CN114628166A - Preparation method of asymmetric fibrous flexible supercapacitor - Google Patents

Preparation method of asymmetric fibrous flexible supercapacitor Download PDF

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CN114628166A
CN114628166A CN202210274992.1A CN202210274992A CN114628166A CN 114628166 A CN114628166 A CN 114628166A CN 202210274992 A CN202210274992 A CN 202210274992A CN 114628166 A CN114628166 A CN 114628166A
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mxene
pedot
fiber
fibers
rgo
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CN114628166B (en
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吴明懋
贺瑾凤
孙科
邹志刚
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Mindu Innovation Laboratory
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • H01G11/48—Conductive polymers

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Abstract

The invention discloses a preparation method of an asymmetric fibrous flexible supercapacitor, and belongs to the technical field of supercapacitors. The invention adopts poly 3, 4-ethylenedioxythiophene/polyaniline (PEDOT/PANI) as the anode and MXene/rGO as the cathode. The addition of high-electrical activity PANI improves the integral capacitance of the fiber, and the stable PEDOT hydrogel framework provides rich ion diffusion channels and a rapid electron transfer path; MXene exhibits excellent performance in electrochemical energy storage and many other applications due to its excellent electrochemical properties and metal conductivity, with a moderate amount of rGO as a binder to keep the MXene material in a fibrous morphology. The asymmetric fibrous supercapacitor obtained after the assembly of the positive electrode and the negative electrode is small in size, has a wider working voltage window, excellent energy density and power density and good flexibility, and is suitable for the fields of portable energy storage and flexible wearable.

Description

Preparation method of asymmetric fibrous flexible supercapacitor
Technical Field
The invention belongs to the technical field of asymmetric fiber super capacitors, and particularly relates to a preparation method of an asymmetric fibrous flexible super capacitor, which is a preparation method of an asymmetric fibrous flexible super capacitor with a wide voltage window.
Background
Supercapacitors have attracted considerable attention in many power supply areas due to their unique properties and great potential for development. Supercapacitors are generally classified into double layer supercapacitors and pseudocapacitive supercapacitors according to the mechanism of energy storage. The electric double layer super capacitor is generally composed of a porous carbon material, and can physically gather a large amount of charges on rich interfaces of electrodes/electrolytes, and the characteristic enables the electric double layer super capacitor to be charged and discharged rapidly, and meanwhile, the electric double layer super capacitor has excellent cycling stability. However, the specific capacitance of the electric double layer supercapacitor is relatively low. In the pseudo capacitor, the active substance and electrolyte ions are subjected to rapid and reversible redox reaction on the surface of or near an electrode through an electrode material, so that capacitance is generated, and the reaction is generated on the surface of the electrode material and in a bulk phase, so that the capacitance of the pseudo capacitor is higher than that of an electric double layer capacitor, but the cycling stability of the pseudo capacitor is generally not good as that of the electric double layer capacitor. Thus, asymmetric supercapacitors have been extensively studied in recent years due to the combination of the advantages of electric double layer supercapacitors and pseudocapacitive supercapacitors. Typical Asymmetric Supercapacitors (ASCs) have good electrochemical performance, such as a wide operating voltage window, suitable capacitance, high energy density and power density.
In recent years, due to rapid development of wearable portable electronic devices in the fields of medical treatment, military, outdoor, and the like, miniaturization, flexibility, and high energy density of energy storage devices have been demanded. To achieve this, Fibrous Supercapacitors (FSCs) are becoming more and more popular due to their advantages of small size, high flexibility, fast charge and discharge, and stable mechanical properties, however, their practical application is limited by the relatively low energy density of fibrous supercapacitors.
MXene is an emerging family of two-dimensional transition metal carbides or nitrides of the general formula Mn+1XnTxWherein M is a transition metal, X is carbon or nitrogen, n is an integer of 1 to 4, TxRepresents a surface functional group. MXene has unique metal conductivity and adjustable surface functional group, so that MXene can be displayed in the field of electrochemistryHas great prospect.
Commercial conductive polymer dispersion poly 3, 4-ethylenedioxythiophene: poly 4-styrenesulfonate (PEDOT: PSS) is of interest because of its solution processability, high pseudocapacitance, and good ionic and electronic conductivity. The ionic conductivity of the conductive polymer can promote the diffusion of electrolyte ions, and the conductivity of the acid-treated PEDOT PSS can reach 4000S cm-1And can promote the rapid transfer of electrons in the electrode. PSS is a promising candidate for fiber electrodes, whereas pure PEDOT fibers still do not meet the requirements for high performance fiber supercapacitors due to their limited capacitance. Therefore, hybrid fiber electrodes prepared by mixing PEDOT as a matrix and other high-electric-activity pseudocapacitance materials are in need.
Disclosure of Invention
Aiming at the problems that the conventional asymmetric fiber supercapacitor electrode is high in cost, complex in preparation process, low in voltage window and unsatisfied in electrochemical performance, the invention aims to provide a preparation method of an asymmetric fibrous flexible supercapacitor, wherein a poly (3, 4-ethylenedioxythiophene) (PEDOT) hydrogel is used as a framework, Aniline (ANI) is used as an adsorbent, and an asymmetric fiber supercapacitor anode is prepared; MXene is used as a framework, and redox graphene (rGO) is used as an adhesive to prepare the asymmetric fiber super capacitor cathode. The addition of the high-electrical-activity polyaniline improves the anode capacitance of the fiber, the stable PEDOT hydrogel framework provides rich ion diffusion channels and a rapid electron transfer approach, and the utilization efficiency of the polyaniline is improved. The surface oxidation reaction between the intercalated protons and the rich oxygen-containing functional groups enables MXene to have ultrahigh volume capacitance, the rGO is used as a binder to enable MXene materials to keep a fiber shape, the obtained MXene/rGO fibers keep a compact layered structure and have rich specific surface area, the contact with electrolyte in a test is facilitated, the rapid reaction is facilitated, the electrochemical performance of the asymmetric fiber super capacitor is improved, poly (3, 4-ethylenedioxythiophene)/polyaniline (PEDOT/PANI) and MXene/rGO are respectively used as the positive electrode and the negative electrode of the asymmetric fiber super capacitor (FASCs), and the obtained asymmetric fiber super capacitor has a wider working voltage window, and excellent energy density and power density.
According to the invention, poly (3, 4-ethylenedioxythiophene)/polyaniline (PEDOT/PANI) is used as the anode, MXene/rGO is used as the cathode, and the obtained asymmetric fibrous super capacitor has a wider working voltage window, excellent energy density and power density and good flexibility. The method comprises the following specific steps: (1) firstly, obtaining PEDOT fibers by carrying out hydrothermal treatment on poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonate (PEDOT: PSS); (2) then adsorbing Aniline (ANI) on the PEDOT fiber and polymerizing to obtain PEDOT/PANI composite fiber; (3) mixing MXene and redox graphene (rGO) and then obtaining MXene/rGO mixed fiber through hydrothermal treatment; (4) assembling the PEDOT/PANI composite fiber obtained in the step (2) and the MXene/rGO mixed fiber obtained in the step (3) on a poly (terephthalic acid) Plastic (PET) plate, and coating a gel electrolyte to obtain the asymmetric fibrous capacitor. The addition of high-electrical activity Polyaniline (PANI) improves the integral capacitance of the fiber, the stable PEDOT hydrogel framework provides rich ion diffusion channels and a rapid electron transfer path, and the utilization efficiency of the PANI is improved. The rGO is used as a binder to enable the MXene material to keep a fiber form, and the MXene/rGO fibers obtained by the method keep a compact layered structure, have rich specific surface area, are convenient to contact with electrolyte in a test, and are beneficial to a rapid redox reaction, so that the electrochemical performance of the asymmetric fiber supercapacitor is improved. The PEDOT/PANI is used as the anode fiber electrode, the MXene/rGO is used as the cathode fiber electrode, the capacity retention rate of the assembled asymmetric fibrous super capacitor is high after 1000 times of bending, the capacity is hardly attenuated at various bending angles, and the capacitor shows good flexibility.
The purpose of the invention is realized by the following technical scheme.
A preparation method of an asymmetric fibrous flexible supercapacitor comprises the following steps:
1) preparing an aniline mixed solution: uniformly mixing the hydrochloric acid solution with aniline;
2) preparing an ammonium persulfate mixed solution: uniformly mixing the hydrochloric acid solution with ammonium persulfate;
3) preparing PEDOT fiber: and mixing PEDOT, PSS and sulfuric acid to form a mixture, carrying out hydrothermal treatment on the mixture to obtain a first fiber, then carrying out acid treatment on the first fiber, and washing the acid-treated fiber with deionized water to obtain the PEDOT fiber.
4) Preparing PEDOT/PANI fiber: and (2) putting the PEDOT fiber prepared in the step 3) into the aniline mixed solution prepared in the step 1), then pouring the ammonium persulfate mixed solution prepared in the step 2) into the aniline mixed solution, taking out after polymerization, and airing to obtain the PEDOT/PANI fiber.
5) Preparation of MXene/rGO fiber: mixing MXene, Graphene Oxide (GO) and ascorbic acid (Vc) to form a mixture, and then placing the mixture in a reaction kettle for hydrothermal treatment to obtain the MXene/rGO fiber.
6) Preparing a capacitor anode by using the PEDOT/PANI fibers obtained in the step 4), preparing a capacitor cathode by using the MXene/rGO fibers obtained in the step 5), and preparing a capacitor by using the anode and the cathode.
The method comprises the steps of using PEDOT hydrogel as a framework, firstly carrying out hydrothermal treatment on PEDOT: PSS suspension, washing with deionized water after acid treatment overnight, optimally regulating and controlling the concentration of sulfuric acid, the dosage ratio of sulfuric acid to PEDOT: PSS suspension, hydrothermal temperature and time, and facilitating the formation of the PEDOT framework. And by adjusting the concentration of MXene and the dosage ratio of MXene to GO, the MXene/rGO fiber has the best electrochemical performance on the basis of forming.
Preferably, in the step 1), the hydrochloric acid solution has a hydrochloric acid concentration of 1M, a volume ratio of hydrochloric acid to aniline of 10:0.3, and an adsorption time of 12 h.
Preferably, the ammonium persulfate mixed solution in the step 2) is a 1M mixed solution of hydrochloric acid and ammonium persulfate, and the mass ratio is 10: 0.18;
further, the hydrothermal treatment in step 3) is carried out in a reaction kettle.
Preferably, the polymerization in the step 4) is carried out at a temperature of-10 to 60 ℃. The polymerization time is 2-8 h. Preferably, the polymerization is carried out at a temperature of 0, 30, 60 ℃.
Preferably, the ammonium persulfate solution in the step 4) is poured into the aniline mixed solution, and the polymerization time is 2, 4 or 6 hours.
Optimally, the ammonium persulfate solution in the step 4) is poured into the aniline mixed solution, and the polymerization time is 4 h.
Preferably, the concentration of MXene in step 5) is 12 mg/mL.
Preferably, in the step 5), the mass ratio of MXene to GO to Vc is 4:1: 5.
Preferably, the concentration of MXene in step 5) is 12 mg/mL.
Preferably, in the step 5), the mass ratio of MXene to GO to Vc is 9:1: 5.
Optimally, the concentration of MXene in step 5) is 28 mg/mL.
Preferably, in the step 5), the mass ratio of MXene to GO to Vc is 21:1: 5.
The PEDPT/PANI and MXene/rGO prepared by the invention have higher specific capacitance as electrodes, and the specific capacitance is 698F cm-3And 1057F cm-3。
Therefore, the invention also claims PEDOT/PANI and MXene/rGO prepared by the method.
The PEDOT hydrogel framework prepared by the method provides abundant ion transmission channels and electron transfer capacity, and maximizes the capacitance utilization rate of Polyaniline (PANI). MXene provides abundant specific surface area, so that subsequent electrodes can be conveniently contacted with electrolyte in a test, a good channel is provided for ion transmission, and the electrochemical performance of the asymmetric fiber supercapacitor is improved.
The PEDOT/PANI and MXene/rGO materials are used as electrodes and have high specific capacitance, and the prepared asymmetric fiber super capacitor has a wide working voltage window which is 0-1.45V, so that the energy density and the power density of the asymmetric fiber super capacitor are improved. Correspondingly, at a power density of 724.9mW cm-3The energy density was 40.47mWh cm-3。
In the invention, the chemical formula of the MXene material is Ti3C2TxThe average thickness and the transverse dimension of the single slice of the two-dimensional layered structure are respectively about 1-2 nm and 2-4 mu m.
As a preferred possible embodiment, the asymmetric fiber supercapacitor is prepared by:
assembling the anode fiber PEDOT/PANI and the cathode fiber MXene/rGO in parallel on a PET plate, and wrapping a layer of polyvinyl alcohol (PVA) gel electrolyte on the PET plate to finally obtain the asymmetric fibrous supercapacitor.
Compared with the prior art, the invention has the following beneficial effects:
according to the method, a PEDOT/PSI suspension is subjected to hydrothermal treatment to obtain a PEDOT hydrogel framework, aniline is adsorbed in an ice bath and polymerized to obtain a PEDOT/PANI positive electrode fiber, the PEDOT has excellent conductivity, the PANI has excellent capacitance performance, and the PEDOT/PANI has high specific capacitance and excellent electrochemical performance under the synergistic effect; the invention also allocates the optimal dosage ratio of MXene and rGO, so that the electrochemical performance is optimal while the fiber is formed, the volume of the MXene/rGO fiber after being suspended and dried is shrunk, the specific surface area inside the fiber is increased, and the specific capacitance of the cathode fiber is obviously improved.
Drawings
FIGS. 1 a-d are SEM images of poly-3, 4-ethylenedioxythiophene/polyaniline (PEDOT/PANI); the e-h images are SEM images of MXene/rGO;
FIG. 2 a is EDS diagram of PEDOT/PANI; b is an EDS map of MXene/rGO;
FIG. 3 a is a cyclic voltammogram of the PEDOT/PANI fibers of example 2 at different sweep rates; b is a volume capacitance change diagram of the PEDOT/PANI fibers of the embodiments 1-3 under different current densities; c is a constant current charge and discharge curve of the PEDOT/PANI fibers of the embodiments 1-3 under different current densities; d is the peak current versus sweep rate curve for the PEDOT/PANI fibers of example 2; e is an EIS diagram of PEDOT/PANI fibers of examples 1-3; f is the change curve of the volume capacitance of the PEDPT/PANI under different cycle turns;
FIG. 4 a is a cyclic voltammogram of the MXene/rGO fiber electrode of example 6 at different scan rates; b is a volume capacitance change diagram of the MXene/rGO fibers of examples 4-6 under different current densities; c is a constant current charge and discharge curve diagram of the MXene/rGO fiber electrode of example 6 under different current densities; d is a variation curve of the peak current and the sweeping speed; e is an EIS diagram of MXene/rGO fiber electrodes of examples 4-6; f is the curve graph of the change of the volume capacitance of the MXene/rGO fiber electrode of example 6 under different cycle numbers;
a in FIG. 5 is the asymmetric fiber capacitor at 5mV s-1A CV curve of (a); b is a CV diagram of the asymmetric fiber capacitor under different scanning speeds; c is a constant current charge-discharge diagram of the asymmetric fiber capacitor under different current densities; d is a volume capacitance change diagram of the asymmetric fibrous supercapacitor at different sweeping speeds;
FIG. 6 is a graph of energy density versus power density for an asymmetric fiber supercapacitor;
FIG. 7 is a graph of volumetric capacitance for different times of bending of an asymmetric fiber supercapacitor;
FIG. 8 is a CV diagram of asymmetric fiber supercapacitors at different bend angles, with a scan rate of 5mV s-1。
Detailed Description
The invention is further illustrated by the following specific examples in which the reagents and materials are commercially available unless otherwise indicated.
Example 1
1) Preparing an aniline mixed solution: uniformly mixing 10mL of 1M hydrochloric acid solution with 0.3mL of aniline;
2) preparing an ammonium persulfate mixed solution: uniformly mixing 10mL of 1M hydrochloric acid solution with 0.18g of ammonium persulfate;
3) preparing PEDOT fiber: 1mL of a suspension of PEDOT: PSS (Clevios (TM) PH1000 available from Hesley, Germany, in which PEDOT was dispersed in water-soluble polystyrene sulfonic acid (PSS) to form a suspension, the content of PEDOT was 13 wt%), and 200. mu.L of 5M sulfuric acid were mixed, sonicated for 5 minutes, injected into a glass capillary, and hydrothermally treated at 90 ℃ for 2 hours. After hydrothermal treatment, the fibers are shaped. The glass capillary is taken out, and the fiber is pushed out from one end of the glass capillary. Then, the fiber is replaced into a concentrated sulfuric acid solution of 18M and is kept stand for 12 hours, and the fiber after acid treatment is washed by deionized water;
4) preparing PEDOT/PANI fiber: putting the fiber prepared in the step 3) into the aniline mixed solution, standing for 12 hours in an ice bath at 0 ℃, pouring the ammonium persulfate mixed solution into the aniline mixed solution, polymerizing for 2 hours in the ice bath at 0 ℃, taking out, and hanging and airing. The diameter of the finally prepared fiber is about 28-32 mu m.
Example 2
1) Preparing an aniline mixed solution: uniformly mixing 10mL of 2M hydrochloric acid solution with 0.5mL of aniline;
2) preparing an ammonium persulfate mixed solution: uniformly mixing 10mL of 2M hydrochloric acid solution with 0.36g of ammonium persulfate;
3) preparing PEDOT fiber: 1mL of a suspension of PEDOT: PSS (Clevios (TM) PH1000 available from Hesley, Germany, in which PEDOT was dispersed in water-soluble polystyrene sulfonic acid (PSS) to form a suspension, the content of PEDOT was 13 wt%), and 200. mu.L of 5M sulfuric acid were mixed, sonicated for 5 minutes, injected into a glass capillary, and hydrothermally treated at 90 ℃ for 5 hours. After hydrothermal treatment, the fibers are shaped. The glass capillary is taken out, and the fiber is pushed out from one end of the glass capillary. Then, the fiber is replaced into a 16M sulfuric acid solution to be kept stand for 12 hours, and the fiber after acid treatment is washed by deionized water;
4) preparing PEDOT/PANI fiber: putting the fiber prepared in the step 3) into the aniline mixed solution, standing for 12 hours in a normal-temperature water bath at the temperature of 30 ℃, pouring the ammonium persulfate mixed solution into the aniline mixed solution, polymerizing for 4 hours in the normal-temperature water bath, taking out, and hanging and airing. The diameter of the finally prepared fiber is about 30-35 mu m.
Example 3
1) Preparing an aniline mixed solution: uniformly mixing 10mL of 2M hydrochloric acid solution with 0.5mL of aniline;
2) preparing an ammonium persulfate mixed solution: uniformly mixing 10mL of 2M hydrochloric acid solution with 0.36g of ammonium persulfate;
3) preparing PEDOT fibers: 1mL of a suspension of PEDOT: PSS (Clevios PH1000 available from Hedys, Germany, in which PEDOT is dispersed in water-soluble polystyrene sulfonic acid (PSS) to form a suspension, the content of PEDOT being 13% by weight) and 200. mu.L of sulfuric acid having a concentration of 5M were mixed, sonicated for 5 minutes, injected into a glass capillary, and hydrothermally treated at 90 ℃ for 5 hours. After hydrothermal treatment, the fibers are formed. The glass capillary tube is taken out, and the fiber is pushed out from one end of the glass capillary tube. Then, the fiber is replaced into a 12M sulfuric acid solution to be kept stand for 12 hours, and the fiber after acid treatment is washed by deionized water;
4) preparing PEDOT/PANI fiber: putting the fiber prepared in the step 3) into the aniline mixed solution, carrying out hydrothermal reaction at 60 ℃ for 12 hours, pouring the ammonium persulfate mixed solution into the aniline mixed solution, carrying out hydrothermal polymerization for 6 hours, taking out, and carrying out suspension drying. The diameter of the finally prepared fiber is about 32-38 mu m.
Example 4
Preparation of MXene/rGO fiber: 0.8mL of Ti3C2TxMXene (12mg/mL) (by etching Ti3AlC2Obtaining Ti from MAX phase3C2TxMXene. Specifically, 1g of Ti3AlC2MAX phase is mixed with 1.6g LiF and 20ml 9M HCl, stirred for 12h at 40 ℃, taken out of solution, diluted and centrifuged until the solution is neutral. And then centrifuging at 10000rpm for 30 minutes, taking out a precipitate, carrying out ultrasonic treatment on the solution after taking out the precipitate for 30 minutes, centrifuging at 10000rpm for 20 minutes, stripping to obtain a low-concentration MXene solution, and concentrating the low-concentration MXene solution to obtain the required MXene solution. Wherein Ti3C2TxMXene is dispersed in an aqueous solution, and the average thickness and the transverse dimension of the single flake are about 1 to 2nm and about 2 to 4 μm, respectively. Ti as mentioned above3AlC2MAX is available from Karen ceramics, Inc. of Lyzhou, CAS 196506-01-1, MW 194.6; LiF is purchased from Michelin corporation, CAS 7789-24-4, L812324), 0.2mL GO (dispersed in water solution) (12mg/mL) and 12mg Vc are mixed and subjected to ultrasonic treatment, then the mixture is injected into a reaction kettle for hydrothermal treatment, the hydrothermal treatment temperature is 90 ℃, and the hydrothermal treatment time is 0.5 h. The diameter of the finally prepared fiber is about 32-38 mu m.
Example 5
Preparation of MXene/rGO fibers: 0.9mL of Ti3C2TxMXene (12mg/mL) (by etching Ti3AlC2Obtaining Ti from MAX phase3C2TxMXene. Specifically, 1g of Ti3AlC2MAX phase is mixed with 1.6g LiF and 20ml 9M HCl, stirred for 12h at 40 ℃, taken out of solution, diluted and centrifuged until the solution is neutral. And then centrifuging at 10000rpm for 30 minutes, taking out a precipitate, carrying out ultrasonic treatment on the solution after taking out the precipitate for 30 minutes, centrifuging at 10000rpm for 20 minutes, stripping to obtain a low-concentration MXene solution, and concentrating the low-concentration MXene solution to obtain the required MXene solution. Wherein Ti3C2TxMXene is dispersed in an aqueous solution, and the average thickness and the transverse dimension of each flake are about 1 to 2nm and about 2 to 4 μm, respectively. Ti as mentioned above3AlC2MAX is available from Karen ceramics, Inc. of Lyzhou, CAS 196506-01-1, MW 194.6; LiF is purchased from Michelin corporation, CAS 7789-24-4, L812324), 0.1mL GO (12mg/mL) (dispersed in aqueous solution) and 6mg Vc (ascorbic acid) are mixed and subjected to ultrasonic treatment, and then the mixture is injected into a reaction kettle for hydrothermal treatment, wherein the hydrothermal treatment temperature is 90 ℃, and the hydrothermal treatment time is 0.5 h. The diameter of the finally prepared fiber is about 30-35 mu m.
Example 6
Preparation of MXene/rGO fiber: 0.9mL of Ti3C2TxMXene (28mg/mL) (by etching Ti3AlC2Obtaining Ti from MAX phase3C2TxMXene. Specifically, 1g of Ti3AlC2MAX phase is mixed with 1.6g LiF and 20ml 9M HCl, stirred for 12h at 40 ℃, taken out of the solution, diluted and centrifuged until the solution is neutral. And then centrifuging at 10000rpm for 30 minutes, taking out a precipitate, carrying out ultrasonic treatment on the solution after taking out the precipitate for 30 minutes, centrifuging at 10000rpm for 20 minutes, stripping to obtain a low-concentration MXene solution, and concentrating the low-concentration MXene solution to obtain the required MXene solution. Wherein Ti3C2TxMXene is dispersed in an aqueous solution, and the average thickness and the transverse dimension of each flake are about 1 to 2nm and about 2 to 4 μm, respectively. Ti as mentioned above3AlC2MAX from Kallen ceramics, Inc. of Laizhou, CAS196506-01-1, MW 194.6; LiF was obtained from Michelin corporation, CAS 7789-24-4, L812324, and was mixed with 0.1mL GO (12mg/mL) (dispersed in aqueous solution) and 6mg Vc (ascorbic acid), sonicated, and then injected into a reaction kettle for hydrothermal treatment at 90 deg.C for 0.5 h. The diameter of the finally prepared fiber is about 28-32 mu m.
EXAMPLE 7 characterization of Single electrode
1. Test method
SEM appearance characterization and EDS characterization are carried out on the samples prepared in the examples 1-6 by using an SUPRA 55 type field emission scanning electron microscope; electrochemical performance tests were performed on the Shanghai Chenghua CHI760E electrochemical workstation, in which a platinum sheet electrode/graphite sheet electrode was used as the counter electrode and a saturated calomel electrode was used as the reference electrode. PEDOT/PANI samples from examples 1 to 3 and MXene/rGO samples from examples 4 to 6 were working electrodes, 1M H2SO4The solution is an electrolyte.
2. Analysis of results
(1) FIGS. 1 a-c are SEM images of PEDOT/PANI prepared in examples 1-3, and d is an enlarged SEM image of example 2, wherein the fibers are seen to have a three-dimensional interconnected porous structure to facilitate ion transport and electron transfer; FIGS. 1, e-g, are SEM images of MXene/rGO prepared in examples 4-6, h is an enlarged SEM image of example 6, from which it can be seen that the fibers have a dense layered structure;
(2) FIG. 2, panel a, is an EDS map of PEDOT/PANI prepared in example 2, from which it can be seen that C, O, S, N elements are uniformly distributed within the fiber; FIG. 2 b is an EDS plot of MXene/rGO prepared in example 6, from which it can be seen that Ti, C, F, O elements are uniformly distributed inside the fiber.
(3) FIG. 3, panel a, is a cyclic voltammogram of PEDOT/PANI fibers prepared in example 2 at different sweep rates, showing a pair of distinct redox peaks, indicating the occurrence of a pseudocapacitive response; b is a volume capacitance change diagram of the PEDOT/PANI fibers prepared in the embodiments 1-3 under different current densities, and it can be seen that compared with pure PEDOT fibers, the capacitance of the compounded PEDOT/PANI fibers is obviously improved, wherein the fibers prepared in the embodiment 2 show the highest volume capacitance; c is a constant current charge and discharge curve of the PEDOT/PANI fiber prepared in the embodiment 2 under different current densities, and no obvious platform exists, so that good pseudo-capacitance performance is indicated; d is a change curve of the peak current and the sweep rate of the PEDOT/PANI fiber prepared in example 2, the slope b reflects the energy storage mechanism of the electrode (b is 0.5, the reaction is the energy storage process controlled by diffusion, b is 1, the reaction is the energy storage process controlled by capacitance), and the slope of the PEDOT/PANI fiber is between 0.5 and 1, which is the result of cooperative control of capacitance and diffusion; e is an EIS diagram of the PEDOT/PANI fibers prepared in the embodiments 1-3, and the PEDOT/PANI fibers prepared in the embodiment 2 have the smallest resistance and the largest ion diffusion coefficient; f is the change curve of the volume capacitance of the PEDPT/PANI under different cycle turns;
(4) FIG. 4 a is a cyclic voltammogram of the MXene/rGO fiber electrode prepared in example 6 at different scan rates, and a pair of distinct redox peaks can also be seen, showing good pseudocapacitance performance; b is a volume specific capacitance change diagram of the MXene/rGO fibers prepared in the embodiments 4-6 under different current densities, and the MXene/rGO prepared in the embodiment 6 has the highest volume capacitance and the best electrochemical performance; c is a constant current charge and discharge curve diagram of the MXene/rGO fiber electrode prepared in example 6 under different current densities, and the MXene/rGO fiber electrode has no obvious platform and good pseudo-capacitance performance; d is a change curve of peak current and sweep rate, the slope b reflects an energy storage mechanism of the electrode (b is 0.5, the reaction is an energy storage process controlled by diffusion, b is 1, the reaction is an energy storage process controlled by capacitance), it can be seen that the slope of the MXene/rGO fiber electrode at the anode is 0.74 and between 0.5 and 1, which is a result of cooperative control of capacitance and diffusion, and the slope of the MXene/rGO fiber electrode at the cathode is 0.95 and very close to 1, which is a result of capacitance control; e is an EIS diagram of the MXene/rGO fiber electrode prepared in the embodiment 4-6, and the MXene/rGO prepared in the embodiment 6 has the smallest resistance and the largest ion diffusion coefficient; f is a volume capacitance change curve diagram of the MXene/rGO fiber electrode prepared in example 6 under different cycle numbers, and it can be seen that after 10000 cycles, the capacitance retention rate is 115%, and the good cycle stability is achieved.
EXAMPLE 8 asymmetric fiber supercapacitor
1. Preparation method
Asymmetric fiber supercapacitors (FASCs) were prepared using PEDOT/PANI prepared in example 2 and MXene/rGO fibers prepared in example 6 by the following procedure:
PEDOT/PANI fibers prepared in example 2 were used as the positive electrode of a capacitor and MXene/rGO fibers prepared in example 6 were used as the negative electrode of a capacitor. Placing a fiber anode (PEDOT/PANI) and a fiber cathode (MXene/rGO) on a poly (terephthalic acid) Plastic (PET) plate in parallel, wherein the distance between the anode and the cathode is 100-200 mu m, then coating a layer of gel electrolyte with the thickness of about 1-2 mm, covering the middle section of the anode and the cathode fibers, leaving the distance of 1-2 cm to be in contact with the outside, and packaging the middle distance of 1-2 cm by using an adhesive tape to ensure that moisture in the gel electrolyte between the adhesive tape and the PET plate cannot evaporate. Wherein the gel electrolyte is 10 wt% of polyvinyl alcohol (PVA) and 10 wt% of H2SO480 wt% deionized water.
2. Analysis of electrochemical performance test results of super capacitor
(1) A in FIG. 5 is the asymmetric fiber capacitor at 5mV s-1A CV curve of (a); b is a CV diagram of the asymmetric fiber capacitor under different sweep speeds, and shows a good charging and discharging process; c is a constant current charge and discharge diagram of the asymmetric fiber capacitor under different current densities, and the current density can be seen from the diagram to be from 1A cm-3To 50A cm-3Exhibit excellent charge and discharge processes; d is a volume capacitance change graph of the asymmetric fibrous supercapacitor at different sweeping speeds, and can be seen from the graph, at 1A cm-3The specific capacitance of the capacitor reaches 138.6F cm under the current density-3；
(2) FIG. 6 is a graph of energy density versus power density for an asymmetric fiber supercapacitor, from which it can be seen that the asymmetric fiber supercapacitor of the present invention has an energy density and a power density superior to those of other asymmetric supercapacitors at a power density of 724.9mW cm-3Then, 40.47mWh cm was obtained-3High energy density.
(3) FIG. 7 is a graph of the volume capacitance of the asymmetric fiber supercapacitor after being bent for different times, and it can be seen that the capacitance is still maintained at 100.5% after being bent for 1000 times, which illustrates that the asymmetric fiber supercapacitor of the present invention has good flexibility;
(4) FIG. 8 is a CV diagram of asymmetric fiber supercapacitors at different bending angles (scan speed of 5mV s)-1) It can be seen that the capacitance is not attenuated basically under different bending angles, which shows that the fibrous supercapacitor of the invention has good flexibility.
The invention has not been described in detail and is part of the common general knowledge of a person skilled in the art. The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and the preferred embodiments are not exhaustive and do not limit the invention to the precise embodiments described. Various modifications and improvements of the technical solution of the present invention may be made by those skilled in the art without departing from the spirit of the present invention, and the technical solution of the present invention is to be covered by the protection scope defined by the claims.

Claims (8)

1. A preparation method of an asymmetric fibrous flexible supercapacitor is characterized by comprising the following steps:
1) preparing an aniline mixed solution: uniformly mixing the hydrochloric acid solution with aniline;
2) preparing an ammonium persulfate mixed solution: uniformly mixing the hydrochloric acid solution with ammonium persulfate;
3) preparing PEDOT fiber: PSS and sulfuric acid are mixed to form a mixture, the mixture is subjected to hydrothermal treatment to obtain first fibers, then the first fibers are subjected to acid treatment, and the fibers subjected to acid treatment are washed by deionized water to obtain PEDOT fibers;
4) preparing PEDOT/PANI fiber: putting the PEDOT fibers prepared in the step 3) into the aniline mixed solution prepared in the step 1), then pouring the ammonium persulfate mixed solution prepared in the step 2) into the aniline mixed solution, taking out after polymerization, and airing to obtain PEDOT/PANI fibers;
5) preparation of MXene/rGO fiber: mixing MXene, Graphene Oxide (GO) and ascorbic acid (Vc) to form a mixture, and then placing the mixture in a reaction kettle for hydrothermal treatment to obtain MXene/rGO fibers;
6) preparing a capacitor anode by using the PEDOT/PANI fibers obtained in the step 4), preparing a capacitor cathode by using the MXene/rGO fibers obtained in the step 5), and preparing a capacitor by using the anode and the cathode.
2. The method according to claim 1, wherein in the step 1), the concentration of hydrochloric acid in the hydrochloric acid solution is 0.5-8M, the volume ratio of hydrochloric acid to aniline is 100: 1-10: 1, and the adsorption time is 12-36 h.
3. The method according to claim 1, wherein in the step 2), the concentration of hydrochloric acid in the hydrochloric acid solution is 0.5-8M, and the mass ratio of hydrochloric acid to ammonium persulfate is 100: 1-5: 1.
4. The method according to claim 1, wherein in the step 3), the concentration of the sulfuric acid is 0.5-5M, and the volume ratio of PEDOT to PSS suspension to sulfuric acid is 10: 1-5: 1.
5. The method of claim 1, wherein the polymerization in step 4) is carried out at a temperature of-10 to 60 ℃ for 2 to 8 hours.
6. The method according to claim 1, wherein the concentration of MXene in step 5) is 7-30 mg/mL; the mass ratio of MXene to GO to Vc is 2-30: 0.5-2: 2-15.
7. The method according to claim 1, wherein the temperature of the hydrothermal treatment in step 5) is 60 to 120 ℃ and the time is 0.5 to 10 hours.
8. The method according to claim 1, wherein in step 6) PEDOT/PANI fibers obtained in step 4) and MXene/rGO fibers obtained in step 5) are assembled on a PET sheet and coated with a gel electrolyte.
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Publication number Priority date Publication date Assignee Title
CN107680824A (en) * 2017-11-17 2018-02-09 浙江大学 A kind of MXene based composite fibres ultracapacitor
CN110085437A (en) * 2019-04-21 2019-08-02 北京工业大学 A kind of Polyglycolic acid fibre/polyaniline composite material and the preparation method and application thereof
CN110970228A (en) * 2018-09-30 2020-04-07 天津大学 Asymmetric super capacitor
WO2020086548A1 (en) * 2018-10-22 2020-04-30 Drexel University Electrochromic devices using transparent mxenes
CN113185193A (en) * 2021-04-07 2021-07-30 东南大学 MXene composite fiber reinforced graphene aerogel wave-absorbing material and preparation method thereof
CN113658806A (en) * 2021-06-29 2021-11-16 广西大学 Gel electrode doped with polyaniline in situ and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107680824A (en) * 2017-11-17 2018-02-09 浙江大学 A kind of MXene based composite fibres ultracapacitor
CN110970228A (en) * 2018-09-30 2020-04-07 天津大学 Asymmetric super capacitor
WO2020086548A1 (en) * 2018-10-22 2020-04-30 Drexel University Electrochromic devices using transparent mxenes
CN110085437A (en) * 2019-04-21 2019-08-02 北京工业大学 A kind of Polyglycolic acid fibre/polyaniline composite material and the preparation method and application thereof
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