sheets. And, I of MrGO and MrGO-AD due to HI reductionD:IGThe ratio of (a) sharply rises to-1.6. Besides, the G band characteristic peak of the GO film is 1600cm-1Has moved 13cm-1To 1587cm-1Indicating the formation of a Ti-O-C covalent bond between GO and MXene. X-ray photoelectron spectroscopy (XPS) tests show that pure MXene film has 4 distinct characteristic peaks at free energies of 455.2eV, 458.2eV, 461.1eV and 463.6eV, which correspond to Ti-C2 p3/2，Ti-O 2p3/2， Ti-C 2p1/2And Ti-O2 p1/2A bond. However, the resulting MGO films produced corresponding migration, such as from 458.2eV to 458.8eV and from 463.6eV to 464.4eV, respectively, which indicates the formation of Ti-O-C covalent bonds between MXene and GO nanoplates. When pure GO films were defunctionalized with MXene nanoplates, the atomic percent C-O of pure GO dropped from 51.7% to 30.2% (MGO). In addition, ultraviolet-visible spectroscopy (UV-vis) tests showed that pure GO films exhibited two characteristic peaks at 230nm and 300nm, corresponding to C ═ C pi-pi transition and carboxyl group n-pi transition, respectively. However, the characteristic peak of MGO red-shifted from 230nm wavelength to 238nm and the shoulder at 300nm began to weaken, these results further demonstrate the formation of Ti-O-C covalent bonds between GO and MXene to reduce GO nanoplates.
Example 2
After MXene functionalization of the GO nanosheets, the half-width of the azimuthal angle of the resulting MrGO film decreased from 36.3 ° to 27.1 ° for the pure GO film, as shown by a-d in fig. 3. When the rGO nano-sheet and the AD molecule are subjected to pi-pi conjugate stacking crosslinking, the azimuth half-peak widths of the rGO-AD and the MrGO-AD are respectively reduced to 26.5 degrees and 26.1 degrees. Thus, the MrGO, rGO-AD, and MrGO-AD films exhibited high degrees of orientation of 84.9%, 85.3%, and 85.5%, respectively, while the pure rGO films were only 79.8%. In addition, MrGO-AD porosity decreased from 15.2% to 4.0% of pure rGO films according to the small angle scattering test, these results indicate that MXene nanosheets can fill the rGO interlayer porosity, thereby making the films more compact. Due to the interface synergistic effect among the MXene nanosheets, the rGO nanosheets and the AD molecules, the rGO film becomes more compact, the orientation degree of the rGO is improved, and the mechanical property of the MXene functionalized reduced graphene oxide film is improved. As shown in i in FIG. 3, due to weak interface action between GO nano-sheets, the pure graphene oxide film shows weak tensile strength of 82.2MPa, strain of 2.6% and toughness of 0.9MJ m-3. The MXene functionalized GO nano-sheets form MGO films with stretching mild degree and toughness respectively increased to 226.3MPa and 6.2MJm-32.8 times and 6.9 times of pure GO film, respectively. After HI reduction, the tensile strength and the toughness of MrGO are further improved to 379.2MPa and 14.2MJ m-3. The MrGO-AD film is formed through pi-pi conjugated stacking and crosslinking with AD molecules, and the tensile strength and the toughness of the MrGO-AD film reach the maximum values of 699.1MPa and 42.7MJ m-34.2 and 17.8 times the strength and toughness of rGO, respectively. The improved toughness and strength are attributed to the interfacial synergy between MXene nanoplates, GO nanoplates, and AD molecules. In addition, the MXene functionalized reduced graphene oxide MrGO-AD film also shows good conductivity of 1329.0S cm due to excellent conductivity of MXene per se-1These are due to pi-pi conjugate stacking between the AD molecules and the rGO nanoplates and interfacial synergy of covalent bonds of Ti-O-C between MXene nanoplates and rGO. Therefore, as shown in k in fig. 3, the MrGO-AD film prepared exhibits the highest toughness compared to other graphene nanocomposites.
Example 3
In-situ Raman spectrum represents the G-band migration volume of the graphene nanosheets, and shows the difference of the loading transfer efficiency of pure rGO, rGO-AD, MrGO and MrGO-AD thin films. As shown in fig. 4 a-d, after MXene nanoplates are crosslinked with human GO nanoplates by Ti-O-C covalent bonds, the resulting MrGO film clearly exhibits a long plateau between strain 0.9% to 4.3%, similar to a pure rGO film (plateaus occur at 0.5% to 3.6%), and the upper limit of the plateau represents that MrGO just begins to crack and MXene functionalized MrGO breaks completely at high strain-6.7%. The appearance of the platform shows that the stress cannot be effectively transferred to the graphene nanosheets due to slippage between the MXene nanosheets, so that plastic deformation is generated, and the tensile strength and toughness of the prepared MXene functionalized graphene nanocomposite film are effectively improved. Meanwhile, the crack propagation is inhibited by the fracture of the Ti-O-C covalent bond, so that the final strain is improved to 6.7 percent. However, no platform appears in the range of 0-6.5% of strain of the rGO-AD thin film, which indicates that stress can be effectively transferred in the loading process to cause rapid fracture of the graphene nanosheets. This shows that pi-pi conjugated stacking effect formed between rGO and AD molecules can effectively inhibit crack propagation and thus improve toughness. Although no platform appears in the MrGO-AD thin film, the MrGO-AD thin film realizes a large strain according to the G band migration amount of the graphene nano-sheets. These results indicate that the achievement of large strain for MXene functionalized graphene nanocomposite films is due to the interfacial synergy of Ti-O-C covalent bonds between MXene nanoplates and rGO nanoplates, slippage between MXene layers, and pi-pi conjugated packing between rGO and AD molecules. The interface synergistic effect improves the toughness and tensile strength of the MXene functionalized graphene nanocomposite film through comprehensive toughening mechanisms such as plastic deformation, crack propagation inhibition and the like. And as shown by e in fig. 4, molecular dynamics simulation revealed a synergistic toughening mechanism of the MXene functionalized graphene nanocomposite film. As shown in the figure, the MrGO-AD film shows a unique synergistic toughening mechanism process, wherein the mechanism process comprises plastic deformation caused by interlayer slippage of MXene nanosheets, a pi-pi conjugated stacking effect between AD molecules and the rGO nanosheets and a process for synergistically inhibiting crack propagation of Ti-O-C covalent bonds between the rGO and the MXene nanosheets. When stretching begins, the wrinkled rGO nanoplates begin to straighten and micro cracks begin to appear. According to the first principle, calculation shows that the potential energy for relative slippage between MXene layers is smaller than that of a Ti-O-C covalent bond generated between MXene nanosheets and rGO nanosheets. Therefore, as the stretching continues, relative slippage occurs between MXene nanosheets, and the relative slippage between the MXene nanosheets and the MXene nanosheets is generated by plastic deformation, which is consistent with the in-situ Raman spectrum test result. Meanwhile, the long-chain AD molecules crosslinked with the rGO nano-sheets through pi-pi conjugated stacking effect begin to be stretched, and crack propagation is inhibited before fracture. As a result, MXene nanosheets completely separated by relative slippage, and AD was snapped. As stretching continues, the Ti-O-C covalent bonds formed between the MXene and rGO nanoplates begin to break to inhibit crack propagation to increase the toughness of the film until the film is completely broken. Meanwhile, as shown in f and g in fig. 4, it can be seen from the fracture morphology of the film that the graphene nanosheets at the fracture edges of the MrGO film exhibit relatively smooth curls, whereas the graphene nanosheets after the MrGO-AD stretching exhibit relatively obvious curly edges. Therefore, the above characterization shows that the interfacial synergy can significantly improve the toughness and strength of the MXene functionalized graphene nanocomposite film.
Example 4
Put 4.750mL of graphene oxide homodisperse (density is 4.0mg mL)-1) In a 25mL reaction flask, 6.583mL of distilled water was added, stirred for 15min, and ultrasonically dispersed for 5min to obtain a yellowish brown solution. 0.667mL of monolayer MXene nanosheet solution (density 1.5mg mL)-1) Slowly adding the mixture into the uniformly dispersed graphene oxide solution, and continuously stirring the mixture to fully react for 6 hours. And carrying out vacuum filtration on the reaction liquid for 18-24h to obtain the MXene nanosheet functionalized MGO nanocomposite film, wherein the MXene mass fraction is 5.5%. In the suction filtration process, due to the fact that the number of MXene nanosheets is small, graphene oxide lamella layers are in ordered orientation self-assembly, and meanwhile, a strong Ti-O-C covalent bond is formed between the MXene nanosheets and the graphene oxide. Then, MGO is reduced by 37-38% hydriodic acid solution for 6h at 25 ℃. After the reduction is finished, washing and soaking by ethanolAnd removing redundant hydriodic acid for 24 hours, and drying in vacuum to obtain the MrGO nano composite material film with the thickness of 2-10 mu m. Mechanical property tests show that the tensile strength of the MGO and MrGO nano composite material films respectively reaches 144.3MPa and 266.9MPa, and the toughness respectively reaches 1.2MJ m-3And 2.8MJ m-3And the conductivity of the MrGO nano composite material film is 412.7S cm-1. Compared with the similar graphene nanocomposite film, the graphene nanocomposite film has unique advantages in toughness and conductivity, and the toughness and the conductivity are respectively improved by 17% and 22.9% compared with rGO.
Example 5
Put 4.250mL of graphene oxide homodisperse (density is 4.0mg mL)-1) In a 25mL reaction flask, 5.750mL of distilled water was added, stirred for 15min, and ultrasonically dispersed for 5min to obtain a yellowish brown solution. 2.000mL of monolayer MXene nanoplatelet solution (density 1.5mg mL)-1) Slowly adding the mixture into the uniformly dispersed graphene oxide solution, and continuously stirring the mixture to fully react for 6 hours. And carrying out vacuum filtration on the reaction liquid for 18-24h to obtain the MXene nanosheet functionalized MGO nanocomposite film, wherein the mass fraction of the MXene nanosheets is 17.7%. In the suction filtration process, due to the fact that the number of MXene nanosheets is small, graphene oxide lamella layers are in ordered orientation self-assembly, and meanwhile, a strong Ti-O-C covalent bond is formed between the MXene nanosheets and the graphene oxide. Then, MGO is reduced by 37-38% hydriodic acid solution for 6h at 25 ℃. And after reduction, cleaning and soaking the film for 24 hours by using ethanol, removing redundant hydriodic acid, and drying the film in vacuum to obtain the MrGO nano composite material film with the thickness of 2-10 mu m. Mechanical property tests show that the tensile strength of the MGO and MrGO nano composite material films respectively reach 226.3MPa and 379.2MPa, and the toughness respectively reaches 6.2MJ m-3And 14.2MJ m-3And the electrical conductivity of the MrGO nano composite material film is 1036.6S cm-1. Compared with the similar graphene nanocomposite film, the graphene nanocomposite film has unique advantages in toughness and conductivity, and the toughness and the conductivity are respectively improved by 158.3% and 208.7% compared with rGO.
Example 6
Put 2.500mL of graphene oxide homodisperse (density is 4.0mg mL)-1) In a 25mL reaction2.833mL of distilled water was added to the flask, and the mixture was stirred for 15min and ultrasonically dispersed for 5min to obtain a yellowish brown solution. 6.667mL of monolayer MXene nanosheet solution (density 1.5mg mL)-1) Slowly adding the mixture into the uniformly dispersed graphene oxide solution, and continuously stirring the mixture to fully react for 6 hours. And carrying out vacuum filtration on the reaction liquid for 18-24h to obtain the MXene nanosheet functionalized MGO nanocomposite film, wherein the MXene mass fraction is 45.1%. In the suction filtration process, due to the fact that the number of MXene nanosheets is small, graphene oxide lamella layers are in ordered orientation self-assembly, and meanwhile, a strong Ti-O-C covalent bond is formed between the MXene nanosheets and the graphene oxide. Then, MGO is reduced by 37-38% hydriodic acid solution for 6h at 25 ℃. And after reduction, cleaning and soaking the film for 24 hours by using ethanol, removing redundant hydriodic acid, and drying the film in vacuum to obtain the MrGO nano composite material film with the thickness of 2-10 mu m. Mechanical property tests show that the tensile strength of the MGO and MrGO nano composite material films respectively reach 129.4MPa and 170.2MPa, and the toughness respectively reaches 1.1MJ m-3And 2.2MJ m-3And the electrical conductivity of the MrGO nano composite material film is 1919.2S cm-1. Compared with the similar graphene nanocomposite film, the graphene nanocomposite film has unique advantages in the aspect of conductivity, and the conductivity is improved by 471.5% compared with rGO.
Example 7
Put 5.000mL of graphene oxide homodisperse (density is 4.0mg mL)-1) In a 25mL reaction flask, 7.000mL of distilled water was added, stirred for 15min, and ultrasonically dispersed for 5min to give a yellowish brown solution. And carrying out vacuum filtration on the reaction liquid for 18-24h to obtain the pure GO film. And reducing the pure GO film by using 37-38% hydriodic acid solution at 25 ℃ for 6 hours. And after reduction, cleaning and soaking the film by using ethanol for 24 hours, removing redundant hydriodic acid, and drying the film in vacuum to obtain the pure rGO film, wherein the thickness of the obtained film is 2-10 mu m. Soaking the prepared pure rGO film in a N, N-dimethylformamide solution of 12mMAD molecules for 24h, taking out the film after the reaction is completed, repeatedly washing the film for 4-5 times by using the N, N-dimethylformamide solvent, continuously washing the film for 5-6 times by using ethanol, and drying the film in a vacuum drying oven to obtain the rGO-AD nano composite material film with the thickness of 2-10 mu m. The mechanical property test shows that the rGO-AD nano composite material film is stretchedThe strength is 510.4MPa, and the toughness is as high as 17.9MJ m-3. Compared with the similar graphene-based nano composite material, the graphene-based nano composite material has certain advantages in the aspect of toughness, and the toughness and the conductivity are respectively improved by 641.7% and 177.2% compared with rGO.
Example 8
Put 4.250mL of graphene oxide homodisperse (density is 4.0mg mL)-1) In a 25mL reaction flask, 5.750mL of distilled water was added, stirred for 15min, and ultrasonically dispersed for 5min to obtain a yellowish brown solution. 2.000mL of monolayer MXene nanoplatelet solution (density 1.5mg mL)-1) Slowly adding the mixture into the uniformly dispersed graphene oxide solution, and continuously stirring the mixture to fully react for 6 hours. And carrying out vacuum filtration on the reaction liquid for 18-24h to obtain the MXene nanosheet functionalized MGO nanocomposite film. Then, MGO is reduced by 37-38% hydriodic acid solution for 6h at 25 ℃. And after reduction is finished, cleaning and soaking the film for 24 hours by using ethanol, removing redundant hydriodic acid, and drying the film in vacuum to obtain the MrGO nano composite material film. Soaking the prepared MrGO nano composite material film in an N, N-dimethylformamide solution of 12mMAD molecules for 24h, taking out the film after the reaction is completed, repeatedly washing the film for 4-5 times by using the N, N-dimethylformamide solvent, repeatedly washing the film for 5-6 times by using ethanol, and drying the film by using a vacuum drying oven to obtain the MrGO-AD nano composite material film with the thickness of 2-10 mu m. Mechanical property tests show that the tensile strength of the MrGO-AD nano composite material film can reach 699.1MPa, and the toughness can reach 42.7MJ m-3And the MrGO-AD nano composite material film also shows the highest conductivity of 1329.0S cm-1. Compared with the similar graphene nano composite material film, the graphene nano composite material film has obvious and unique advantages in the aspects of toughness and conductivity, and the toughness and the conductivity are respectively improved by 1679.2% and 295.8% compared with rGO.
Example 9
6g was added to 60mL of water and heated to 90 ℃ until all dissolved. 6g H was then added to the clear PVA solution3PO4Stirring for 12 h. Then soaking the prepared MrGO-AD graphene nano composite material film in PVA/H3PO4And (4) reserving blank positions with the width of 0.5cm at two ends in gel electrolysis for 4 hours. Then soaking the MThe rGO-AD thin film electrode is taken out from the gel electrolyte, assembled together face to form a flexible super capacitor, the blank positions at two ends are connected with copper leads by silver glue, and then the relevant electrochemical performance is tested. All tests were measured using the Chenghua CHI 660e workstation at room temperature. Besides the MXene functionalized graphene nanocomposite film MrGO-AD having the highest toughness, tensile strength and conductivity, the flexible supercapacitor made of the MXene functionalized graphene nanocomposite film MrGO-AD also shows excellent electrochemical energy storage performance. As shown in a in FIG. 5, PVA/H was used3PO4As a gel electrolyte, the MrGO-AD film is assembled into a flexible super capacitor. The cyclic voltammetry curve of the assembled flexible super capacitor is swept at the speed of 10 mV s-1To 1000mV s-1No obvious deformation phenomenon is generated between the MXene nano sheets and the rGO nano sheets due to the Ti-O-C covalent bond formed by the MXene nano sheets and the rGO nano sheets. Meanwhile, the assembled flexible super capacitor also shows good rate performance, and the current density is from 1.0A cm-3To 8.6A cm-3The capacity retention rate still reaches 75.3 percent, and the coulombic efficiency is kept at 100 percent. Furthermore, as shown in fig. 5, e, the assembled flexible supercapacitor exhibited an ultra-long cycle life of titanium carbide, with a capacity retention of-100% after 20000 cycles. Meanwhile, as can be seen from f in FIG. 5, the assembled flexible supercapacitor also exhibits high volumetric energy density and power density, up to 13.0mWh cm each-3And 1994.9mWh cm-3. In addition to satisfactory electrochemical energy storage performance, the assembled flexible supercapacitor also exhibits excellent stability. As shown in a of fig. 6, the capacity retention of the assembled flexible supercapacitor is still 100% at a bending ratio of from 1.0 to 0.2. And the flexible super capacitor assembled by the MrGO-AD film can almost reach 98% after 17000 cycles in a 180-degree bent state, but the capacity retention rate of the rGO-AD and the MrGO is only 87%. In addition, the impedance of the flexible supercapacitor assembled by the MrGO-AD thin film is measured between 0 and 17000 cycles, and the test result shows that the impedance is respectively 1.3 omega and 1.4 omega after 1600 and 17000 cycles, the impedance is not obviously increased after multiple cycles, and excellent bending is shownStability of the koji. Meanwhile, as shown by d-f in fig. 6, the voltage and discharge time of the flexible supercapacitors in series and in parallel are respectively 3 times that of a single flexible supercapacitor, and good stability is maintained in a 0 ° to 180 ° bent state. Meanwhile, the device with the flexible super capacitors connected in series can enable the red 1.7V LED lamp to work normally in the states of tiling, bending and twisting.
The ultrahigh toughness of the MXene functionalized graphene composite material film is caused by Ti-O-C covalent bonds formed by MXene and reduced graphene oxide, slippage between MXene nanosheet layers and interface synergy of pi-pi conjugated stacking of rGO and AD molecules. Through wide angle scattering and small angle scattering, because the interface synergism between MXene nanometer piece, rGO nanometer piece and AD molecule makes the rGO film become inseparabler and promoted the orientation degree of rGO. Meanwhile, MXene nanosheets can fill the rGO interlayer pores, so that the thin film becomes more compact. Due to the interface synergistic effect among the MXene nanosheets, the rGO nanosheets and the AD molecules, the rGO film becomes more compact, the orientation degree of the rGO is improved, and the mechanical property of the MXene functionalized reduced graphene oxide film is improved. In addition, the in-situ Raman spectrum represents the G-band migration volume of the graphene nanosheets, and shows the difference of the loading transfer efficiency of pure rGO, rGO-AD, MrGO and MrGO-AD thin films. Analysis from the results of the tests shows that the achievement of large strain of the MXene functionalized graphene nanocomposite films is due to Ti-O-C covalent bonds between MXene nanosheets and rGO nanosheets, slippage between MXene layers, and interfacial synergy of pi-pi conjugated stacking between rGO and AD molecules. The interface synergistic effect improves the toughness and tensile strength of the MXene functionalized graphene nanocomposite film through comprehensive toughening mechanisms such as plastic deformation, crack propagation inhibition and the like. Meanwhile, the molecular dynamics simulation proves the toughening mechanism of the MXene functionalized graphene nanocomposite film. Therefore, the toughening strategy is used for preparing the MrGO-AD film with super toughness and high conductivity, and the maximum thickness of the MrGO-AD film is 42.7MJ m-3And 1329.0S cm-1. And the MXene functionalized graphene nanocomposite film is assembled into a super capacitor, and has high volume energy densityThe maximum is 13.0mWhcm-3And almost 98% after 17000 cycles in the 180 ° bent state, showing excellent flexibility. Therefore, the ultra-tough graphene nanocomposite film prepared by adopting the toughening strategy promotes wide application in the related fields of flexible devices, aerospace and the like.
It should be noted that, according to the above embodiments of the present invention, those skilled in the art can fully realize the full scope of the present invention as claimed in claim 1 and the appended claims, and the realization process and method are the same as those of the above embodiments; and the invention has not been described in detail so as not to obscure the present invention.
The above description is only a part of the embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. A preparation method of a titanium carbide MXene functionalized graphene nanocomposite film is characterized by comprising the following steps:
(1) mixing raw material Ti3AlC2Stirring and etching by adopting a chemical etching method and taking lithium fluoride (LiF) and hydrochloric acid (HCl) as etching agents to obtain an organ-shaped MXene phase; then preparing a single-layer MXene nanosheet uniform aqueous solution by means of ultrasonic stripping and centrifugal separation;
(2) adding a uniform aqueous solution of single-layer MXene nanosheets prepared by means of ultrasonic stripping and centrifugal separation into an aqueous solution of Graphene Oxide (GO), and performing ultrasonic treatment to form a uniform dispersion liquid of the single-layer MXene nanosheets and the graphene oxide;
(3) stirring and chemically reacting the single-layer MXene nanosheet and the graphene oxide uniform dispersion liquid in the step (2), and reacting to obtain an MXene nanosheet and graphene oxide uniform dispersion liquid;
(4) carrying out vacuum filtration on the MXene nanosheet and the graphene oxide uniform dispersion liquid obtained in the step (3), wherein the MXene nanosheet and the graphene oxide nanosheet in the uniform dispersion liquid are subjected to self-assembly to prepare an MXene functionalized graphene oxide nanocomposite film MGO, and the thickness of the prepared film is 2-10 microns;
(5) regulating the quality of the single-layer MXene nanosheets, repeating the steps (2), (3) and (4) to prepare MXene functionalized graphene oxide nanocomposite films with different MXene nanosheet contents;
(6) reducing the MXene functionalized graphene oxide nanocomposite film obtained in the step (5) by adopting hydroiodic acid (HI) to prepare an MXene functionalized reduced graphene oxide nanocomposite film MrGO, wherein the thickness of the prepared film is 2-10 μm;
(7) and (3) placing the MXene functionalized reduced graphene oxide nano composite material film in the step (6) into an N, N-dimethylformamide solution of 1-aminopyrene-suberic acid bis (N-hydroxysuccinimide ester) (AD) molecules to be soaked for 2-24h, wherein 20-24h is the preferred time, so that the MXene functionalized graphene nano composite material film MrGO-AD is obtained, and the thickness of the prepared film is 2-10 μm.
2. The method for preparing the titanium carbide MXene functionalized graphene nanocomposite film according to claim 1, wherein the method comprises the following steps: the step (2) adopts ultrasonic stripping and centrifugal separation to prepare a uniform aqueous solution of a single-layer MXene nanosheet, and comprises the following steps: dispersing organ-shaped MXene phase in water, performing closed ultrasonic treatment for 0.5-1h, and performing centrifugal separation to obtain MXene nanosheet dispersion liquid; then the mass ratio of the MXene nanosheet solution to the added graphene oxide is controlled to be 5-50%, wherein 15-20% is the preferred mass ratio, and the high toughness (14.2-42.7MJ m) is prepared through the preferred ratio in the range-3) And high conductivity (412.7-1329.0S cm-1) The graphene nanocomposite film of (1).
3. The method for preparing the titanium carbide MXene functionalized graphene nanocomposite film according to claim 1, wherein the method comprises the following steps: in the step (3), the ultrasonic time is 5-10 minutes, the stirring reaction is carried out for 6-8 hours, and the monolayer MXene nanosheets and the GO nanosheets can be fully reacted at the time without generating precipitates.
4. The method for preparing the titanium carbide MXene functionalized graphene nanocomposite film according to claim 1, wherein the method comprises the following steps: in the step (4), the process of preparing the MXene functionalized graphene oxide nanocomposite film MGO by self-assembly is as follows: firstly, adding MXene nanosheet and graphene oxide uniform dispersion liquid into a suction filtration funnel, and enabling the vacuum degree of a suction filtration device to reach 0.09-0.1 MPa; and after the filtration is finished, obtaining the MXene functionalized graphene oxide nanocomposite film with the thickness of 2-10 mu m, and obtaining the graphene oxide nanocomposite film with obvious and compact layer shape by a filtration mode.
5. The method for preparing the titanium carbide MXene functionalized graphene nanocomposite film according to claim 1, wherein the method comprises the following steps: in the step (5), the mass fraction of the MXene nanosheets is regulated to be 5-50%, wherein 15-20% is a preferred mass ratio, namely the mass of the added graphene oxide accounts for 95-50% of the total mass, and 85-80% is the preferred mass ratio. The mass fraction of the MXene nanosheet solution with the optimal mechanical property is determined by representing the mechanical property of MXene functionalized graphene oxide nanocomposite films with different mass fractions.
6. The method for preparing the titanium carbide MXene functionalized graphene nanocomposite film according to claim 1, wherein the method comprises the following steps: in the step (6), the MXene functionalized reduced graphene oxide nanocomposite film is treated by using a HI solution with the concentration of 37.0-38.0% for 6-12h, then washed by using ethanol, soaked for 12-24h, and dried in vacuum at the temperature of 50-60 ℃ to obtain the MXene functionalized reduced graphene oxide nanocomposite film.
7. The method for preparing the titanium carbide MXene functionalized graphene nanocomposite film according to claim 1, wherein the method comprises the following steps: the step (7) is specifically as follows: the method comprises the steps of soaking a reduced graphene oxide-MXene nanocomposite in a N, N-Dimethylformamide (DMF) solution of 12mM AD molecules for 2-24h, wherein 20-24h is the preferred time, washing with the DMF solution for 4-5 times, continuing washing with ethanol for 5-6 times, and then drying in vacuum at 50-60 ℃ to obtain an MXene functionalized graphene nanocomposite film.
8. The application of the preparation method of the titanium carbide MXene functionalized graphene nanocomposite film in the flexible supercapacitor according to any one of claims 1 to 6 is characterized in that: and (5) assembling the MXene functionalized graphene nanocomposite film obtained in the step (7) into a flexible supercapacitor.
9. The application of the preparation method of the titanium carbide MXene functionalized graphene nanocomposite film in the flexible supercapacitor is characterized in that: measuring the volume energy density of the flexible super capacitor up to 13.0mWh cm-3And the assembled flexible super capacitor keeps excellent flexibility, and the capacity retention rate is still 87-98% after the flexible super capacitor is bent for 17000 times at 180 degrees.
10. The application of the preparation method of the titanium carbide MXene functionalized graphene nanocomposite film in the flexible supercapacitor is characterized in that: the preparation method of the flexible supercapacitor comprises the following steps: mixing PVA and water at a mass ratio of 1:10, heating to 90 deg.C until all PVA and phosphoric acid (H) are dissolved, adding transparent PVA and phosphoric acid3PO4) The mass ratio of the components is 1:1, stirring is carried out for 12 hours, and then the prepared MrGO-AD graphene nano composite material film is soaked in PVA/H3PO4And (3) reserving blank positions with the width of 0.5cm at two ends in gel electrolysis for 4 hours, taking out the soaked MrGO-AD thin film electrode from the gel electrolyte, assembling the electrode face to form a flexible supercapacitor, connecting the blank positions at the two ends with copper leads by using silver adhesive, and then testing related electrochemical performances, wherein all tests are tested by using an electrochemical workstation at room temperature.
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| CN116836418A (en) * | 2023-08-31 | 2023-10-03 | 广州双一乳胶制品有限公司 | Anti-aging condom and preparation method thereof |
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