CN115312332B - MXene-based fiber capacitor electrode and preparation method thereof - Google Patents

MXene-based fiber capacitor electrode and preparation method thereof Download PDF

Info

Publication number
CN115312332B
CN115312332B CN202210919872.2A CN202210919872A CN115312332B CN 115312332 B CN115312332 B CN 115312332B CN 202210919872 A CN202210919872 A CN 202210919872A CN 115312332 B CN115312332 B CN 115312332B
Authority
CN
China
Prior art keywords
mxene
silk fibroin
solution
fiber
suspension
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210919872.2A
Other languages
Chinese (zh)
Other versions
CN115312332A (en
Inventor
王琳
万军民
武慧
王秉
彭志勤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Sci Tech University ZSTU
Original Assignee
Zhejiang Sci Tech University ZSTU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Sci Tech University ZSTU filed Critical Zhejiang Sci Tech University ZSTU
Priority to CN202210919872.2A priority Critical patent/CN115312332B/en
Publication of CN115312332A publication Critical patent/CN115312332A/en
Application granted granted Critical
Publication of CN115312332B publication Critical patent/CN115312332B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—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 OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention relates to the field of intelligent textiles and discloses an MXene-based fiber capacitor electrode and a preparation method thereof. The preparation method comprises the following steps: adding silk fibroin into a solvent I, stirring to obtain flocculent solid suspension, adding polyurethane, uniformly mixing, adding silver nanowires, and stirring to obtain uniform viscous liquid to obtain spinning solution; carrying out wet spinning by adopting a spinning solution, and drying to obtain a silk fibroin/polyurethane/silver nanowire composite fiber; adding silk fibroin/polyurethane/silver nanowire composite fibers into MXene-based electrode material suspension, taking out after fully soaking, drying, and repeating the above process for a plurality of times to obtain the fiber capacitor electrode. The silk fibroin/polyurethane blend material is adopted as a fiber substrate, the conductive doping agent silver nanowire is added, and the MXene-based electrode material is attached to the fiber, so that the fiber capacitor electrode has good wearable performance, conductivity and electrochemical energy storage performance.

Description

MXene-based fiber capacitor electrode and preparation method thereof
Technical Field
The invention relates to the field of intelligent textiles, in particular to an MXene-based fiber capacitor electrode and a preparation method thereof.
Background
In order to solve the problems of environmental pollution, carbon emission and the like, people have widely studied on the utilization of renewable energy sources such as solar energy, hydroenergy, wind energy and the like. However, because of the intermittent nature of these energy sources, the demand for energy storage devices has greatly increased. Fibrous Supercapacitors (FSCs) are a promising energy storage solution for powering miniaturized or wearable electronic devices. Fiber electrodes with high conductivity and excellent energy storage properties used in FSCs are a big research focus.
Two-dimensional (2D) materials are the most promising advanced capacitorsOne of the electrode materials. Due to their high specific surface area, two-dimensional materials provide more electrochemically active sites to store charge through either an Electric Double Layer Capacitance (EDLC) or a rapid surface redox reaction (pseudocapacitance). Mxenes (M) n+1 X n T x N=1, 2 or 3, m represents a transition metal, X represents carbon and/or nitrogen, T x Representing different surface functional groups) is an emerging two-dimensional transition metal carbide and nitride that has proven to be a very promising candidate electrode material for supercapacitors, promising for use in flexible wearable supercapacitors. However, how to combine the wearable performance with the conductivity and the energy storage performance is still an important challenge faced by the flexible wearable supercapacitor at present.
Disclosure of Invention
In order to solve the technical problems, the invention provides an MXene-based fiber capacitor electrode and a preparation method thereof. The silk fibroin/polyurethane blend material is adopted as a fiber substrate, the conductive doping agent silver nanowire is added, and the MXene-based electrode material is attached to the fiber, so that the MXene-based fiber capacitor electrode has good wearability, conductivity and electrochemical energy storage performance.
The specific technical scheme of the invention is as follows:
a preparation method of an MXene-based fiber capacitor electrode comprises the following steps:
(1) Adding silk fibroin into the solvent I, and stirring to form flocculent solid suspension; adding polyurethane into flocculent solid suspension, uniformly mixing, adding silver nanowires, and stirring to uniform viscous liquid to obtain spinning solution;
(2) Carrying out wet spinning by adopting a spinning solution, and drying the obtained fiber to obtain a silk fibroin/polyurethane/silver nanowire composite fiber;
(3) And adding the silk fibroin/polyurethane/silver nanowire composite fiber into the MXene-based electrode material suspension, taking out after full soaking, drying, and repeating the processes of adding into the MXene-based electrode material suspension, taking out after full soaking and drying for a plurality of times to obtain the MXene-based fiber capacitor electrode.
The invention takes silk fibroin/polyurethane blend material as a substrate, silver nanowires are added to prepare spinning solution, and wet spinning is adopted to prepare the composite fiber. And then soaking the obtained fiber with MXene-based electrode material suspension, and drying to obtain the fiber electrode.
The invention selects silk fibroin/polyurethane as a substrate of the fiber, and the silk fibroin/polyurethane can lead the fiber to have good biocompatibility, flexibility and mechanical property, so that the fiber has good application prospect in the application of wearable textiles. In addition, the MXene-based electrode material is attached to the surface of the fiber through soaking, so that the fiber electrode can be endowed with good electrochemical energy storage performance. On the basis, the silver nanowire is selected as the conductive doping agent, so that the mechanical deformation of the fiber does not influence the conductivity of the fiber, the transfer of charges between sheets of the MXene-based electrode material is facilitated, and the transport efficiency of electrolyte ions is improved.
Preferably, in step (1), the preparation method of silk fibroin comprises the following steps: adding silk cocoons into NaCO 3 Degumming in the solution, repeating the degumming process for 2-4 times, and drying to obtain silk fibroin; adding silk fibroin extract into silk fibroin, stirring at 55-65deg.C for 1-2 hr, dialyzing, and lyophilizing to obtain silk fibroin.
Preferably, the silk fibroin extracting solution is CaCl with the mol ratio of 1:1.5-2.5:7-9 2 、CH 3 CH 2 OH and H 2 And (3) mixing liquid of O.
Preferably, in the dialysis process, the molecular weight cut-off is 9000-14000kDa and the dialysis time is 72-84h.
Preferably, in the step (1), the preparation method of the silver nanowire comprises the following steps: preparing a mixed solution from polyvinylpyrrolidone, a solvent II and ferric chloride; heating the mixed solution to 145-155 ℃, dropwise adding a silver nitrate solution into the mixed solution, uniformly mixing, reacting for 5-8 hours at 155-165 ℃, separating out precipitate, and washing the precipitate to obtain the silver nanowire.
Preferably, in the step (3), the method for preparing the MXene-based electrode material suspension includes the steps of:
(1.1) stirring LiF and hydrochloric acid vigorously for 30-40min to obtain a mixed solution; then Ti is added in 10-20min 3 AlC 2 Slowly adding the precursor into the mixed solution, and continuing stirring for reaction; after the reaction is finished, carrying out centrifugation, acid washing and water washing to be neutral, carrying out ultrasonic treatment, and finally centrifuging and collecting supernatant to obtain MXene single-layer suspension;
(1.2) preparing N-phenyl-1, 4-phenylenediamine, ferric trichloride hexahydrate and hydrochloric acid into a reaction solution, reacting for 2-3 hours at 20-30 ℃, and separating and purifying the product to obtain the tetra-aniline;
(1.3) dissolving 5-azido valeric acid, dicyclohexylcarbodiimide, trimethylamine, 4-dimethylaminopyridine and tetraaniline in a solvent III, and separating a reaction product after stirring reaction to obtain modified tetraaniline containing azido groups;
(1.4) dissolving the modified tetraaniline containing the azide group in the solvent IV, dropwise adding the MXene single-layer suspension into the solvent IV, stirring the mixture, performing ultraviolet irradiation treatment, centrifuging the mixture, washing the mixture with ethanol, washing the mixture with water, and adding water to obtain the MXene-based electrode material suspension. In the step, under the irradiation of ultraviolet light, in the modified tetraaniline containing the azide group, the azide group is decomposed into nitrogen and nitrene, and the nitrene is very active and can be combined with H on MXene to form a stable covalent bond.
The invention firstly prepares MXene monolayer suspension, then grafts polyaniline conjugated repetitive unit tetra-aniline with minimum polyaniline onto MXene nano-sheets through photochemical action of organic azide, and realizes the compounding of the tetra-aniline and the MXene.
The tetraaniline has the advantages of pseudocapacitance, high conductivity and the like, and can increase the interlayer spacing of the MXene after being stably combined with the MXene as an intercalation agent, promote the transportation of electrolyte ions, effectively increase the specific surface area and electrochemical active sites of the MXene, and further improve the electrochemical energy storage performance of the MXene. Compared with common polyaniline, the polyaniline (aniline tetramer) has a shorter chain length, and can reduce the volume degradation easily occurring in the repeated charge and discharge process.
In addition, the invention utilizes the photochemical action of amino and 5-azido valeric acid in the tetraaniline and the organic azido compound to enable the MXene and the tetraaniline to be combined in a covalent bond mode, thereby reducing the risk of falling off the tetraaniline, being beneficial to ensuring the synergy between the two and increasing the cycle stability during energy storage.
Preferably, in the step (1), the mass-volume ratio of the silk fibroin, polyurethane, silver nanowires and the solvent I is 1 g:3-5 g:0.1-0.2 g:15-25 mL.
Preferably, in the step (2), the wet spinning speed of the spinning solution is 1-3mL/min.
Preferably, in step (2), the wet spinning specifically includes the steps of: and pouring the spinning solution into a syringe, sleeving a spinning head on the syringe, fixing the syringe on a digital injection pump, and starting wet spinning, wherein the coagulation bath is deionized water.
Preferably, in the step (3), the soaking time is 1-3 hours.
An MXene-based fiber capacitor electrode prepared by the preparation method.
Compared with the prior art, the invention has the following advantages:
(1) The silk fibroin/polyurethane blend material is adopted as a fiber substrate, the conductive doping agent silver nanowire is added, and the MXene-based electrode material is attached to the fiber, so that the MXene-based fiber capacitor electrode has good wearability, conductivity and electrochemical energy storage performance;
(2) In the MXene-based electrode material used in the invention, the composite of the tetraaniline and the MXene is adopted, so that the electrochemical energy storage performance of the MXene can be improved, and meanwhile, the shorter chain length of the tetraaniline can be utilized, so that the volume degradation easily occurring in the repeated charge and discharge process can be reduced;
(3) In the process of preparing the MXene-based electrode material, the organic azide compound is utilized to bond the tetraaniline to the MXene nanosheets, and the organic azide compound and the MXene nanosheets are combined in a covalent bond mode, so that the risk of falling off of the tetraaniline is reduced, the synergy is ensured, and the cycle stability in energy storage is increased.
Detailed Description
The invention is further described below with reference to examples.
The following examples will enable those skilled in the art to more fully understand the present invention and are not intended to limit the same in any way.
An MXene-based fiber capacitor electrode was prepared by the steps of:
(1) Preparation of MXene-based electrode material suspension:
(1.1) stirring LiF and hydrochloric acid vigorously for 30-40min to obtain a mixed solution; then Ti is added in 10-20min 3 AlC 2 Slowly adding the precursor into the mixed solution, and continuing stirring for reaction; after the reaction is finished, carrying out centrifugation, acid washing and water washing to be neutral, carrying out ultrasonic treatment, and finally centrifuging and collecting supernatant to obtain MXene single-layer suspension;
(1.2) preparing N-phenyl-1, 4-phenylenediamine, ferric trichloride hexahydrate and hydrochloric acid into a reaction solution, reacting for 2-3 hours at 20-30 ℃, and separating and purifying the product to obtain the tetra-aniline;
(1.3) dissolving 5-azido valeric acid, dicyclohexylcarbodiimide, trimethylamine, 4-dimethylaminopyridine and tetraaniline in a solvent III, and separating a reaction product after stirring reaction to obtain modified tetraaniline containing azido groups;
(1.4) dissolving the modified tetraaniline containing the azide group in the solvent IV, dropwise adding the MXene single-layer suspension into the solvent IV, stirring the mixture, performing ultraviolet irradiation treatment, centrifuging the mixture, washing the mixture with ethanol, washing the mixture with water, and adding water to obtain the MXene-based electrode material suspension.
(2) Preparation of silk fibroin: adding silk cocoons into NaCO 3 Degumming in the solution, repeating the degumming process for 2-4 times, and drying to obtain silk fibroin; caCl with the mol ratio of 1:1.5-2.5:7-9 2 、CH 3 CH 2 OH and H 2 O is mixed to prepare silk fibroin extract; adding silk fibroin extract into silk fibroin, stirring at 55-65deg.C for 1-2 hr, dialyzing, retaining molecular weight 9000-14000kDa, dialyzing for 72-84 hr, and lyophilizing to obtain silk fibroin.
(3) Preparation of silver nanowires: preparing a mixed solution from polyvinylpyrrolidone, a solvent II and ferric chloride; heating the mixed solution to 145-155 ℃, dropwise adding a silver nitrate solution into the mixed solution, uniformly mixing, reacting for 5-8 hours at 155-165 ℃, separating out precipitate, and washing the precipitate to obtain the silver nanowire.
(4) Preparation of spinning solution: adding silk fibroin into the solvent I, and stirring to form flocculent solid suspension; adding polyurethane into flocculent solid suspension, uniformly mixing, adding silver nanowires, wherein the mass volume ratio of silk fibroin to polyurethane to silver nanowires to solvent I is 1 g:3-5 g:0.1-0.2 g:15-25 mL, and stirring to obtain spinning solution.
(5) Preparation of silk fibroin/polyurethane/silver nanowire composite fiber: and (3) carrying out wet spinning by adopting a spinning solution, wherein the wet spinning speed of the spinning solution is 1-3mL/min, and drying the obtained fiber to obtain the silk fibroin/polyurethane/silver nanowire composite fiber.
(6) Compounding of MXene-based electrode materials: and adding the silk fibroin/polyurethane/silver nanowire composite fiber into the MXene-based electrode material suspension, soaking for 1-3h, taking out, drying, and repeating the processes of adding into the MXene-based electrode material suspension, soaking for 1-3h, taking out and drying for 3-9 times to obtain the MXene-based fiber capacitor electrode.
Example 1
An MXene-based fiber capacitor electrode was prepared by the steps of:
(1) Preparation of MXene-based electrode material suspension:
(1.1) preparation of an MXene monolayer suspension: 2.3g LiF and 40mL 9M hydrochloric acid were vigorously stirred in a polytetrafluoroethylene liner (volume 100 mL) for 30min, to obtain a mixture. Then 2g Ti is added within 10min 3 AlC 2 The precursor is slowly added to the mixture to avoid the risk of exothermic violent reactions. The polytetrafluoroethylene liner was then placed in a 40 ℃ water bath and stirred continuously for 48 hours. Then, the reaction solution was centrifuged 5 times at 3500rpm, washed with 1M HCl, then with distilled water until the pH value of the supernatant was neutral, sonicated in an ice bath environment for 120min, and finally centrifuged at 3500rpm for 20min, and the black supernatant was collected to obtain a MXene monolayerSuspension, i.e. Ti 3 C 2 T x The concentration of the Mxene monolayer suspension is 3.0mg/mL.
(1.2) preparation of Tetraaniline: 2.83g N-phenyl-1, 4-phenylenediamine powder was added to a 250 ml round bottom flask with 75ml of 1.0m hydrochloric acid and stirred rapidly for 30 minutes. 4.14g of ferric trichloride hexahydrate was dissolved in 75mL of 1.0M hydrochloric acid and quickly poured into a round bottom flask, followed by 75mL of 1.0M hydrochloric acid and stirred at room temperature of 25℃for 2h. The precipitate was then centrifuged at 9000rpm for 30min and washed 4 times with 0.1M hydrochloric acid. The precipitate was then mixed with 75mL of 2.0M ammonium hydroxide and 450mL of acetone for 30min to give a bright blue solution. Acetone was removed using a rotary evaporator. The dispersion was then centrifuged and washed 4 times with deionized water and the supernatant brought to neutral pH. The powder was collected, rinsed with ethanol and air dried for 12h at night to give the blue solid, tetra-aniline.
(1.3) preparation of modified tetraaniline containing an azide group: 0.8238 g of 5-azidopentanoic acid, 0.786g of dicyclohexylcarbodiimide, 0.390g of trimethylamine, 0.433 g of 4-dimethylaminopyridine and 1.665g of tetraaniline were dissolved in 15mL of Dichloromethane (DCM) and stirred at room temperature for 48h. The reaction mixture was then washed with deionized water. And then carrying out vacuum drying to obtain the modified tetraaniline containing the azide group.
(1.4) modified tetraaniline containing an azide group was dissolved in ethanol to prepare a modified tetraaniline ethanol solution having a concentration of 200. Mu.g/mL. 9mL of the MXene monolayer suspension (3 mg/mL) was added dropwise to 15mL of the modified tetraaniline ethanol solution (200. Mu.g/mL), and the mixture was vigorously stirred at room temperature at 25℃for 3 hours. The solution was exposed to uv light for 30min, then the liquid was centrifuged and washed with ethanol for 6 times to remove unreacted azide group-containing modified tetraaniline, then repeatedly washed with deionized water for 8 times, and deionized water was added to obtain an MXene-based electrode material suspension having a concentration of 3.0 mg/mL.
(2) Preparation of silk fibroin: 6g of silk cocoons are weighed and 600mL of 0.5wt% NaCO is added 3 The solution was placed in a water bath to boil for 1h, and then the above "600 mL of 0.5wt% NaCO was added" was repeated 3 Placing the solution into a water bath kettle, boiling for 1h for 4 times, and oven drying at 60deg.C for 8h to obtain silkAnd (5) plain. CaCl with the mol ratio of 1:2:8 2 、CH 3 CH 2 OH and H 2 O is mixed to prepare the silk fibroin extract. Taking 3g of silk fibroin, adding 150mL of silk fibroin extract, continuously stirring at a constant temperature of 60 ℃ for 2 hours, dialyzing with a dialysis bag with a molecular weight cut-off of 10000kDa, and replacing deionized water every 2 hours for 2 times initially; then deionized water is replaced once every 4 hours and twice; after 12 hours, deionized water is replaced every 8 hours until 72 hours later, the silk fibroin solution is taken out and frozen at low temperature, and after the silk fibroin solution is completely frozen, the silk fibroin solution is frozen and dried for 48 hours by using a vacuum freeze dryer, so that silk fibroin is obtained, and the silk fibroin is ground into powder and then is put into a sealed bottle for storage for standby.
(3) Preparation of silver nanowires: 3g of polyvinylpyrrolidone was added to 150mL of ethylene glycol and stirred, and then 0.15g of ferric chloride was added thereto and stirred to obtain a mixed solution. Then, the mixed solution was placed in a 250mL reaction kettle, heated to 150 ℃, and 37mL of 0.12m silver nitrate solution was added dropwise to the mixed solution, and the mixture was stirred well and reacted at 160 ℃ for 6 hours. After cooling to room temperature, the precipitate was separated, washed with ethanol, and subjected to centrifugal washing at 3000rpm for 3 times. Finally, the supernatant is poured off to obtain silver nanowire sediment which is stored in N, N-dimethylformamide.
(4) Preparation of spinning solution: 1g of silk fibroin was weighed into 20mLN, N-dimethylformamide and stirred with a magnet to a flocculent solid suspension. 4g of polyurethane particles are weighed and added into flocculent solid suspension, stirring is carried out for 1.5h, 0.1g of silver nano wires are added, stirring is carried out, and stirring is carried out until uniform viscous liquid is obtained, thus obtaining spinning solution.
(5) Preparation of silk fibroin/polyurethane/silver nanowire composite fiber: pouring the spinning solution into a 5mL disposable sterile syringe, sleeving the syringe on a spinning head, fixing the syringe on a digital injection pump, setting the injection speed to be 2mL/min, starting wet spinning, setting a coagulation bath to be deionized water, and placing the obtained fiber in a drying box to be dried at 60 ℃ for 4 hours to obtain the silk fibroin/polyurethane/silver nanowire composite fiber.
(6) Compounding of MXene-based electrode materials: soaking silk fibroin/polyurethane/silver nanowire composite fiber in MXene-based electrode material suspension for 1h, taking out, placing in a vacuum drying oven, drying at 60 ℃ for 2h, taking out the fiber, then repeating the process of soaking in MXene-based electrode material suspension for 1h, taking out, placing in the vacuum drying oven, drying at 60 ℃ for 2h, and taking out the fiber for 3 times to obtain the MXene-based fiber capacitor electrode.
Cutting the electrode of the prepared MXene-based fiber capacitor into 1cm long, clamping with an electrode clamp to serve as a working electrode, silver/silver chloride as a reference electrode, and a platinum sheet electrode as a counter electrode, wherein 1M H is selected 2 SO 4 As an electrolyte solution. The conductivity was 1033S/cm by digital source meter testing, CV, GCD and cycling were performed at 5mV/S with a volume capacitance of 296.5F/cm3, cycling 5000 times, and a capacitance retention of 77.3%.
Example 2
An MXene-based fiber capacitor electrode was prepared by the steps of:
(1) Preparation of MXene-based electrode material suspension:
(1.1) preparation of an MXene monolayer suspension: 2.3g LiF and 40mL 9M hydrochloric acid were vigorously stirred in a polytetrafluoroethylene liner (volume 100 mL) for 30min, to obtain a mixture. Then 2g Ti is added within 10min 3 AlC 2 The precursor is slowly added to the mixture to avoid the risk of exothermic violent reactions. The polytetrafluoroethylene liner was then placed in a 40 ℃ water bath and stirred continuously for 48 hours. Then centrifuging the reaction solution at 3500rpm for 5 times, washing with 1M HCl, washing with distilled water until the pH value of the supernatant is neutral, performing ultrasonic treatment in ice bath environment for 120min, centrifuging at 3500rpm for 20min, and collecting black supernatant to obtain MXene monolayer suspension, namely Ti 3 C 2 T x The concentration of the Mxene monolayer suspension is 3.0mg/mL.
(1.2) preparation of Tetraaniline: 2.83g N-phenyl-1, 4-phenylenediamine powder was added to a 250 ml round bottom flask with 75ml of 1.0m hydrochloric acid and stirred rapidly for 30 minutes. 4.14g of ferric trichloride hexahydrate was dissolved in 75mL of 1.0M hydrochloric acid and quickly poured into a round bottom flask, followed by 75mL of 1.0M hydrochloric acid and stirred at room temperature of 25℃for 2h. The precipitate was then centrifuged at 9000rpm for 30min and washed 4 times with 0.1M hydrochloric acid. The precipitate was then mixed with 75mL of 2.0M ammonium hydroxide and 450mL of acetone for 30min to give a bright blue solution. Acetone was removed using a rotary evaporator. The dispersion was then centrifuged and washed 4 times with deionized water and the supernatant brought to neutral pH. The powder was collected, rinsed with ethanol and air dried for 12h at night to give the blue solid, tetra-aniline.
(1.3) preparation of modified tetraaniline containing an azide group: 0.8238 g of 5-azidopentanoic acid, 0.786g of dicyclohexylcarbodiimide, 0.390g of trimethylamine, 0.431g of 4-dimethylaminopyridine and 1.665g of tetraaniline were dissolved in 15mL of DCM and stirred at room temperature for 48h. The reaction mixture was then washed with deionized water. And then carrying out vacuum drying to obtain the modified tetraaniline containing the azide group.
(1.4) modified tetraaniline containing an azide group was dissolved in ethanol to prepare a modified tetraaniline ethanol solution having a concentration of 200. Mu.g/mL. 9mL of the Mxene monolayer suspension (3 mg/mL) was added dropwise to 15mL of the modified tetraaniline ethanol solution (200. Mu.g/mL) and stirred vigorously at room temperature for 3h at 25 ℃. The solution was exposed to uv light for 30min, then the liquid was centrifuged and washed with ethanol for 6 times to remove unreacted azide group-containing modified tetraaniline, then repeatedly washed with deionized water for 8 times, and deionized water was added to obtain an MXene-based electrode material suspension having a concentration of 3.0 mg/mL.
(2) Preparation of silk fibroin: 6g of silk cocoons are weighed and 600mL of 0.5wt% NaCO is added 3 The solution was placed in a water bath to boil for 1h, and then the above "600 mL of 0.5wt% NaCO was added" was repeated 3 The solution is placed in a water bath kettle for boiling for 1 h' for 4 times, and is placed in a baking oven at 60 ℃ for drying for 8h, so as to obtain the silk fibroin. CaCl with the mol ratio of 1:2:8 2 、CH 3 CH 2 OH and H 2 O is mixed to prepare the silk fibroin extract. Taking 3g of silk fibroin, adding 150mL of silk fibroin extract, continuously stirring at a constant temperature of 60 ℃ for 2 hours, dialyzing with a dialysis bag with a molecular weight cut-off of 10000kDa, and replacing deionized water every 2 hours for 2 times initially; then deionized water is replaced once every 4 hours and twice; after 12 hours, the deionized water is replaced every 8 hours until the silk fibroin solution is taken out after 72 hours and the temperature is low Freezing, freeze drying silk fibroin solution for 48 hr with vacuum freeze drier to obtain silk fibroin, grinding into powder, and storing in sealed bottle.
(3) Preparation of silver nanowires: 3g of polyvinylpyrrolidone was added to 150mL of ethylene glycol and stirred, and then 0.15g of ferric chloride was added thereto and stirred to obtain a mixed solution. Then, the mixed solution was placed in a 250mL reaction kettle, heated to 150 ℃, and 37mL of 0.12m silver nitrate solution was added dropwise to the mixed solution, and the mixture was stirred well and reacted at 160 ℃ for 6 hours. After cooling to room temperature, the precipitate was separated, washed with ethanol, and subjected to centrifugal washing at 3000rpm for 3 times. Finally, the supernatant is poured off to obtain silver nanowire sediment which is stored in N, N-dimethylformamide.
(4) Preparation of spinning solution: 1g of silk fibroin was weighed into 20mLN, N-dimethylformamide and stirred with a magnet to a flocculent solid suspension. 4g of polyurethane particles are weighed and added into flocculent solid suspension, stirring is carried out for 1.5h, 0.1g of silver nano wires are added, stirring is carried out, and stirring is carried out until uniform viscous liquid is obtained, thus obtaining spinning solution.
(5) Preparation of silk fibroin/polyurethane/silver nanowire composite fiber: pouring the spinning solution into a 5mL disposable sterile syringe, sleeving the syringe on a spinning head, fixing the syringe on a digital injection pump, setting the injection speed to be 2mL/min, starting wet spinning, setting a coagulation bath to be deionized water, and placing the obtained fiber in a drying box to be dried at 60 ℃ for 4 hours to obtain the silk fibroin/polyurethane/silver nanowire composite fiber.
(6) Compounding of MXene-based electrode materials: soaking silk fibroin/polyurethane/silver nanowire composite fiber in MXene-based electrode material suspension for 1h, taking out, placing in a vacuum drying oven, drying at 60 ℃ for 2h, taking out the fiber, then repeating the above-mentioned process of soaking in MXene-based electrode material suspension for 1h, taking out, placing in the vacuum drying oven, drying at 60 ℃ for 2h, and taking out the fiber for 6 times to obtain the MXene-based fiber capacitor electrode.
Cutting the electrode of the prepared MXene-based fiber capacitor to length of 1cm, clamping the electrode with an electrode clamp to obtain a working electrode, and silver/chloridizingSilver is used as reference electrode, platinum sheet electrode is used as counter electrode, 1M H is selected 2 SO 4 As an electrolyte solution. The conductivity was 1289S/cm by digital source meter testing, CV, GCD and cycling were performed at 5mV/S with a volume capacitance of 396.5F/cm3, cycling 5000 times, and a capacitance retention of 87.2%.
Example 3
An MXene-based fiber capacitor electrode was prepared by the steps of:
(1) Preparation of MXene-based electrode material suspension:
(1.1) preparation of an MXene monolayer suspension: 2.3g LiF and 40mL 9M hydrochloric acid were vigorously stirred in a polytetrafluoroethylene liner (volume 100 mL) for 30min, to obtain a mixture. Then 2g Ti is added within 10min 3 AlC 2 The precursor is slowly added to the mixture to avoid the risk of exothermic violent reactions. The polytetrafluoroethylene liner was then placed in a 40 ℃ water bath and stirred continuously for 48 hours. Then centrifuging the reaction solution at 3500rpm for 5 times, washing with 1M HCl, washing with distilled water until the pH value of the supernatant is neutral, performing ultrasonic treatment in ice bath environment for 120min, centrifuging at 3500rpm for 20min, and collecting black supernatant to obtain MXene monolayer suspension, namely Ti 3 C 2 T x The concentration of the Mxene monolayer suspension is 3.0mg/mL.
(1.2) preparation of Tetraaniline: 2.83g N-phenyl-1, 4-phenylenediamine powder was added to a 250 ml round bottom flask with 75ml of 1.0m hydrochloric acid and stirred rapidly for 30 minutes. 4.14g of ferric trichloride hexahydrate was dissolved in 75mL of 1.0M hydrochloric acid and quickly poured into a round bottom flask, followed by 75mL of 1.0M hydrochloric acid and stirred at room temperature of 25℃for 2h. The precipitate was then centrifuged at 9000rpm for 30min and washed 4 times with 0.1M hydrochloric acid. The precipitate was then mixed with 75mL of 2.0M ammonium hydroxide and 450mL of acetone for 30min to give a bright blue solution. Acetone was removed using a rotary evaporator. The dispersion was then centrifuged and washed 4 times with deionized water and the supernatant brought to neutral pH. The powder was collected, rinsed with ethanol and air dried for 12h at night to give the blue solid, tetra-aniline.
(1.3) preparation of modified tetraaniline containing an azide group: 0.8238 g of 5-azidopentanoic acid, 0.786g of dicyclohexylcarbodiimide, 0.390g of trimethylamine, 0.431g of 4-dimethylaminopyridine and 1.665g of tetraaniline were dissolved in 15mL of DCM and stirred at room temperature for 48h. The reaction mixture was then washed with deionized water. And then carrying out vacuum drying to obtain the modified tetraaniline containing the azide group.
(1.4) modified tetraaniline containing an azide group was dissolved in ethanol to prepare a modified tetraaniline ethanol solution having a concentration of 200. Mu.g/mL. 9mL of the MXene monolayer suspension (3 mg/mL) was added dropwise to 15mL of the modified tetraaniline ethanol solution (200. Mu.g/mL), and the mixture was vigorously stirred at room temperature at 25℃for 3 hours. The solution was exposed to uv light for 30min, then the liquid was centrifuged and washed with ethanol for 6 times to remove unreacted azide group-containing modified tetraaniline, then repeatedly washed with deionized water for 8 times, and deionized water was added to obtain an MXene-based electrode material suspension having a concentration of 3.0 mg/mL.
(2) Preparation of silk fibroin: 6g of silk cocoons are weighed and 600mL of 0.5wt% NaCO is added 3 The solution was placed in a water bath to boil for 1h, and then the above "600 mL of 0.5wt% NaCO was added" was repeated 3 The solution is placed in a water bath kettle for boiling for 1 h' for 4 times, and is placed in a baking oven at 60 ℃ for drying for 8h, so as to obtain the silk fibroin. CaCl with the mol ratio of 1:2:8 2 、CH 3 CH 2 OH and H 2 O is mixed to prepare the silk fibroin extract. Taking 3g of silk fibroin, adding 150mL of silk fibroin extract, continuously stirring at a constant temperature of 60 ℃ for 2 hours, dialyzing with a dialysis bag with a molecular weight cut-off of 10000kDa, and replacing deionized water every 2 hours for 2 times initially; then deionized water is replaced once every 4 hours and twice; after 12 hours, deionized water is replaced every 8 hours until 72 hours later, the silk fibroin solution is taken out and frozen at low temperature, and after the silk fibroin solution is completely frozen, the silk fibroin solution is frozen and dried for 48 hours by using a vacuum freeze dryer, so that silk fibroin is obtained, and the silk fibroin is ground into powder and then is put into a sealed bottle for storage for standby.
(3) Preparation of silver nanowires: 3g of polyvinylpyrrolidone was added to 150mL of ethylene glycol and stirred, and then 0.15g of ferric chloride was added thereto and stirred to obtain a mixed solution. Then, the mixed solution was placed in a 250mL reaction kettle, heated to 150 ℃, and 37mL of 0.12m silver nitrate solution was added dropwise to the mixed solution, and the mixture was stirred well and reacted at 160 ℃ for 6 hours. After cooling to room temperature, the precipitate was separated, washed with ethanol, and subjected to centrifugal washing at 3000rpm for 3 times. Finally, the supernatant is poured off to obtain silver nanowire sediment which is stored in N, N-dimethylformamide.
(4) Preparation of spinning solution: 1g of silk fibroin was weighed into 20mLN, N-dimethylformamide and stirred with a magnet to a flocculent solid suspension. 4g of polyurethane particles are weighed and added into flocculent solid suspension, stirring is carried out for 1.5h, 0.1g of silver nano wires are added, stirring is carried out, and stirring is carried out until uniform viscous liquid is obtained, thus obtaining spinning solution.
(5) Preparation of silk fibroin/polyurethane/silver nanowire composite fiber: pouring the spinning solution into a 5mL disposable sterile syringe, sleeving the syringe on a spinning head, fixing the syringe on a digital injection pump, setting the injection speed to be 2mL/min, starting wet spinning, setting a coagulation bath to be deionized water, and placing the obtained fiber in a drying box to be dried at 60 ℃ for 4 hours to obtain the silk fibroin/polyurethane/silver nanowire composite fiber.
(6) Compounding of MXene-based electrode materials: soaking silk fibroin/polyurethane/silver nanowire composite fiber in MXene-based electrode material suspension for 1h, taking out, placing in a vacuum drying oven, drying at 60 ℃ for 2h, taking out the fiber, then repeating the process of soaking in MXene-based electrode material suspension for 1h, taking out, placing in the vacuum drying oven, drying at 60 ℃ for 2h, and taking out the fiber for 9 times to obtain the MXene-based fiber capacitor electrode.
Cutting the electrode of the prepared MXene-based fiber capacitor into 1cm long, clamping with an electrode clamp to serve as a working electrode, silver/silver chloride as a reference electrode, and a platinum sheet electrode as a counter electrode, wherein 1M H is selected 2 SO 4 As an electrolyte solution. The conductivity was 1589S/cm by digital source meter testing, CV, GCD and cycling were performed at 5mV/S with a volume capacitance of 332.6F/cm3, cycling 5000 times and a capacitance retention of 73.3%.
Comparative example 1
An MXene-based fiber capacitor electrode was prepared by the steps of:
(1) Preparation of MXene-based electrode material suspension:
(1.1) preparation of an MXene monolayer suspension: 2.3g LiF and 40mL 9M hydrochloric acid were vigorously stirred in a polytetrafluoroethylene liner (volume 100 mL) for 30min, to obtain a mixture. Then 2g Ti is added within 10min 3 AlC 2 The precursor is slowly added to the mixture to avoid the risk of exothermic violent reactions. The polytetrafluoroethylene liner was then placed in a 40 ℃ water bath and stirred continuously for 48 hours. Then centrifuging the reaction solution at 3500rpm for 5 times, washing with 1M HCl, washing with distilled water until the pH value of the supernatant is neutral, performing ultrasonic treatment in ice bath environment for 120min, centrifuging at 3500rpm for 20min, and collecting black supernatant to obtain MXene monolayer suspension, namely Ti 3 C 2 T x The concentration of the Mxene monolayer suspension is 3.0mg/mL.
(1.2) preparation of Tetraaniline: 2.83g N-phenyl-1, 4-phenylenediamine powder was added to a 250 ml round bottom flask with 75ml of 1.0m hydrochloric acid and stirred rapidly for 30 minutes. 4.14g of ferric trichloride hexahydrate was dissolved in 75mL of 1.0M hydrochloric acid and quickly poured into a round bottom flask, followed by 75mL of 1.0M hydrochloric acid and stirred at room temperature of 25℃for 2h. The precipitate was then centrifuged at 9000rpm for 30min and washed 4 times with 0.1M hydrochloric acid. The precipitate was then mixed with 75mL of 2.0M ammonium hydroxide and 450mL of acetone for 30min to give a bright blue solution. Acetone was removed using a rotary evaporator. The dispersion was then centrifuged and washed 4 times with deionized water and the supernatant brought to neutral pH. The powder was collected, rinsed with ethanol and air dried for 12h at night to give the blue solid, tetra-aniline.
(1.3) preparation of modified tetraaniline containing an azide group: 0.8238 g of 5-azidopentanoic acid, 0.786g of dicyclohexylcarbodiimide, 0.390g of trimethylamine, 0.433 g of 4-dimethylaminopyridine and 1.665g of tetraaniline were dissolved in 15mL of Dichloromethane (DCM) and stirred at room temperature for 48h. The reaction mixture was then washed with deionized water. And then carrying out vacuum drying to obtain the modified tetraaniline containing the azide group.
(1.4) modified tetraaniline containing an azide group was dissolved in ethanol to prepare a modified tetraaniline ethanol solution having a concentration of 200. Mu.g/mL. 9mL of the MXene monolayer suspension (3 mg/mL) was added dropwise to 15mL of the modified tetraaniline ethanol solution (200. Mu.g/mL), and the mixture was vigorously stirred at room temperature at 25℃for 3 hours. The solution was exposed to uv light for 30min, then the liquid was centrifuged and washed with ethanol for 6 times to remove unreacted azide group-containing modified tetraaniline, then repeatedly washed with deionized water for 8 times, and deionized water was added to obtain an MXene-based electrode material suspension having a concentration of 3.0 mg/mL.
(2) Preparation of silk fibroin: 6g of silk cocoons are weighed and 600mL of 0.5wt% NaCO is added 3 The solution was placed in a water bath to boil for 1h, and then the above "600 mL of 0.5wt% NaCO was added" was repeated 3 The solution is placed in a water bath kettle for boiling for 1 h' for 4 times, and is placed in a baking oven at 60 ℃ for drying for 8h, so as to obtain the silk fibroin. CaCl with the mol ratio of 1:2:8 2 、CH 3 CH 2 OH and H 2 O is mixed to prepare the silk fibroin extract. Taking 3g of silk fibroin, adding 150mL of silk fibroin extract, continuously stirring at a constant temperature of 60 ℃ for 2 hours, dialyzing with a dialysis bag with a molecular weight cut-off of 10000kDa, and replacing deionized water every 2 hours for 2 times initially; then deionized water is replaced once every 4 hours and twice; after 12 hours, deionized water is replaced every 8 hours until 72 hours later, the silk fibroin solution is taken out and frozen at low temperature, and after the silk fibroin solution is completely frozen, the silk fibroin solution is frozen and dried for 48 hours by using a vacuum freeze dryer, so that silk fibroin is obtained, and the silk fibroin is ground into powder and then is put into a sealed bottle for storage for standby.
(3) Preparation of spinning solution: 1g of silk fibroin was weighed into 20mLN, N-dimethylformamide and stirred with a magnet to a flocculent solid suspension. 4g of polyurethane particles are weighed and added into flocculent solid suspension, and the mixture is stirred to be uniform viscous liquid, so as to obtain spinning solution.
(4) Preparation of silk fibroin/polyurethane/silver nanowire composite fiber: pouring the spinning solution into a 5mL disposable sterile syringe, sleeving the syringe on a spinning head, fixing the syringe on a digital injection pump, setting the injection speed to be 2mL/min, starting wet spinning, setting a coagulation bath to be deionized water, and placing the obtained fiber in a drying box to be dried at 60 ℃ for 4 hours to obtain the silk fibroin/polyurethane/silver nanowire composite fiber.
(5) Compounding of MXene-based electrode materials: soaking silk fibroin/polyurethane/silver nanowire composite fiber in MXene-based electrode material suspension for 1h, taking out, placing in a vacuum drying oven, drying at 60 ℃ for 2h, taking out the fiber, then repeating the process of soaking in MXene-based electrode material suspension for 1h, taking out, placing in the vacuum drying oven, drying at 60 ℃ for 2h, and taking out the fiber for 3 times to obtain the MXene-based fiber capacitor electrode.
Cutting the electrode of the prepared MXene-based fiber capacitor into 1cm long, clamping with an electrode clamp to serve as a working electrode, silver/silver chloride as a reference electrode, and a platinum sheet electrode as a counter electrode, wherein 1M H is selected 2 SO 4 As an electrolyte solution. The conductivity was 670S/cm by digital source meter testing, CV, GCD and cycling were performed at 5mV/S with a volume capacitance of 203.2F/cm3, cycling 5000 times, and a capacitance retention of 50.8%.
Comparative example 2
An MXene-based fiber capacitor electrode was prepared by the steps of:
(1) Preparation of MXene-based electrode material suspension:
(1.1) preparation of an MXene monolayer suspension: 2.3g LiF and 40mL 9M hydrochloric acid were vigorously stirred in a polytetrafluoroethylene liner (volume 100 mL) for 30min, to obtain a mixture. Then 2g Ti is added within 10min 3 AlC 2 The precursor is slowly added to the mixture to avoid the risk of exothermic violent reactions. The polytetrafluoroethylene liner was then placed in a 40 ℃ water bath and stirred continuously for 48 hours. Then centrifuging the reaction solution at 3500rpm for 5 times, washing with 1M HCl, washing with distilled water until the pH value of the supernatant is neutral, performing ultrasonic treatment in ice bath environment for 120min, centrifuging at 3500rpm for 20min, and collecting black supernatant to obtain MXene monolayer suspension, namely Ti 3 C 2 T x The concentration of the Mxene monolayer suspension is 3.0mg/mL.
(1.2) polyaniline was dissolved in N-methylpyrrolidone to prepare a polyaniline solution having a concentration of 200. Mu.g/mL. 9mL of the MXene monolayer suspension (3 mg/mL) was added dropwise to 15mL of polyaniline solution (200. Mu.g/mL), and the mixture was vigorously stirred at room temperature for 3 hours at 25 ℃. The liquid was then centrifuged and washed 6 times with N-methylpyrrolidone, repeatedly rinsed 8 times with deionized water, and deionized water was added to obtain a MXene-based electrode material suspension having a concentration of 3.0mg/mL.
(2) Preparation of silk fibroin: 6g of silk cocoons are weighed and 600mL of 0.5wt% NaCO is added 3 The solution was placed in a water bath to boil for 1h, and then the above "600 mL of 0.5wt% NaCO was added" was repeated 3 The solution is placed in a water bath kettle for boiling for 1 h' for 4 times, and is placed in a baking oven at 60 ℃ for drying for 8h, so as to obtain the silk fibroin. CaCl with the mol ratio of 1:2:8 2 、CH 3 CH 2 OH and H 2 O is mixed to prepare the silk fibroin extract. Taking 3g of silk fibroin, adding 150mL of silk fibroin extract, continuously stirring at a constant temperature of 60 ℃ for 2 hours, dialyzing with a dialysis bag with a molecular weight cut-off of 10000kDa, and replacing deionized water every 2 hours for 2 times initially; then deionized water is replaced once every 4 hours and twice; after 12 hours, deionized water is replaced every 8 hours until 72 hours later, the silk fibroin solution is taken out and frozen at low temperature, and after the silk fibroin solution is completely frozen, the silk fibroin solution is frozen and dried for 48 hours by using a vacuum freeze dryer, so that silk fibroin is obtained, and the silk fibroin is ground into powder and then is put into a sealed bottle for storage for standby.
(3) Preparation of silver nanowires: 3g of polyvinylpyrrolidone was added to 150mL of ethylene glycol and stirred, and then 0.15g of ferric chloride was added thereto and stirred to obtain a mixed solution. Then, the mixed solution was placed in a 250mL reaction kettle, heated to 150 ℃, and 37mL of 0.12m silver nitrate solution was added dropwise to the mixed solution, and the mixture was stirred well and reacted at 160 ℃ for 6 hours. After cooling to room temperature, the precipitate was separated, washed with ethanol, and subjected to centrifugal washing at 3000rpm for 3 times. Finally, the supernatant is poured off to obtain silver nanowire sediment which is stored in N, N-dimethylformamide.
(4) Preparation of spinning solution: 1g of silk fibroin was weighed into 20mLN, N-dimethylformamide and stirred with a magnet to a flocculent solid suspension. 4g of polyurethane particles are weighed and added into flocculent solid suspension, stirring is carried out for 1.5h, 0.1g of silver nano wires are added, stirring is carried out, and stirring is carried out until uniform viscous liquid is obtained, thus obtaining spinning solution.
(5) Preparation of silk fibroin/polyurethane/silver nanowire composite fiber: pouring the spinning solution into a 5mL disposable sterile syringe, sleeving the syringe on a spinning head, fixing the syringe on a digital injection pump, setting the injection speed to be 2mL/min, starting wet spinning, setting a coagulation bath to be deionized water, and placing the obtained fiber in a drying box to be dried at 60 ℃ for 4 hours to obtain the silk fibroin/polyurethane/silver nanowire composite fiber.
(6) Compounding of MXene-based electrode materials: soaking silk fibroin/polyurethane/silver nanowire composite fiber in MXene-based electrode material suspension for 1h, taking out, placing in a vacuum drying oven, drying at 60 ℃ for 2h, taking out the fiber, then repeating the process of soaking in MXene-based electrode material suspension for 1h, taking out, placing in the vacuum drying oven, drying at 60 ℃ for 2h, and taking out the fiber for 3 times to obtain the MXene-based fiber capacitor electrode.
Cutting the electrode of the prepared MXene-based fiber capacitor into 1cm long, clamping with an electrode clamp to serve as a working electrode, silver/silver chloride as a reference electrode, and a platinum sheet electrode as a counter electrode, wherein 1M H is selected 2 SO 4 As an electrolyte solution. Conductivity was 956S/cm by digital source meter testing, CV, GCD and cycle testing were performed at electrochemical workstation with a volume capacitance of 241.9F/cm at 5mV/S 3 The cycle was 5000 times, and the capacitance retention was 62.1%.
Comparative example 3
An MXene-based fiber capacitor electrode was prepared by the steps of:
(1) Preparation of MXene-based electrode material suspension:
(1.1) preparation of an MXene monolayer suspension: 2.3g LiF and 40mL 9M hydrochloric acid were vigorously stirred in a polytetrafluoroethylene liner (volume 100 mL) for 30min, to obtain a mixture. Then 2g of Ti3AlC are added within 10min 2 The precursor is slowly added to the mixture to avoid the risk of exothermic violent reactions. The polytetrafluoroethylene liner was then placed in a 40 ℃ water bath and stirred continuously for 48 hours. Then, the reaction solution was centrifuged at 3500rpm for 5 times, washed with 1M HCl, then with distilled water until the pH of the supernatant was neutral, sonicated in an ice bath environment for 120min, and finally centrifuged at 3500rpm for 20min, and black was collected Supernatant to obtain MXene monolayer suspension, namely Ti 3 C 2 T x The concentration of the Mxene monolayer suspension is 3.0mg/mL.
(1.2) preparation of Tetraaniline: 2.83g N-phenyl-1, 4-phenylenediamine powder was added to a 250 ml round bottom flask with 75ml of 1.0m hydrochloric acid and stirred rapidly for 30 minutes. 4.14g of ferric trichloride hexahydrate was dissolved in 75mL of 1.0M hydrochloric acid and quickly poured into a round bottom flask, followed by 75mL of 1.0M hydrochloric acid and stirred at room temperature of 25℃for 2h. The precipitate was then centrifuged at 9000rpm for 30min and washed 4 times with 0.1M hydrochloric acid. The precipitate was then mixed with 75mL of 2.0M ammonium hydroxide and 450mL of acetone for 30min to give a bright blue solution. Acetone was removed using a rotary evaporator. The dispersion was then centrifuged and washed 4 times with deionized water and the supernatant brought to neutral pH. The powder was collected, rinsed with ethanol and air dried for 12h at night to give the blue solid, tetra-aniline.
(1.3) Tetraaniline was dissolved in ethanol to prepare a solution of 200. Mu.g/mL in ethanol. 9mL of the MXene monolayer suspension (3 mg/mL) was added dropwise to 15mL of a tetraaniline ethanol solution (200. Mu.g/mL) and stirred vigorously at room temperature for 3h at 25 ℃. The liquid was then centrifuged and washed 6 times with ethanol, repeatedly rinsed 8 times with deionized water, and deionized water was added to obtain a suspension of the MXene-based electrode material at a concentration of 3.0mg/mL.
(2) Preparation of silk fibroin: 6g of silk cocoons are weighed and 600mL of 0.5wt% NaCO is added 3 The solution was placed in a water bath to boil for 1h, and then the above "600 mL of 0.5wt% NaCO was added" was repeated 3 The solution is placed in a water bath kettle for boiling for 1 h' for 4 times, and is placed in a baking oven at 60 ℃ for drying for 8h, so as to obtain the silk fibroin. CaCl with the mol ratio of 1:2:8 2 、CH 3 CH 2 OH and H 2 O is mixed to prepare the silk fibroin extract. Taking 3g of silk fibroin, adding 150mL of silk fibroin extract, continuously stirring at a constant temperature of 60 ℃ for 2 hours, dialyzing with a dialysis bag with a molecular weight cut-off of 10000kDa, and replacing deionized water every 2 hours for 2 times initially; then deionized water is replaced once every 4 hours and twice; after 12 hours, deionized water is replaced every 8 hours until the silk fibroin solution is taken out after 72 hours and frozen at low temperature, and the silk fibroin solution is completely frozen and then is madeFreeze-drying the silk fibroin solution for 48 hours by using a vacuum freeze dryer to obtain silk fibroin, grinding the silk fibroin into powder, and then placing the powder into a sealed bottle for storage for later use.
(3) Preparation of silver nanowires: 3g of polyvinylpyrrolidone was added to 150mL of ethylene glycol and stirred, and then 0.15g of ferric chloride was added thereto and stirred to obtain a mixed solution. Then, the mixed solution was placed in a 250mL reaction kettle, heated to 150 ℃, and 37mL of 0.12m silver nitrate solution was added dropwise to the mixed solution, and the mixture was stirred well and reacted at 160 ℃ for 6 hours. After cooling to room temperature, the precipitate was separated, washed with ethanol, and subjected to centrifugal washing at 3000rpm for 3 times. Finally, the supernatant is poured off to obtain silver nanowire sediment which is stored in N, N-dimethylformamide.
(4) Preparation of spinning solution: 1g of silk fibroin was weighed into 20mLN, N-dimethylformamide and stirred with a magnet to a flocculent solid suspension. 4g of polyurethane particles are weighed and added into flocculent solid suspension, stirring is carried out for 1.5h, 0.1g of silver nano wires are added, stirring is carried out, and stirring is carried out until uniform viscous liquid is obtained, thus obtaining spinning solution.
(5) Preparation of silk fibroin/polyurethane/silver nanowire composite fiber: pouring the spinning solution into a 5mL disposable sterile syringe, sleeving the syringe on a spinning head, fixing the syringe on a digital injection pump, setting the injection speed to be 2mL/min, starting wet spinning, setting a coagulation bath to be deionized water, and placing the obtained fiber in a drying box to be dried at 60 ℃ for 4 hours to obtain the silk fibroin/polyurethane/silver nanowire composite fiber.
(6) Compounding of MXene-based electrode materials: soaking silk fibroin/polyurethane/silver nanowire composite fiber in MXene-based electrode material suspension for 1h, taking out, placing in a vacuum drying oven, drying at 60 ℃ for 2h, taking out the fiber, then repeating the process of soaking in MXene-based electrode material suspension for 1h, taking out, placing in the vacuum drying oven, drying at 60 ℃ for 2h, and taking out the fiber for 3 times to obtain the MXene-based fiber capacitor electrode.
Cutting the prepared MXene-based fiber capacitor electrode into 1cm long, clamping with electrode clamp as working electrode, silver/silver chloride as reference electrode, and platinum sheet electrodeAs a counter electrode, 1M H was selected 2 SO 4 As an electrolyte solution. Conductivity was 988S/cm by digital source meter testing, CV, GCD and cycle testing were performed at electrochemical workstation with a volume capacitance of 264.3F/cm at 5mV/S 3 The cycle was 5000 times, and the capacitance retention was 69.3%.
Comparative example 4
An MXene-based fiber capacitor electrode was prepared by the steps of:
(1) Preparation of MXene-based electrode material suspension:
(1.1) preparation of an MXene monolayer suspension: 2.3g LiF and 40mL 9M hydrochloric acid were vigorously stirred in a polytetrafluoroethylene liner (volume 100 mL) for 30min, to obtain a mixture. Then 2g Ti is added within 10min 3 AlC 2 The precursor is slowly added to the mixture to avoid the risk of exothermic violent reactions. The polytetrafluoroethylene liner was then placed in a 40 ℃ water bath and stirred continuously for 48 hours. Then centrifuging the reaction solution at 3500rpm for 5 times, washing with 1M HCl, washing with distilled water until the pH value of the supernatant is neutral, performing ultrasonic treatment in ice bath environment for 120min, centrifuging at 3500rpm for 20min, and collecting black supernatant to obtain MXene monolayer suspension, namely Ti 3 C 2 T x The concentration of the Mxene monolayer suspension is 3.0mg/mL.
(1.2) 9mL of the MXene monolayer suspension (3 mg/mL) was added dropwise to 15mL of ethanol solution, and the mixture was vigorously stirred at room temperature at 25℃for 3 hours. The liquid was then centrifuged and washed 6 times with ethanol, repeatedly rinsed 8 times with deionized water, and deionized water was added to obtain a suspension of the MXene-based electrode material at a concentration of 3.0mg/mL.
(2) Preparation of silk fibroin: 6g of silk cocoons are weighed and 600mL of 0.5wt% NaCO is added 3 The solution was placed in a water bath to boil for 1h, and then the above "600 mL of 0.5wt% NaCO was added" was repeated 3 The solution is placed in a water bath kettle for boiling for 1 h' for 4 times, and is placed in a baking oven at 60 ℃ for drying for 8h, so as to obtain the silk fibroin. CaCl with the mol ratio of 1:2:8 2 、CH 3 CH 2 OH and H 2 O is mixed to prepare the silk fibroin extract. Taking 3g of silk fibroin, adding 150mL of silk fibroin extract, continuously stirring at 60 ℃ for 2 hours, usingDialyzing with dialysis bag with molecular weight cut-off of 10000kDa, and changing deionized water every 2h for the first 2 times; then deionized water is replaced once every 4 hours and twice; after 12 hours, deionized water is replaced every 8 hours until 72 hours later, the silk fibroin solution is taken out and frozen at low temperature, and after the silk fibroin solution is completely frozen, the silk fibroin solution is frozen and dried for 48 hours by using a vacuum freeze dryer, so that silk fibroin is obtained, and the silk fibroin is ground into powder and then is put into a sealed bottle for storage for standby.
(3) Preparation of silver nanowires: 3g of polyvinylpyrrolidone was added to 150mL of ethylene glycol and stirred, and then 0.15g of ferric chloride was added thereto and stirred to obtain a mixed solution. Then, the mixed solution was placed in a 250mL reaction kettle, heated to 150 ℃, and 37mL of 0.12m silver nitrate solution was added dropwise to the mixed solution, and the mixture was stirred well and reacted at 160 ℃ for 6 hours. After cooling to room temperature, the precipitate was separated, washed with ethanol, and subjected to centrifugal washing at 3000rpm for 3 times. Finally, the supernatant is poured off to obtain silver nanowire sediment which is stored in N, N-dimethylformamide.
(4) Preparation of spinning solution: 1g of silk fibroin was weighed into 20mLN, N-dimethylformamide and stirred with a magnet to a flocculent solid suspension. 4g of polyurethane particles are weighed and added into flocculent solid suspension, stirring is carried out for 1.5h, 0.1g of silver nano wires are added, stirring is carried out, and stirring is carried out until uniform viscous liquid is obtained, thus obtaining spinning solution.
(5) Preparation of silk fibroin/polyurethane/silver nanowire composite fiber: pouring the spinning solution into a 5mL disposable sterile syringe, sleeving the syringe on a spinning head, fixing the syringe on a digital injection pump, setting the injection speed to be 2mL/min, starting wet spinning, setting a coagulation bath to be deionized water, and placing the obtained fiber in a drying box to be dried at 60 ℃ for 4 hours to obtain the silk fibroin/polyurethane/silver nanowire composite fiber.
(6) Compounding of MXene-based electrode materials: soaking silk fibroin/polyurethane/silver nanowire composite fiber in MXene-based electrode material suspension for 1h, taking out, placing in a vacuum drying oven, drying at 60 ℃ for 2h, taking out the fiber, then repeating the process of soaking in MXene-based electrode material suspension for 1h, taking out, placing in the vacuum drying oven, drying at 60 ℃ for 2h, and taking out the fiber for 3 times to obtain the MXene-based fiber capacitor electrode.
Cutting the electrode of the prepared MXene-based fiber capacitor into 1cm long, clamping with an electrode clamp to serve as a working electrode, silver/silver chloride as a reference electrode, and a platinum sheet electrode as a counter electrode, wherein 1M H is selected 2 SO 4 As an electrolyte solution. The conductivity was 876S/cm by digital source meter testing, the electrochemical workstation performed CV, GCD and cycling tests, the volume capacitance at 5mV/S was 223.5F/cm3, cycling 5000 times, and the capacitance retention was 53.6%.
The electrochemical properties of the MXene-based fiber capacitor electrodes measured in examples 1-3 and comparative examples 1-4 are shown in Table 1.
TABLE 1
Conductivity (S/cm) Volume capacitance (F/cm) 3 ) Capacitance retention (%)
Example 1 1033 296.5 77.3
Example 2 1289 396.5 87.2
Example 3 1589 332.6 73.3
Comparative example 1 670 203.2 50.8
Comparative example 2 956 241.9 62.1
Comparative example 3 988 264.3 69.3
Comparative example 4 876 223.5 53.6
As can be seen from table 1:
(1) The significantly higher conductivity of examples 1-3 compared to comparative example 1 demonstrates that the addition of the conductive dopant silver nanowires to the fibers can increase the conductivity of the MXene-based fiber capacitor electrode.
(2) Compared with comparative example 4, the volume capacitance and the capacitance retention rate of examples 1-3 and comparative examples 2-3 are obviously higher, which indicates that the addition of polyaniline or aniline oligomer can obviously improve the energy storage performance of the MXene-based fiber capacitor electrode in the preparation process of the MXene-based electrode material.
(2) Compared with comparative example 2, the volume capacitance and the capacitance retention rate of comparative example 3 are obviously higher, which indicates that the addition of the aniline oligomer tetra-aniline is superior to the energy storage effect of polyaniline in the preparation process of the MXene-based electrode material. The reason is that polyaniline has higher rigidity than that of tetra-aniline, has poor dispersion, can not be well mixed with MXene uniformly, and affects electrochemical performance; while the molecular chain length of the polyaniline is shorter on the premise of having the advantages of the conductivity of the polyaniline and the like, the interlayer spacing of the MXene is easy to adjust, the dispersibility in water is better, and the energy storage effect of the composite material is well improved.
(3) Compared with comparative example 3, the volume capacitance and capacitance retention of examples 1-3 are significantly higher, demonstrating that the photochemical action of the organic azide compound is utilized to bond the tetraphenylamine to the MXene nanoplatelets during the preparation of the MXene-based electrode material, enabling the MXene-based fibrous capacitor electrode to have better energy storage properties. The functional groups of the tetraaniline and the MXene are stable under the condition of only physical stirring, do not generate chemical reaction, cannot form covalent bonds and can only form hydrogen bonds, while the modified tetraaniline containing the azide groups is decomposed into nitrogen and nitrene under the irradiation of ultraviolet light, the nitrene is very active, can be combined with H on the MXene to form stable covalent bonds, can better promote charge transfer between MXene layers and increase more electrochemical active sites, and greatly promotes the electrochemical energy storage performance of the MXene-based electrode material.
Finally, it should be noted that the above list is only specific embodiments of the present invention. Obviously, the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.

Claims (9)

1. The preparation method of the MXene-based fiber capacitor electrode is characterized by comprising the following steps of:
(1) Adding silk fibroin into the solvent I, and stirring to form flocculent solid suspension; adding polyurethane into flocculent solid suspension, uniformly mixing, adding silver nanowires, and stirring to uniform viscous liquid to obtain spinning solution;
(2) Carrying out wet spinning by adopting a spinning solution, and drying the obtained fiber to obtain a silk fibroin/polyurethane/silver nanowire composite fiber;
(3) Adding silk fibroin/polyurethane/silver nanowire composite fibers into an MXene-based electrode material suspension, fully soaking, taking out, drying, and repeating the processes of adding into the MXene-based electrode material suspension, fully soaking, taking out and drying for a plurality of times to obtain an MXene-based fiber capacitor electrode;
in the step (3), the preparation method of the MXene-based electrode material suspension comprises the following steps:
(1.1) stirring LiF and hydrochloric acid vigorously for 30-40min to obtain a mixed solution; then Ti is added in 10-20min 3 AlC 2 Slowly adding the precursor into the mixed solution, and continuing stirring for reaction; after the reaction is finished, carrying out centrifugation, acid washing and water washing to be neutral, carrying out ultrasonic treatment, and finally centrifuging and collecting supernatant to obtain MXene single-layer suspension;
(1.2) preparing N-phenyl-1, 4-phenylenediamine, ferric trichloride hexahydrate and hydrochloric acid into a reaction solution, reacting for 2-3 hours at 20-30 ℃, and separating and purifying the product to obtain the tetra-aniline;
(1.3) dissolving 5-azido valeric acid, dicyclohexylcarbodiimide, trimethylamine, 4-dimethylaminopyridine and tetraaniline in a solvent III, and separating a reaction product after stirring reaction to obtain modified tetraaniline containing azido groups;
(1.4) dissolving the modified tetraaniline containing the azide group in the solvent IV, dropwise adding the MXene single-layer suspension into the solvent IV, stirring the mixture, performing ultraviolet irradiation treatment, centrifuging the mixture, washing the mixture with ethanol, washing the mixture with water, and adding water to obtain the MXene-based electrode material suspension.
2. The method of claim 1, wherein in step (1), the method of preparing silk fibroin comprises the steps of: adding silk cocoons into NaCO 3 Degumming in the solution, repeating the degumming process for 2-4 times, and drying to obtain silkA hormone; adding silk fibroin extract into silk fibroin, stirring at 55-65deg.C for 1-2 hr, dialyzing, and lyophilizing to obtain silk fibroin.
3. The method of claim 2, wherein the silk fibroin extract is CaCl in a molar ratio of 1:1.5-2.5:7-9 2 、CH 3 CH 2 OH and H 2 And (3) mixing liquid of O.
4. The method according to claim 2, wherein the molecular weight cut-off is 9000-14000kDa and the dialysis time is 72-84h.
5. The method of preparing as claimed in claim 1, wherein in the step (1), the method of preparing silver nanowires comprises the steps of: preparing a mixed solution from polyvinylpyrrolidone, a solvent II and ferric chloride; heating the mixed solution to 145-155 ℃, dropwise adding a silver nitrate solution into the mixed solution, uniformly mixing, reacting for 5-8 hours at 155-165 ℃, separating out precipitate, and washing the precipitate to obtain the silver nanowire.
6. The method of claim 1, wherein in step (1), the mass to volume ratio of silk fibroin, polyurethane, silver nanowires, and solvent I is 1g:3-5g:0.1-0.2g:15-25mL.
7. The method according to claim 1, wherein in the step (2), the wet spinning speed of the spinning solution is 1 to 3mL/min.
8. The method of claim 1, wherein in step (3), the soaking time is 1 to 3 hours.
9. An MXene-based fiber capacitor electrode made by the method of one of claims 1-8.
CN202210919872.2A 2022-07-27 2022-07-27 MXene-based fiber capacitor electrode and preparation method thereof Active CN115312332B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210919872.2A CN115312332B (en) 2022-07-27 2022-07-27 MXene-based fiber capacitor electrode and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210919872.2A CN115312332B (en) 2022-07-27 2022-07-27 MXene-based fiber capacitor electrode and preparation method thereof

Publications (2)

Publication Number Publication Date
CN115312332A CN115312332A (en) 2022-11-08
CN115312332B true CN115312332B (en) 2023-12-22

Family

ID=83859628

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210919872.2A Active CN115312332B (en) 2022-07-27 2022-07-27 MXene-based fiber capacitor electrode and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115312332B (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108529611A (en) * 2018-05-14 2018-09-14 华南理工大学 A kind of azido functional graphene oxide and preparation method thereof
CN109192533A (en) * 2018-09-28 2019-01-11 江苏科技大学 A kind of electrode material for super capacitor and preparation method thereof
CN109238522A (en) * 2018-09-21 2019-01-18 南开大学 A kind of wearable flexibility stress sensor and its preparation method and application
CN111223687A (en) * 2020-01-13 2020-06-02 常州大学 Preparation method of MXene/PANI-based high-capacity linear supercapacitor electrode
CN112923954A (en) * 2021-01-25 2021-06-08 西安工业大学 Integrated flexible sensor based on sandwich type spinning film and manufacturing method
CN113481718A (en) * 2021-07-19 2021-10-08 青岛大学 Preparation method and application of intelligent heat-storage temperature-regulation nano aerogel fiber
US20210396607A1 (en) * 2018-11-08 2021-12-23 Drexel University Mxene-based sensor devices
CN114496399A (en) * 2022-01-20 2022-05-13 复旦大学 Preparation method of breathable sweat-removing flexible electrode
CN114522275A (en) * 2021-12-17 2022-05-24 淮阴工学院 Three-dimensional porous composite scaffold of oriented conductive fibers and preparation method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108529611A (en) * 2018-05-14 2018-09-14 华南理工大学 A kind of azido functional graphene oxide and preparation method thereof
CN109238522A (en) * 2018-09-21 2019-01-18 南开大学 A kind of wearable flexibility stress sensor and its preparation method and application
CN109192533A (en) * 2018-09-28 2019-01-11 江苏科技大学 A kind of electrode material for super capacitor and preparation method thereof
US20210396607A1 (en) * 2018-11-08 2021-12-23 Drexel University Mxene-based sensor devices
CN111223687A (en) * 2020-01-13 2020-06-02 常州大学 Preparation method of MXene/PANI-based high-capacity linear supercapacitor electrode
CN112923954A (en) * 2021-01-25 2021-06-08 西安工业大学 Integrated flexible sensor based on sandwich type spinning film and manufacturing method
CN113481718A (en) * 2021-07-19 2021-10-08 青岛大学 Preparation method and application of intelligent heat-storage temperature-regulation nano aerogel fiber
CN114522275A (en) * 2021-12-17 2022-05-24 淮阴工学院 Three-dimensional porous composite scaffold of oriented conductive fibers and preparation method thereof
CN114496399A (en) * 2022-01-20 2022-05-13 复旦大学 Preparation method of breathable sweat-removing flexible electrode

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
张胜民等著.《高等生物材料学实验》.华中科技大学出版社,2019,第58页. *
陈乐培等编著.《中级有机化学》.中国环境科学出版社,2004,第86-87页. *

Also Published As

Publication number Publication date
CN115312332A (en) 2022-11-08

Similar Documents

Publication Publication Date Title
CN105633372B (en) Nickel sulfide nanoparticles/N doping fiber base carbon aerogel composite material and preparation method thereof
CN107731545B (en) A kind of polyaniline MOF nanocomposite flexible super capacitor and preparation method
CN104466134B (en) The preparation method of self-supporting graphene/carbon nano-tube hybrid foam support amino anthraquinones base polymer
CN107785565B (en) Sn-TiO2Electrostatic spinning preparation method of-C nanofibers
Ji et al. Cellulose and poly (vinyl alcohol) composite gels as separators for quasi-solid-state electric double layer capacitors
CN106816603B (en) A kind of three-dimensional grapheme aeroge carries sulphur composite material and preparation method and application
CN110707323B (en) Anion layer-expanding carbon material and preparation method and application thereof
CN108807923A (en) The preparation method of sodium-ion battery modifying titanium dioxide-graphene negative material
CN110371970A (en) A kind of preparation method of the rich nitrogen grading porous carbon material of high-specific surface area
CN113675004A (en) MnO2Preparation method of coated MXene/C nanofiber material
CN114203952A (en) Sodium ion battery cathode, preparation method and application
CN109686576A (en) A kind of lithium-ion capacitor negative electrode material three-dimensional MoS2The preparation method of the compound porous fiber of@C
CN115312332B (en) MXene-based fiber capacitor electrode and preparation method thereof
CN115424874B (en) MXene-based flexible supercapacitor electrode material and preparation method thereof
CN112018383A (en) Boron-phosphorus co-doped MXene material and preparation method thereof
CN108831749B (en) Electrochemical energy storage composite material and preparation method thereof
CN113991069B (en) In g-C 3 N 4 Preparation process of lead-carbon battery cathode with/ZnO as carbon source
CN113816425B (en) MoS 2 Nitrogen-doped carbon/modified activated carbon sodium ion battery negative electrode material and preparation method thereof
CN112863893B (en) Composite biochar-based material, and preparation method and application thereof
CN114974930A (en) Preparation and application of 1-aminoanthraquinone modified reduced graphene oxide composite material
CN113964306A (en) In g-C3N4Lead-carbon battery cathode material with hydrogen evolution inhibitor as carbon source and cathode
CN113130905A (en) Ultra-small cobalt sulfide nanosheet/carbon cloth composite material and preparation method thereof
CN110627047A (en) Preparation method of graphene/carbon nanotube/nickel disulfide composite aerogel
CN115394564B (en) Preparation method and application of copper triazole/polypyrrole composite electrode material
CN111900345B (en) Silicon-carbon anode material with core-shell structure

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant