CN114628166B - Preparation method of asymmetric fibrous flexible supercapacitor - Google Patents
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- 239000000243 solution Substances 0.000 claims description 41
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- 229910052723 transition metal Inorganic materials 0.000 description 2
- MAGFQRLKWCCTQJ-UHFFFAOYSA-M 4-ethenylbenzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-M 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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Classifications
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
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 positive electrode and MXene/rGO as the negative electrode. The addition of the PANI with high electric activity improves the overall capacitance of the fiber, and the stable PEDOT hydrogel framework provides rich ion diffusion channels and a rapid electron transfer path; MXene exhibits excellent properties in electrochemical energy storage and many other applications due to its excellent electrochemical properties and metallic conductivity, and an appropriate amount of rGO acts as a binder to retain the MXene material in fibrous form. The asymmetric fibrous supercapacitor obtained after the positive and negative electrodes are assembled has small volume, wide 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
Technical Field
the invention belongs to the technical field of asymmetric fiber supercapacitors, and particularly relates to a preparation method of an asymmetric fiber flexible supercapacitor, which is a preparation method of an asymmetric fiber flexible supercapacitor with a wide voltage window.
Background
Supercapacitors have attracted considerable attention in numerous power fields due to their unique properties and great potential for development. Supercapacitors are generally classified into electric double layer supercapacitors and pseudocapacitance supercapacitors according to energy storage mechanisms. The electric double layer supercapacitor is generally composed of a porous carbon material, and a large amount of charges can be physically accumulated at a rich interface of an electrode/electrolyte, which enables the electric double layer supercapacitor to be rapidly charged and discharged while having excellent cycle stability. However, the specific capacitance of the electric double layer supercapacitor is relatively low. In pseudocapacitance capacitors, the active species undergo a rapid reversible redox reaction at or near the electrode surface through the electrode material and electrolyte ions, thereby producing capacitance, which is higher than the electric double layer capacitance due to the reaction occurring at the surface and bulk of the electrode material, but its cycling stability is generally less than that of electric double layer capacitors. Therefore, the asymmetric supercapacitor has been widely studied in recent years due to the combination of the advantages of the double-layer supercapacitor and the pseudocapacitance supercapacitor. Typical Asymmetric Supercapacitors (ASCs) have good electrochemical properties such as a wide operating voltage window, suitable capacitance, higher energy density and power density.
In recent years, due to rapid development of wearable portable electronic devices in medical, military, outdoor, etc., miniaturization, flexibility, and high energy density of energy storage devices are demanded. In order to achieve the purpose, fibrous Supercapacitors (FSCs) are increasingly favored due to their small size, high flexibility, fast charge and discharge, stable mechanical properties, etc., but 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 between 1 and 4, TxRepresenting a surface functional group. MXene has unique metal conductivity and adjustable surface functional groups, so that the MXene has great prospect in the field of electrochemistry.
Commercial conductive polymer dispersions poly 3, 4-ethylenedioxythiophene: poly-4-styrenesulfonate (PEDOT: PSS) has been attracting attention because of its solution processability, high pseudocapacitance, and good ionic conductivity and electronic conductivity. The ion conductivity of the conductive polymer can promote the ion diffusion of electrolyte, and the conductivity of PEDOT: PSS after acid treatment can reach 4000S cm-1Can promote the rapid transfer of electrons in the electrode. Therefore, recently reported PEDOT: PSS after composite treatment is a promising candidate material for fiber electrodes, however pure PEDOT fibers still cannot meet the requirements of high performance fiber supercapacitors due to their limited capacitance. Therefore, a hybrid fiber electrode obtained by mixing PEDOT as a matrix and other high-electroactive pseudocapacitance materials is strongly demanded.
Disclosure of Invention
Aiming at the problems that the electrode of the existing asymmetric fiber supercapacitor is high in cost, complex in preparation process, low in voltage window and incapable of meeting electrochemical performance, the invention aims to provide a preparation method of the asymmetric fiber supercapacitor, which is to prepare the anode of the asymmetric fiber supercapacitor by taking poly-3, 4-ethylenedioxythiophene (PEDOT) hydrogel as a framework and Aniline (ANI) as an adsorbent; and (3) taking MXene as a framework and redox graphene (rGO) as an adhesive to prepare the negative electrode of the asymmetric fiber supercapacitor. The addition of high-electrical activity polyaniline improves the anode capacitance of the fiber, and the stable PEDOT hydrogel framework provides rich ion diffusion channels and rapid electron transfer paths, so that the utilization efficiency of the polyaniline is improved. The surface oxidation reaction between the intercalation protons and rich oxygen-containing functional groups enables the MXene to have ultrahigh volume capacitance, rGO is used as a binder to enable the MXene material to keep a fiber form, the obtained MXene/rGO fiber keeps a compact lamellar structure, has rich specific surface area, is convenient for contact with electrolyte in a test, is beneficial to rapid reaction, the electrochemical performance of the asymmetric fiber supercapacitor is improved, and the 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 supercapacitor (FASCs), so that the obtained asymmetric fiber supercapacitor has a wider working voltage window and excellent energy density and power density.
The invention adopts poly 3, 4-ethylenedioxythiophene/polyaniline (PEDOT/PANI) as the positive electrode and MXene/rGO as the negative electrode, and the obtained asymmetric fibrous supercapacitor has wider working voltage window, excellent energy density and power density and better flexibility. The method comprises the following specific steps: (1) Firstly, obtaining PEDOT fibers by hydrothermally treating poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonate (PEDOT: PSS); (2) Then adsorbing Aniline (ANI) on the PEDOT fiber and polymerizing to obtain the PEDOT/PANI composite fiber; (3) Mixing MXene and redox graphene (rGO) and then obtaining MXene/rGO mixed fiber through hydrothermal treatment; (4) And (3) assembling the PEDOT/PANI composite fiber obtained in the step (2) and the MXene/rGO mixed fiber obtained in the step (3) on a polyethylene terephthalate (PET) plate, and coating gel electrolyte to obtain the asymmetric fibrous capacitor. The addition of high-electro-activity Polyaniline (PANI) improves the overall capacitance of the fiber, and the stable PEDOT hydrogel framework provides rich ion diffusion channels and rapid electron transfer paths, thereby improving the utilization efficiency of PANI. The rGO is used as a binder to keep the MXene material in a fiber form, and the MXene/rGO fiber obtained by the method keeps a compact layered structure, has a rich specific surface area, is convenient to contact with electrolyte in a test, and is beneficial to rapid oxidation-reduction reaction, so that the electrochemical performance of the asymmetric fiber supercapacitor is improved. The PEDOT/PANI is used as the positive electrode fiber electrode, the MXene/rGO is used as the negative electrode fiber electrode, the assembled asymmetric fibrous supercapacitor has high capacitance retention rate after 1000 times of bending, and the capacitance is hardly attenuated at various bending angles, so that the asymmetric fibrous supercapacitor has better flexibility.
The aim of the invention is achieved by the following technical scheme.
the preparation method of the asymmetric fibrous flexible supercapacitor comprises the following steps:
1) Preparing an aniline mixed solution: uniformly mixing hydrochloric acid solution and aniline;
2) Preparing ammonium persulfate mixed solution: uniformly mixing hydrochloric acid solution and ammonium persulfate;
3) Preparation of PEDOT fiber: and mixing PEDOT, PSS and sulfuric acid to form a mixture, carrying out hydrothermal treatment on the mixture to obtain first fibers, then carrying out acid treatment on the first fibers, and washing the fibers subjected to acid treatment with deionized water to obtain the PEDOT fibers.
4) Preparation of PEDOT/PANI fibers: and 3) putting the PEDOT fiber prepared in the step 3) into the aniline mixed solution prepared in the step 1), 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 fibers: and 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 positive electrode of a capacitor by using the PEDOT/PANI fiber obtained in the step 4), preparing a negative electrode of the capacitor by using the MXene/rGO fiber obtained in the step 5), and preparing the capacitor by using the positive electrode and the negative electrode.
According to the method, PEDOT hydrogel is taken as a skeleton, firstly, PEDOT PSS suspension is subjected to hydro-thermal treatment, and then washed with deionized water after acid treatment is carried out overnight, and the shaping of the PEDOT skeleton is facilitated by optimally regulating and controlling the sulfuric acid concentration, the dosage ratio of sulfuric acid to the PEDOT PSS suspension, the hydro-thermal temperature and the hydro-thermal time. And by adjusting the concentration of the MXene and the dosage ratio of the MXene to the GO, the MXene/rGO fiber has the best electrochemical performance on the basis of molding.
Preferably, in the step 1), the hydrochloric acid concentration in the hydrochloric acid solution is 1M, the volume ratio of hydrochloric acid to aniline is 10:0.3, and the adsorption time is 12 hours.
Preferably, the ammonium persulfate mixed solution in the step 2) is a mixed solution of 1M hydrochloric acid and ammonium persulfate, and the mass ratio is 10:0.18;
Further, the hydrothermal treatment described in step 3) is performed in a reaction vessel.
Preferably, the polymerization described in step 4) is carried out at a temperature of from-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 4h.
Preferably, the concentration of MXene in step 5) is 12mg/mL.
Preferably, in step 5), the mass ratio of MXene, GO and Vc is 4:1:5.
Preferably, the concentration of MXene in step 5) is 12mg/mL.
Preferably, in step 5), the mass ratio of MXene, GO and Vc is 9:1:5.
optimally, the concentration of MXene in step 5) is 28mg/mL.
Preferably, in step 5), the mass ratio of MXene, GO and Vc is 21:1:5.
The PEDT/PANI and MXene/rGO prepared by the method have relatively high specific capacitance as electrodes, and are 698F cm respectively-3And 1057F cm-3。
Therefore, the invention also claims the PEDOT/PANI and the MXene/rGO prepared by the method.
The PEDOT hydrogel skeleton prepared by the method provides rich ion transmission channels and electron transfer capability, and maximizes the capacitance utilization rate of Polyaniline (PANI). The MXene provides rich specific surface area, is convenient for the subsequent electrode to contact with electrolyte in the test, and provides a good channel for ion transmission, thereby improving the electrochemical performance of the asymmetric fiber supercapacitor.
the asymmetric fiber super capacitor prepared based on the PEDOT/PANI and the MXene/rGO materials as electrodes has higher specific capacitance, and has a wider working voltage window of 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-3At an energy density of 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 are about 1-2 nm and about 2-4 mu m respectively.
As a preferred embodiment, the asymmetric fibrous supercapacitor is prepared by:
And (3) parallelly assembling the anode fiber PEDOT/PANI and the cathode fiber MXene/rGO on a PET plate, and wrapping a layer of polyvinyl alcohol (PVA) gel electrolyte, thereby finally obtaining the asymmetric fibrous supercapacitor.
compared with the prior art, the invention has the following beneficial effects:
According to the method provided by the invention, PEDOT is subjected to hydrothermal treatment of PSS suspension to obtain a PEDOT hydrogel skeleton, aniline is adsorbed in an ice bath and polymerized to obtain PEDOT/PANI positive electrode fibers, the PEDOT has excellent conductive performance, and the PANI has excellent capacitance performance, so that the PEDOT/PANI has high specific capacitance and excellent electrochemical performance through synergistic effect; the invention also prepares the optimal dosage ratio of MXene and rGO, so that the electrochemical performance is optimal while the fiber is formed, the suspended and dried MXene/rGO fiber volume is contracted, 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); e-h are SEM images of MXene/rGO;
FIG. 2, panel a, is an EDS diagram of PEDOT/PANI; b is an EDS diagram of MXene/rGO;
FIG. 3a is a cyclic voltammogram of PEDOT/PANI fiber of example 2 at different sweep rates; b is the volume capacitance change graph of the PEDOT/PANI fibers of examples 1-3 at different current densities; c is a constant current charge-discharge curve of the PEDOT/PANI fibers of examples 1-3 under different current densities; d is the peak current versus sweep rate curve for the PEDOT/PANI fiber of example 2; e is the EIS diagram of the PEDOT/PANI fibers of examples 1-3; f is the change curve of the volume capacitance of PEDT/PANI under different cycle numbers;
FIG. 4a is a cyclic voltammogram of an MXene/rGO fiber electrode of example 6 at different sweep rates; b is the volume capacitance change plot of the MXene/rGO fibers of examples 4-6 at different current densities; c is a constant current charge-discharge curve graph of the MXene/rGO fiber electrode of example 6 at different current densities; d is a change curve of peak current and sweep speed; e is the EIS diagram of the MXene/rGO fiber electrodes of examples 4-6; f is a plot of the change in volume capacitance of the MXene/rGO fiber electrode of example 6 at different cycles;
FIG. 5a is an asymmetric fiber capacitor at 5mV s-1is a CV curve of (c); b is a CV diagram of the asymmetric fiber capacitor at different sweeping speeds; c is constant-current charge-discharge electricity of the asymmetric fiber capacitor under different current densities; d is a volume capacitance change chart 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 an asymmetric fiber supercapacitor flexed different times;
FIG. 8 is a CV plot of an asymmetric fiber supercapacitor at different bend angles, wherein the scan speed is 5mV s-1。
Detailed Description
the invention is further illustrated below in connection with specific examples, except as otherwise indicated, the reagents and materials used in the following examples are commercially available.
Example 1
1) Preparing an aniline mixed solution: uniformly mixing 10mL of 1M hydrochloric acid solution with 0.3mL of aniline;
2) Preparing ammonium persulfate mixed solution: uniformly mixing 10mL of 1M hydrochloric acid solution with 0.18g of ammonium persulfate;
3) Preparation of PEDOT fiber: 1mL of PEDOT/PSS suspension (Clevelos (TM) PH1000 from He Lishi, germany, in which PEDOT was dispersed in water-soluble polystyrene sulfonic acid (PSS) to form a suspension, the content of PEDOT was 13% by weight) was mixed with 200. Mu.L of sulfuric acid having a concentration of 5M, and then sonicated for 5 minutes, poured into a glass capillary tube, and subjected to a hydrothermal treatment at 90℃for 2 hours. After hydrothermal treatment, the fibers are formed. The glass capillary is taken out, and the fiber is pushed out from one end of the glass capillary. Then, the fiber is changed into 18M concentrated sulfuric acid solution to stand for 12 hours, and the fiber after acid treatment is washed by deionized water;
4) Preparation of PEDOT/PANI fibers: and 3) placing the fiber prepared in the step 3) into the aniline mixed solution, standing for 12 hours in an ice bath at the temperature of 0 ℃, pouring the ammonium persulfate mixed solution into the aniline mixed solution, polymerizing for 2 hours in the ice bath at the temperature of 0 ℃, taking out, and hanging and airing. The diameter of the finally produced fiber is about 28-32 μm.
Example 2
1) Preparing an aniline mixed solution: uniformly mixing 10mL of 2M hydrochloric acid solution with 0.5mL of aniline;
2) Preparing ammonium persulfate mixed solution: uniformly mixing 10mL of 2M hydrochloric acid solution with 0.36g of ammonium persulfate;
3) Preparation of PEDOT fiber: 1mL of PEDOT/PSS suspension (Clevelos (TM) PH1000 from He Lishi, germany, in which PEDOT was dispersed in water-soluble polystyrene sulfonic acid (PSS) to form a suspension, the content of PEDOT was 13% by weight) was mixed with 200. Mu.L of sulfuric acid having a concentration of 5M, and then sonicated for 5 minutes, poured into a glass capillary tube, and subjected to hydrothermal treatment at 90℃for 5 hours. After hydrothermal treatment, the fibers are formed. The glass capillary is taken out, and the fiber is pushed out from one end of the glass capillary. Then, the fiber is changed into 16M sulfuric acid solution to stand for 12 hours, and the fiber after acid treatment is washed by deionized water;
4) Preparation of PEDOT/PANI fibers: and 3) placing the fiber prepared in the step 3) into the aniline mixed solution, standing for 12 hours in a water bath at the normal temperature of 30 ℃, pouring the ammonium persulfate mixed solution into the aniline mixed solution, polymerizing for 4 hours in the water bath at the normal temperature, taking out, hanging and airing. The diameter of the finally produced fiber is about 30-35 μm.
Example 3
1) Preparing an aniline mixed solution: uniformly mixing 10mL of 2M hydrochloric acid solution with 0.5mL of aniline;
2) Preparing ammonium persulfate mixed solution: uniformly mixing 10mL of 2M hydrochloric acid solution with 0.36g of ammonium persulfate;
3) Preparation of PEDOT fiber: 1mL of PEDOT/PSS suspension (Clevelos (TM) PH1000 from He Lishi, germany, in which PEDOT was dispersed in water-soluble polystyrene sulfonic acid (PSS) to form a suspension, the content of PEDOT was 13% by weight) was mixed with 200. Mu.L of sulfuric acid having a concentration of 5M, and then sonicated for 5 minutes, poured into a glass capillary tube, and subjected to hydrothermal treatment at 90℃for 5 hours. After hydrothermal treatment, the fibers are formed. The glass capillary is taken out, and the fiber is pushed out from one end of the glass capillary. Then, the fiber is changed into a sulfuric acid solution of 12M for standing for 12 hours, and the fiber after acid treatment is washed by deionized water;
4) Preparation of PEDOT/PANI fibers: and 3) putting the fiber prepared in the step 3) into the aniline mixed solution, carrying out hydrothermal treatment 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 hanging and airing. The diameter of the finally produced fiber is about 32-38 μm.
Example 4
Preparation of MXene/rGO fibers: will be 0.8mL Ti3C2TxMXene (12 mg/mL) (using etching Ti3AlC2MAX phase to obtain Ti3C2TxMXene. Specifically, 1g of Ti3AlC2The MAX phase was mixed with 1.6g LiF, 20ml 9M HCl, and after stirring at 40℃for 12h, the solution was removed, diluted and centrifuged until the solution was neutral. And then centrifuging at 10000rpm for 30 minutes, taking out the precipitate, carrying out ultrasonic treatment on the solution after taking out the precipitate for 30 minutes, centrifuging at 10000rpm for 20 minutes, stripping the solution after ultrasonic treatment to obtain a low-concentration MXene solution, and concentrating the low-concentration MXene solution to obtain the required MXene solution. Wherein Ti is3C2TxMXene is dispersed in the aqueous solution, and the average thickness and the transverse dimension of the single slice are about 1-2 nm and 2-4 mu m respectively. Ti as referred to above3AlC2MAX is available from Kaien ceramic materials, inc., lycra, CAS 196506-01-1, MW 194.6; liF is purchased from Michelin Corp, CAS 7789-24-4, L812324) and 0.2mL GO (dispersed in aqueous solution) (12 mg/mL) and 12mg Vc are mixed and then sonicated, and then injected into a reaction kettle for hydrothermal treatment at 90 ℃ for 0.5h. The diameter of the finally produced fiber is about 32-38 μm.
Example 5
Preparation of MXene/rGO fibers: will be 0.9mL Ti3C2TxMXene (12 mg/mL) (using etching Ti3AlC2MAX phase to obtain Ti3C2TxMXene. Specifically, 1g of Ti3AlC2The MAX phase was mixed with 1.6g LiF, 20ml 9M HCl, and after stirring at 40℃for 12h, the solution was removed, diluted and centrifuged until the solution was neutral. And then centrifuging at 10000rpm for 30 minutes, taking out the precipitate, carrying out ultrasonic treatment on the solution after taking out the precipitate for 30 minutes, centrifuging at 10000rpm for 20 minutes, stripping the solution after ultrasonic treatment to obtain a low-concentration MXene solution, and concentrating the low-concentration MXene solution to obtain the required MXene solution. Wherein Ti is3C2TxMXene is dispersed in the aqueous solution, and the average thickness and the transverse dimension of the single slice are about 1-2 nm and 2-4 mu m respectively. Ti as referred to above3AlC2MAX is available from Kaien ceramic materials, inc., lycra, CAS 196506-01-1, MW 194.6; liF is purchased from Michelin Corp, CAS 7789-24-4, L812324) and 0.1mL GO (12 mg/mL) (dispersed in aqueous solution) and 6mg Vc (ascorbic acid) are mixed and then sonicated, and then injected into a reaction kettle for hydrothermal treatment at 90 ℃ for 0.5h. The diameter of the finally produced fiber is about 30-35 μm.
Example 6
Preparation of MXene/rGO fibers: will be 0.9mL Ti3C2TxMXene (28 mg/mL) (using etching Ti3AlC2MAX phase to obtain Ti3C2TxMXene. Specifically, 1g of Ti3AlC2The MAX phase was mixed with 1.6g LiF, 20ml 9M HCl, and after stirring at 40℃for 12h, the solution was removed, diluted and centrifuged until the solution was neutral. And then centrifuging at 10000rpm for 30 minutes, taking out the precipitate, carrying out ultrasonic treatment on the solution after taking out the precipitate for 30 minutes, centrifuging at 10000rpm for 20 minutes, stripping the solution after ultrasonic treatment to obtain a low-concentration MXene solution, and concentrating the low-concentration MXene solution to obtain the required MXene solution. Wherein Ti is3C2TxMXene is dispersed in the aqueous solution, and the average thickness and the transverse dimension of the single slice are about 1-2 nm and 2-4 mu m respectively. Ti as referred to above3AlC2MAX is available from Kaien ceramic materials, inc., lycra, CAS 196506-01-1, MW 194.6; liF is purchased from Michelin Corp, CAS 7789-24-4, L812324) and 0.1mL GO (12 mg/mL) (dispersed in aqueous solution) and 6mg Vc (ascorbic acid) are mixed and then sonicated, and then injected into a reaction kettle for hydrothermal treatment at 90 ℃ for 0.5h. The diameter of the finally produced fiber is about 28-32 μm.
example 7 characterization of Single electrode
1. test method
Carrying out SEM morphology characterization and EDS characterization on the samples prepared in examples 1 to 6 by using a SUPRA 55 type field emission scanning electron microscope; electrochemical performance tests were performed on the Shanghai Chen Hua 760E electrochemical workstation, wherein the platinum sheet electrode/graphite sheet electrode was the counter electrode and the saturated calomel electrode was the reference electrode. Examples 1 to 3 sample PEDOT/PANI and 4 to 6 sample MXene/rGO 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, from which it can be seen that the fibers exhibit a three-dimensional interconnected porous structure, facilitating ion transport and electron transfer; FIGS. 1 e-g are SEM images of MXene/rGO prepared in examples 4-6, h being an enlarged SEM image of example 6, from which it can be seen that the fibers exhibit a dense layered structure;
(2) FIG. 2a is an EDS diagram of PEDOT/PANI prepared in example 2, in which C, O, S, N elements are uniformly distributed inside the fiber; FIG. 2b is an EDS diagram of MXene/rGO prepared in example 6, from which it can be seen that the Ti, C, F, O element is 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 that pseudocapacitive reactions have occurred; b is a volume capacitance change graph of the PEDOT/PANI fibers prepared in examples 1-3 under different current densities, and it can be seen that the capacitance of the composite PEDOT/PANI fiber is obviously improved compared with that of the pure PEDOT fiber, wherein the fiber prepared in example 2 shows the highest volume capacitance; c is a constant current charge-discharge curve of the PEDOT/PANI fiber prepared in the embodiment 2 under different current densities, and no obvious platform is seen, so that good pseudocapacitance performance is shown; d is the change curve of peak current and sweep rate of the PEDOT/PANI fiber prepared in example 2, the slope b reflects the energy storage mechanism of the electrode (b=0.5, the reaction is a diffusion-controlled energy storage process; b=1, the reaction is a capacitance-controlled energy storage process), and it can be seen that the slope of the PEDOT/PANI fiber is between 0.5 and 1, which is the result of the cooperative control of capacitance and diffusion; e is an EIS graph of the PEDOT/PANI fibers prepared in examples 1-3, and it can be seen that the PEDOT/PANI prepared in example 2 has the smallest resistance and the largest ion diffusion coefficient; f is the change curve of the volume capacitance of PEDT/PANI under different cycle numbers;
(4) FIG. 4a is a cyclic voltammogram of an MXene/rGO fiber electrode prepared in example 6 at different sweep rates, as well as a pair of distinct redox peaks, showing good pseudocapacitive performance; b is a volume ratio capacitance change chart of the MXene/rGO fibers prepared in the examples 4-6 under different current densities, and it can be seen that the MXene/rGO fibers prepared in the example 6 have the highest volume capacitance and the best electrochemical performance; c is a constant current charge-discharge curve graph of the MXene/rGO fiber electrode prepared in the embodiment 6 under different current densities, no obvious platform is seen, and the MXene/rGO fiber electrode has good pseudo-capacitance performance; d is a change curve of peak current and sweep speed, the slope b reflects an energy storage mechanism of an electrode (b=0.5, the reaction is an energy storage process of diffusion control; b=1, the reaction is an energy storage process of capacitance control), the slope of the MXene/rGO fiber electrode at the anode is 0.74 and is between 0.5 and 1, the slope of the MXene/rGO fiber electrode at the cathode is 0.95, the slope of the MXene/rGO fiber electrode is very close to 1, and the slope of the MXene/rGO fiber electrode at the cathode is the result of capacitance control; e is an EIS diagram of the MXene/rGO fiber electrodes prepared in examples 4-6, and it can be seen that the MXene/rGO prepared in example 6 has the minimum resistance and the maximum ion diffusion coefficient; f is a graph of the change of volume capacitance of the MXene/rGO fiber electrode prepared in example 6 under different cycle numbers, and after 10000 cycles, the capacitance retention rate is 115%, and the MXene/rGO fiber electrode has good cycle stability.
example 8 asymmetric fiber supercapacitor
1. Preparation method
Asymmetric fiber supercapacitors (FASCs) were prepared using the PEDOT/PANI prepared in example 2 and the MXene/rGO fibers prepared in example 6, in particular by the following method:
The PEDOT/PANI fiber prepared in example 2 was used as the positive electrode of the capacitor, and the MXene/rGO fiber prepared in example 6 was used as the negative electrode of the capacitor. The fiber anode (PEDOT/PANI) and the fiber cathode (MXene/rGO) are placed on a polyethylene terephthalate (PET) plate in parallel, the distance between the anode and the cathode is 100-200 mu m, then a layer of gel electrolyte is coated, the thickness is about 1-2 mm, the middle section of the anode and the cathode fiber is covered, the distance between 1-2 cm is left to be in contact with the outside, and the middle distance between 1-2 cm is packaged by using an adhesive tape, so that the moisture in the gel electrolyte between the adhesive tape and the PET plate can not evaporate. Wherein the gel electrolyte is 10wt% of polyvinyl alcohol (PVA), 10wt% of H2SO480wt% of deionized water.
2. Analysis of electrochemical performance test results of supercapacitor
(1) FIG. 5a is an asymmetric fiber capacitor at 5mV s-1Is a CV curve of (c); b is a CV diagram of the asymmetric fiber capacitor under different sweeping speeds, and a good charging and discharging process is shown; c is constant-current charge-discharge diagram of asymmetric fiber capacitor under different current densities, from which it can be seen that the current density is from 1A cm-3To 50A cm-3All show 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, the volume capacitance change graph is 1A cm in length-3the specific capacitance of the capacitor under the current density of (C) reaches 138.6F cm-3；
(2) FIG. 6 is a graph of energy density versus power density for an asymmetric fibrous supercapacitor according to the present invention, from which it can be seen that the asymmetric fibrous supercapacitor of the present invention has an energy density and power density superior to other asymmetric supercapacitors at a power density of 724.9mW cm-3When 40.47mWh cm of the product was obtained-3Is a high energy density of (a).
(3) FIG. 7 is a graph of the volumetric capacitance of an asymmetric fiber supercapacitor bent different times, showing that the capacitance remains at 100.5% after 1000 bends, demonstrating that the asymmetric fiber capacitor of the present invention has good flexibility;
(4) FIG. 8 is a CV diagram of an asymmetric fiber supercapacitor at different bending angles (scan speed of 5mV s-1) It can be seen that the capacitance is basically not attenuated under different bending angles, which indicates that the fibrous supercapacitor of the invention has good flexibility.
The present invention is not described in detail in part as being well known to those skilled in the art. The above examples are merely illustrative of preferred embodiments of the invention, which are not exhaustive of all details, nor are they intended to limit the invention to the particular embodiments disclosed. Various modifications and improvements of the technical scheme of the present invention will fall within the protection scope of the present invention as defined in the claims without departing from the design spirit of the present invention.
Claims (2)
1. the preparation method of the asymmetric fibrous flexible supercapacitor is characterized by comprising the following steps of:
1) Preparing an aniline mixed solution: uniformly mixing hydrochloric acid solution and aniline;
2) Preparing ammonium persulfate mixed solution: uniformly mixing hydrochloric acid solution and ammonium persulfate;
3) Preparation of PEDOT fiber: mixing PEDOT, PSS and sulfuric acid to form a mixture, injecting the mixture into a glass capillary, performing hydrothermal treatment to obtain first fibers, performing acid treatment on the first fibers, and washing the fibers subjected to acid treatment with deionized water to obtain PEDOT fibers;
4) Preparation of PEDOT/PANI fibers: 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, hanging and airing to obtain the PEDOT/PANI fiber; the diameter of the PEDOT/PANI fiber is 28-38 microns;
5) Preparation of MXene/rGO fibers: mixing MXene, graphene oxide and ascorbic acid to form a mixture, and then placing the mixture in a reaction kettle for hydro-thermal treatment to obtain MXene/rGO fibers, wherein the diameters of the MXene/rGO fibers are 28-38 microns; the chemical formula of the MXene is Ti3C2Txthe two-dimensional layered structure has the average thickness and the transverse dimension of a single slice of 1-2 nm and 2-4 mu m respectively;
6) Preparing a positive electrode of a capacitor by using the PEDOT/PANI fiber obtained in the step 4), preparing a negative electrode of the capacitor by using the MXene/rGO fiber obtained in the step 5), and preparing the capacitor by using the positive electrode and the negative electrode; the prepared asymmetric fibrous flexible supercapacitor has a wider working voltage window, and the working voltage window is 0-1.45V;
in the step 1), the concentration of hydrochloric acid in the hydrochloric acid solution is 1-8M, the volume ratio of hydrochloric acid to aniline is 10:0.3-10:1, and the adsorption time is 12-36 h;
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;
In the step 3), the sulfuric acid concentration is 0.5~5 M,PEDOT:PSS, and the volume ratio of the suspension to the sulfuric acid is 10:1-5:1;
the polymerization in the step 4) is carried out at the temperature of-10 to 60 ℃ and the polymerization time is 2 to 8 hours;
The concentration of MXene in the step 5) is 7-30 mg/mL; the mass ratio of the MXene to the graphene oxide to the ascorbic acid is 2-30:0.5-2:2-15;
And 5) carrying out hydrothermal treatment at the temperature of 60-120 ℃ for 0.5-10 h.
2. The method according to claim 1, wherein in step 6), the PEDOT/PANI fibers obtained in step 4) and the MXene/rGO fibers obtained in step 5) are assembled on a PET plate coated with a gel electrolyte.
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| CN107680824A (en) * | 2017-11-17 | 2018-02-09 | 浙江大学 | A kind of MXene based composite fibres ultracapacitor |
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| 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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| 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 |
| 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 |
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