CN111627719A - Conductive polymer hollow sphere PACP @ titanium carbide composite material and preparation method thereof - Google Patents

Conductive polymer hollow sphere PACP @ titanium carbide composite material and preparation method thereof Download PDF

Info

Publication number
CN111627719A
CN111627719A CN202010538068.0A CN202010538068A CN111627719A CN 111627719 A CN111627719 A CN 111627719A CN 202010538068 A CN202010538068 A CN 202010538068A CN 111627719 A CN111627719 A CN 111627719A
Authority
CN
China
Prior art keywords
pacp
solution
composite material
hollow sphere
titanium carbide
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.)
Granted
Application number
CN202010538068.0A
Other languages
Chinese (zh)
Other versions
CN111627719B (en
Inventor
武文玲
柴玉梅
赵春辉
王成威
刘恬甜
卫丹
朱建锋
方园
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.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and Technology
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 Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN202010538068.0A priority Critical patent/CN111627719B/en
Publication of CN111627719A publication Critical patent/CN111627719A/en
Application granted granted Critical
Publication of CN111627719B publication Critical patent/CN111627719B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • 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
    • 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
    • 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 discloses a conductive polymer hollow sphere PACP @ titanium carbide composite material and a preparation method thereof3C2The @ PACP hollow sphere nanocomposite is used as an electrode material of a supercapacitor, the in-situ polymerization method is simple and efficient to operate and environment-friendly, and hollow spherical PACP and layered ultrathin Ti are utilized3C2The composite material is compounded, so that the two materials can be in more sufficient contact, the specific surface area is larger, the particle transmission and diffusion are facilitated, and the energy storage performance of the electrode for the super capacitor is improved.

Description

Conductive polymer hollow sphere PACP @ titanium carbide composite material and preparation method thereof
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of preparation of electrode materials of supercapacitors, and particularly relates to a conductive polymer hollow sphere PACP @ titanium carbide composite material and a preparation method thereof.
[ background of the invention ]
The global consumption of fossil energy and the aggravation of environmental problems have stimulated the interest of people in developing green new energy, and as a novel energy storage device, a super capacitor is widely concerned due to the outstanding advantages of the super capacitor. Compared with the traditional battery, the super capacitor has the advantages of short charging time, outstanding cycling stability, high safety, simple assembly, high power performance, good reversibility and the like, and is widely concerned by scientific researchers. Needless to say, in the near future, the super capacitor will be spread over the aspects of people's life, from small to clothes-wearing and living, to industrial military and military, and has a wide development prospect and an application market. Depending on the energy storage mechanism, supercapacitors can be divided into three categories: (1) electric Double Layer Capacitors (EDLCs), a typical electrode material is a carbon material, such as activated carbon, carbon nanotubes, carbon nanofibers, porous carbon, etc., and has low cost and good stability, but the improvement of energy storage performance is limited due to the limited contact area between the carbon material and the electrolyte; (2) faradaic pseudocapacitors, i.e., pseudo-capacitive capacitors (PCs), typically made of metal oxides and conductive polymers; (3) hybrid Supercapacitors (HCs) whose energy storage principle is based on the combination of the former two electrodes use different electrode materials, wherein the positive electrode generally uses metal oxide or conductive polymer, and the negative electrode is mostly carbon-based material.
Two-dimensional titanium carbide emerging in recent years is a graphene-like lamellar material, and an ultrathin two-dimensional nanosheet has super-strong catalytic performance, photovoltaic performance and electrochemical performance due to the unique morphology structure, smaller particle size, larger surface-to-volume ratio and atomic-level lamellar thickness, and is widely applied to aspects of functional ceramics, photocatalysis, lithium ion batteries, solar cells, biosensors and the like. Polyaniline (PANI) and polypyrrole (PPy) are used as key members in a large family of conductive polymers, and have the characteristics of unique doping/dedoping mechanism, high pseudocapacitance, good conductivity, corrosion resistance, high specific energy, environmental friendliness, easiness in modification and the like, and are widely concerned by the electrode research and development field. However, in operation, the material is likely to be at risk of degradation when the voltage window is above a certain threshold, and below a certain potential window, the material is likely to transform into an insulator. In the working process, the intercalation and deintercalation of ions easily cause the expansion and contraction of polymers, so that the cycling stability of the material is greatly influenced, and the application of the material is limited, therefore, the electrochemical performance needs to be enhanced through modification so as to realize the practical application of the material in the field of energy storage.
[ summary of the invention ]
The invention aims to overcome the defects of the prior art and provides a conductive polymer hollow sphere PACP @ titanium carbide composite material and a preparation method thereof; the method is used for solving the problem that the cycle characteristic of the existing two-dimensional titanium carbide material is unstable in the application process.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a preparation method of a conductive polymer hollow sphere PACP @ titanium carbide composite material comprises the following steps:
step 1, through LiF and Ti3AlC2Preparation of lamellar Ti3C2；
Step 2, adding aniline, pyrrole and TX-100 into deionized water, and sequentially stirring, performing ultrasonic treatment and performing water bath to obtain a mixed solution C; adding the precooled ammonium persulfate solution into the mixed solution C, and stirring for reaction to obtain a reaction solution D;
step 3, Ti obtained in the step 13C2Precooling after ultrasonic dispersion to obtain a dispersion liquid E; mixing the reaction solution D and the dispersion solution E, stirring, standing to obtain a suspension F, suction-filtering the suspension F to obtain a precipitate, and mixingAnd cleaning the precipitate by deionized water, and freeze-drying the cleaned precipitate to obtain the powdery conductive polymer hollow sphere PACP @ titanium carbide composite material.
The invention is further improved in that:
preferably, the specific process of step 1 is as follows: dispersing LiF into a hydrochloric acid solution to obtain LiF dispersion liquid, and adding Ti into the LiF dispersion liquid3AlC2Magnetically stirring to obtain reaction liquid A, wherein LiF dispersion liquid and Ti3AlC2The mixing ratio of (A) to (B) was 20 mL: 2g of the total weight of the mixture; washing the reaction solution A by deionized water until the pH value of the reaction solution A is more than 6, then centrifuging, dispersing the centrifuged precipitate in water to obtain a dispersion solution B, carrying out vacuum oxygen discharge and ultrasonic treatment on the dispersion solution B, centrifuging, and freeze-drying the centrifuged supernatant to obtain lamellar Ti3C2And (3) powder.
Preferably, in the LiF dispersion, the ratio of LiF to hydrochloric acid solution is 2 g: 20 mL.
Preferably, the vacuum oxygen discharge time is 2h, the ultrasonic treatment time is 1h, and the centrifugal treatment time is 1 h.
Preferably, in the step 2, the ammonium persulfate solution is pre-cooled to the temperature of less than 5 ℃; dropwise adding ammonium persulfate into the mixed solution C; and adding ammonium persulfate into the mixed solution C, stirring for 30min, and reacting for 4h to obtain a reaction solution D.
Preferably, in step 2, the ratio of aniline, pyrrole, TX-100 and deionized water is: 0.38 mL: 0.29 mL: 0.06 g: 60 mL; the ammonium persulfate solution was a mixed solution of 1.9g of ammonium persulfate and 15mL of deionized water.
Preferably, in step 3, 80-95mg of Ti is taken3C2Adding the mixture into deionized water for ultrasonic dispersion, and precooling to obtain a dispersion liquid E.
Preferably, in step 3, when mixing the reaction solution D and the dispersion solution E, the reaction solution D is added dropwise to the dispersion solution E, and then stirred for 30s and left standing for 8h to obtain a suspension F.
A conductive polymer hollow sphere PACP @ titanium carbide composite material prepared by any one of the preparation methods is disclosed, wherein the PACP is a hollow sphere,the titanium carbide is in a sheet layer shape, and the PACP hollow spheres are uniformly distributed in the Ti3C2The monolithic layer surface of (a).
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a conductive polymer hollow sphere PACP @ titanium carbide composite material, which comprises the steps of firstly synthesizing a PACP (copolymer of polyaniline PANI and polypyrrole PPy) hollow sphere by a chemical oxidation method under a low temperature condition, and then compounding the PACP hollow sphere with ultrathin titanium carbide to obtain Ti3C2The @ PACP hollow sphere nano composite material is used as an electrode material of the supercapacitor; in the process of forming the hollow sphere, TX-100 is used as a surfactant, micelles can be formed in a solution, aniline and pyrrole are sequentially used as soft templates, and the hollow sphere is formed after polymerization; in the later compounding process, the hollow spherical PACP and the layered ultrathin Ti are utilized3C2The composite material is compounded, so that the two materials can be in more sufficient contact, the specific surface area is larger, particle transmission and diffusion are facilitated, the compounding process is simple, efficient and environment-friendly, and the energy storage performance of the composite material for the supercapacitor electrode can be improved.
Further, LiF is dispersed through a hydrochloric acid solution, so that the LiF dispersion liquid is dispersed more uniformly, and Ti is added into the LiF dispersion liquid3AlC2Magnetically stirring the reaction solution to etch Ti with fluorine ions3AlC2In Al to obtain lamellar Ti3AlC2。
Further, the dispersion liquid B is subjected to vacuum oxygen removal to remove oxygen in the dispersion liquid, so that Ti and C are prevented from being oxidized.
Furthermore, in the step 2, ammonium persulfate is pre-cooled, so that the reaction process of generating the PACP is slow, and the whole reaction can be fully carried out.
The invention also discloses a conductive polymer hollow sphere PACP @ titanium carbide composite material which is lamellar Ti3C2The surface of the monolithic layer is adhered with PACP hollow spheres, and the structure enlarges Ti3C2The surface of the lamella is wrinkled, and Ti is greatly enriched3C2The specific surface area and active sites of the lamella effectively avoid pure PACPStacking and self-assembling, the hollow spherical structure Ti3C2The @ PACP has a large specific surface area, is more favorable for electron transmission and ion diffusion, and enhances the cycle stability of the two-dimensional titanium carbide material in the application process, so that the material is more widely applied, and the preparation work of precursors is well performed for further application in the fields of supercapacitors, lithium ion batteries, electronic induction products and the like.
[ description of the drawings ]
FIG. 1 is a drawing showing hollow spherical PACP @ Ti prepared in example 13C2SEM image of sample
FIG. 2 is a diagram of hollow spherical PACP @ Ti prepared in example 13C2TEM image of a sample
FIG. 3 is a diagram of hollow spherical PACP @ Ti prepared in example 13C2Cyclic voltammogram of the sample.
[ detailed description ] embodiments
The invention is described in further detail below with reference to the accompanying drawings:
in the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention; the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance; furthermore, unless expressly stated or limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly and encompass, for example, both fixed and removable connections; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Step 1, preparation of tabletsLayer Ti3C2Preparation of
Weighing 2g of LiF and 20mL of 9M HCl (specifically, 15mL of concentrated HCl with the mass concentration of 36% and 5mL of water) into a polytetrafluoroethylene beaker, and stirring for 10min to uniformly disperse the LiF into a hydrochloric acid solution to obtain a LiF dispersion solution; 2g of Ti are slowly added to the LiF dispersion3AlC2Magnetically stirring for 24 hr to obtain reaction liquid A, in which the fluorine ions are coupled to Ti3And etching the AlC to etch away Al ions in the AlC. Washing the reaction solution A with ionized water until the pH value is more than 6, then centrifuging, dissolving the centrifuged precipitate in 300mL of ultrapure water to obtain a dispersion solution B, carrying out vacuum oxygen discharge on the dispersion solution B for 2h, carrying out ultrasonic treatment for 1h after the completion, centrifuging for 1h, and freeze-drying the centrifuged supernatant to obtain lamellar Ti3C2And (3) powder.
Step 2, preparing PACP mixed liquid
Weighing 0.38mL of aniline and 0.29mL of pyrrole, mixing in a beaker, adding 60mL of deionized water and 0.06gTX-100 (surfactant), and sequentially stirring, performing ultrasonic treatment and performing water bath for 30min to obtain a mixed solution C; weighing 1.9g of Ammonium Persulfate (APS) and 15mL of deionized water, mixing to obtain an ammonium persulfate solution, precooling the ammonium persulfate solution, cooling to the temperature of the ammonium persulfate less than 5 ℃, dropwise adding the precooled ammonium persulfate solution into the mixed solution C, reacting slowly in the whole process, stirring for 30min, and reacting for 4h to obtain a reaction solution D;
step 3, preparing Ti3C2@ PACP hollow nanospheres
Taking 80-95mg of Ti3C2Adding into deionized water, performing ultrasonic dispersion for 5min, stirring for 25min, and precooling for 10min to obtain dispersion E; dropwise adding the reaction liquid D into the dispersion liquid E, stirring for 30s, standing for reaction for 8h to obtain a suspension F, carrying out suction filtration on the suspension F to obtain a precipitate, washing the precipitate with deionized water for three times, and freeze-drying the washed precipitate to obtain Ti3C2@ PACP, wherein PACP is hollow sphere, and PACP hollow sphere is uniformly distributed on Ti3C2The monolithic layer surface of (a).
Example 1
Step 1, lamellar Ti3C2Preparation of
Weighing 2g of LiF and 20mL of 9M HCl (specifically, 15mL of concentrated HCl +5mL of water at a mass concentration of 36% + 15mL of concentrated HCl +5mL of water) into a 50mL polytetrafluoroethylene beaker, stirring for 10min to uniformly disperse LiF into the hydrochloric acid solution, and slowly adding 2g of Ti into the mixed solution3AlC2And magnetically stirring for 24 hours to obtain reaction liquid A. Washing the reaction solution A with ionized water until the pH value is more than 6, then centrifuging, dissolving the centrifuged precipitate in 300mL of ultrapure water to obtain a dispersion solution B, carrying out vacuum oxygen discharge on the dispersion solution B for 2h, carrying out ultrasonic treatment for 1h after the ultrasonic treatment is finished, centrifuging for 1h, and freeze-drying the centrifuged supernatant to obtain a lamellar Ti3C2And (3) powder.
Step 2, preparing PACP mixed liquid
Weighing 0.38mL of aniline and 0.29mL of pyrrole, mixing in a beaker, adding 60mL of deionized water and 0.06gTX-100 (surfactant), and sequentially stirring, performing ultrasonic treatment and performing water bath for 30min to obtain a mixed solution C; weighing 1.9g of Ammonium Persulfate (APS) and 15mL of deionized water, mixing to obtain an ammonium persulfate solution, precooling the ammonium persulfate solution, cooling to the temperature of the ammonium persulfate less than 5 ℃, dropwise adding the precooled ammonium persulfate solution into the mixed solution C, reacting slowly in the whole process, stirring for 30min, and reacting for 4h to obtain a reaction solution D;
step 3, preparing Ti3C2@ PACP hollow nanospheres
80mg of Ti are taken3C2Adding into deionized water, performing ultrasonic dispersion for 5min, stirring for 25min, and precooling for 10min to obtain dispersion E; dropwise adding the reaction liquid D into the dispersion liquid E, stirring for 30s, standing for reaction for 8h to obtain a suspension F, carrying out suction filtration on the suspension F to obtain a precipitate, washing the precipitate with deionized water for three times, and freeze-drying the washed precipitate to obtain Ti3C2@PACP。
Referring to FIGS. 1 and 2, Ti prepared in this example is shown3C2SEM and TEM images of @ PACP, from which it can be seen that the PACP hollow spheres are uniformly distributed in Ti3C2The surface of the monolithic layer of (a),increase Ti3C2The surface of the lamella is wrinkled, and Ti is greatly enriched3C2The specific surface area and active sites of the lamella effectively avoid the accumulation and self-assembly of pure PACP. The results show that Ti is present3C2In the @ PACP nano-multilevel structure, two-phase Ti3C2The hollow structure of the multi-stage structure provides a good buffer structure in the electrode charging and discharging processes, maintains the stability of the electrode structure, and provides a shorter path for charge transmission and ion diffusion in the electrochemical transmission process, thereby providing more electrochemical energy storage capacity.
Ti obtained by the present invention3C2The @ PACP hollow nanosphere material can be directly used as a working electrode of a three-electrode system, the pt electrode is a counter electrode, the SCE is a reference electrode, and the thickness of the material is 0.5M H2SO4As electrolyte, the capacitor performance was tested by electrochemical workstation, the electrochemical performance was tested by Cyclic Voltammetry (CV), and the Ti was tested by testing3C2The electrochemical performance of the @ PACP hollow nanospheres is shown in FIG. 3, and it can be obviously seen that the shape of the cyclic voltammetry curve does not deform along with the increase of the scanning rate, which indicates the good rate performance and chemical stability of the cyclic voltammetry curve; in addition, the electrochemical specific capacity is large as calculated by CV specific capacitance, and Ti is added when the scanning speed is 5mv/s3C2The specific capacitance of the @ PACP nano hollow sphere electrode material can reach 260.43F g-1。
Example 2
Step 1, lamellar Ti3C2Preparation of
Weighing 2g of LiF and 20mL of 9M HCl (specifically, 15mL of concentrated HCl +5mL of water at a mass concentration of 36% + 15mL of concentrated HCl +5mL of water) into a 50mL polytetrafluoroethylene beaker, stirring for 10min to uniformly disperse LiF into the hydrochloric acid solution, and slowly adding 2g of Ti into the mixed solution3AlC2And magnetically stirring for 24 hours to obtain reaction liquid A. Washing the reaction solution A with ionized water until the pH is more than 6, centrifuging, and centrifugingDissolving the precipitate in 300mL of ultrapure water to obtain dispersion liquid B, performing vacuum oxygen discharge on the dispersion liquid B for 2h, performing ultrasonic treatment for 1h, centrifuging for 1h, and freeze-drying the centrifuged supernatant to obtain lamellar Ti3C2And (3) powder.
Step 2, preparing PACP mixed liquid
Weighing 0.38mL of aniline and 0.29mL of pyrrole, mixing in a beaker, adding 60mL of deionized water and 0.06gTX-100 (surfactant), and sequentially stirring, performing ultrasonic treatment and performing water bath for 30min to obtain a mixed solution C; weighing 1.9g of Ammonium Persulfate (APS) and 15mL of deionized water, mixing to obtain an ammonium persulfate solution, precooling the ammonium persulfate solution, cooling to the temperature of the ammonium persulfate less than 5 ℃, dropwise adding the precooled ammonium persulfate solution into the mixed solution C, reacting slowly in the whole process, stirring for 30min, and reacting for 4h to obtain a reaction solution D;
step 3, preparing Ti3C2@ PACP hollow nanospheres
85mg of Ti are taken3C2Adding into deionized water, performing ultrasonic dispersion for 5min, stirring for 25min, and precooling for 10min to obtain dispersion E; dropwise adding the reaction liquid D into the dispersion liquid E, stirring for 30s, standing for reaction for 8h to obtain a suspension F, carrying out suction filtration on the suspension F to obtain a precipitate, washing the precipitate with deionized water for three times, and freeze-drying the washed precipitate to obtain Ti3C2@PACP。
Example 3
Step 1, lamellar Ti3C2Preparation of
Weighing 2g of LiF and 20mL of 9M HCl (specifically, 15mL of concentrated HCl +5mL of water at a mass concentration of 36% + 15mL of concentrated HCl +5mL of water) into a 50mL polytetrafluoroethylene beaker, stirring for 10min to uniformly disperse LiF into the hydrochloric acid solution, and slowly adding 2g of Ti into the mixed solution3AlC2And magnetically stirring for 24 hours to obtain reaction liquid A. Washing the reaction solution A with ionized water until the pH value is more than 6, then centrifuging, dissolving the centrifuged precipitate in 300mL of ultrapure water to obtain a dispersion solution B, carrying out vacuum oxygen discharge on the dispersion solution B for 2h, carrying out ultrasonic treatment for 1h after the ultrasonic treatment is finished, centrifuging for 1h, and freeze-drying the centrifuged supernatant to obtain the productLamellar Ti3C2And (3) powder.
Step 2, preparing PACP mixed liquid
Weighing 0.38mL of aniline and 0.29mL of pyrrole, mixing in a beaker, adding 60mL of deionized water and 0.06gTX-100 (surfactant), and sequentially stirring, performing ultrasonic treatment and performing water bath for 30min to obtain a mixed solution C; weighing 1.9g of Ammonium Persulfate (APS) and 15mL of deionized water, mixing to obtain an ammonium persulfate solution, precooling the ammonium persulfate solution, cooling to the temperature of the ammonium persulfate less than 5 ℃, dropwise adding the precooled ammonium persulfate solution into the mixed solution C, reacting slowly in the whole process, stirring for 30min, and reacting for 4h to obtain a reaction solution D;
step 3, preparing Ti3C2@ PACP hollow nanospheres
Taking 90mg of Ti3C2Adding into deionized water, performing ultrasonic dispersion for 5min, stirring for 25min, and precooling for 10min to obtain dispersion E; dropwise adding the reaction liquid D into the dispersion liquid E, stirring for 30s, standing for reaction for 8h to obtain a suspension F, carrying out suction filtration on the suspension F to obtain a precipitate, washing the precipitate with deionized water for three times, and freeze-drying the washed precipitate to obtain Ti3C2@PACP。
Example 4
Step 1, lamellar Ti3C2Preparation of
Weighing 2g of LiF and 20mL of 9M HCl (specifically, 15mL of concentrated HCl +5mL of water at a mass concentration of 36% + 15mL of concentrated HCl +5mL of water) into a 50mL polytetrafluoroethylene beaker, stirring for 10min to uniformly disperse LiF into the hydrochloric acid solution, and slowly adding 2g of Ti into the mixed solution3AlC2And magnetically stirring for 24 hours to obtain reaction liquid A. Washing the reaction solution A with ionized water until the pH value is more than 6, then centrifuging, dissolving the centrifuged precipitate in 300mL of ultrapure water to obtain a dispersion solution B, carrying out vacuum oxygen discharge on the dispersion solution B for 2h, carrying out ultrasonic treatment for 1h after the ultrasonic treatment is finished, centrifuging for 1h, and freeze-drying the centrifuged supernatant to obtain a lamellar Ti3C2And (3) powder.
Step 2, preparing PACP mixed liquid
Weighing 0.38mL of aniline and 0.29mL of pyrrole, mixing in a beaker, adding 60mL of deionized water and 0.06gTX-100 (surfactant), and sequentially stirring, performing ultrasonic treatment and performing water bath for 30min to obtain a mixed solution C; weighing 1.9g of Ammonium Persulfate (APS) and 15mL of deionized water, mixing to obtain an ammonium persulfate solution, precooling the ammonium persulfate solution, cooling to the temperature of the ammonium persulfate less than 5 ℃, dropwise adding the precooled ammonium persulfate solution into the mixed solution C, reacting slowly in the whole process, stirring for 30min, and reacting for 4h to obtain a reaction solution D;
step 3, preparing Ti3C2@ PACP hollow nanospheres
Taking 95mg of Ti3C2Adding into deionized water, performing ultrasonic dispersion for 5min, stirring for 25min, and precooling for 10min to obtain dispersion E; dropwise adding the reaction liquid D into the dispersion liquid E, stirring for 30s, standing for reaction for 8h to obtain a suspension F, carrying out suction filtration on the suspension F to obtain a precipitate, washing the precipitate with deionized water for three times, and freeze-drying the washed precipitate to obtain Ti3C2@PACP。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. A preparation method of a conductive polymer hollow sphere PACP @ titanium carbide composite material is characterized by comprising the following steps:
step 1, through LiF and Ti3AlC2Preparation of lamellar Ti3C2；
Step 2, adding aniline, pyrrole and TX-100 into deionized water, and sequentially stirring, performing ultrasonic treatment and performing water bath to obtain a mixed solution C; adding the precooled ammonium persulfate solution into the mixed solution C, and stirring for reaction to obtain a reaction solution D;
step 3, Ti obtained in the step 13C2Precooling after ultrasonic dispersion to obtain a dispersion liquid E; mixing the reaction solution D and the dispersion solution E, stirring, standing to obtain a suspension F, and performing suction filtration on the suspension F to obtain the dispersionAnd cleaning the precipitate with deionized water, and freeze-drying the cleaned precipitate to obtain the powdery conductive polymer hollow sphere PACP @ titanium carbide composite material.
2. The preparation method of the conductive polymer hollow sphere PACP @ titanium carbide composite material according to claim 1, wherein the specific process in the step 1 is as follows: dispersing LiF into a hydrochloric acid solution to obtain LiF dispersion liquid, and adding Ti into the LiF dispersion liquid3AlC2Magnetically stirring to obtain reaction liquid A, wherein LiF dispersion liquid and Ti3AlC2The mixing ratio of (A) to (B) was 20 mL: 2g of the total weight of the mixture; washing the reaction solution A by deionized water until the pH value of the reaction solution A is more than 6, then centrifuging, dispersing the centrifuged precipitate in water to obtain a dispersion solution B, carrying out vacuum oxygen discharge and ultrasonic treatment on the dispersion solution B, centrifuging, and freeze-drying the centrifuged supernatant to obtain lamellar Ti3C2And (3) powder.
3. The preparation method of the conductive polymer hollow sphere PACP @ titanium carbide composite material as claimed in claim 2, wherein in the LiF dispersion, the ratio of LiF to the hydrochloric acid solution is 2 g: 20 mL.
4. The preparation method of the conductive polymer hollow sphere PACP @ titanium carbide composite material as claimed in claim 2, wherein the vacuum oxygen discharge time is 2 hours, the ultrasonic treatment time is 1 hour, and the centrifugal treatment time is 1 hour.
5. The preparation method of the conductive polymer hollow sphere PACP @ titanium carbide composite material according to claim 1, wherein in the step 2, an ammonium persulfate solution is pre-cooled to a temperature of less than 5 ℃; dropwise adding ammonium persulfate into the mixed solution C; and adding ammonium persulfate into the mixed solution C, stirring for 30min, and reacting for 4h to obtain a reaction solution D.
6. The preparation method of the conductive polymer hollow sphere PACP @ titanium carbide composite material according to claim 1, wherein in the step 2, the ratio of aniline, pyrrole, TX-100 and deionized water is as follows: 0.38 mL: 0.29 mL: 0.06 g: 60 mL; the ammonium persulfate solution was a mixed solution of 1.9g of ammonium persulfate and 15mL of deionized water.
7. The preparation method of the conductive polymer hollow sphere PACP @ titanium carbide composite material as claimed in claim 6, wherein in the step 3, 80-95mg of Ti is taken3C2Adding the mixture into deionized water for ultrasonic dispersion, and precooling to obtain a dispersion liquid E.
8. The preparation method of the conductive polymer hollow sphere PACP @ titanium carbide composite material as claimed in claim 1, wherein in the step 3, when the reaction solution D and the dispersion solution E are mixed, the reaction solution D is dropwise added into the dispersion solution E, and then the mixture is stirred for 30s and kept stand for 8h to obtain a suspension F.
9. A conductive polymer hollow sphere PACP @ titanium carbide composite material prepared by the preparation method of any one of claims 1 to 8, wherein the PACP is in the shape of a hollow sphere, the titanium carbide is in the shape of a sheet, and the PACP hollow spheres are uniformly distributed in Ti3C2The monolithic layer surface of (a).
CN202010538068.0A 2020-06-12 2020-06-12 Conductive polymer hollow sphere PACP @ titanium carbide composite material and preparation method thereof Active CN111627719B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010538068.0A CN111627719B (en) 2020-06-12 2020-06-12 Conductive polymer hollow sphere PACP @ titanium carbide composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010538068.0A CN111627719B (en) 2020-06-12 2020-06-12 Conductive polymer hollow sphere PACP @ titanium carbide composite material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111627719A true CN111627719A (en) 2020-09-04
CN111627719B CN111627719B (en) 2022-06-21

Family

ID=72261284

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010538068.0A Active CN111627719B (en) 2020-06-12 2020-06-12 Conductive polymer hollow sphere PACP @ titanium carbide composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111627719B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112292015A (en) * 2020-11-10 2021-01-29 上海海事大学 MXene/PPy composite wave absorbing agent and preparation method thereof
CN112409657A (en) * 2020-12-04 2021-02-26 深圳市腾顺电子材料有限公司 Improved conductive rubber composition and method for making same
CN114883115A (en) * 2022-04-14 2022-08-09 净海新能源科技创新(镇江)有限公司 Composite material with high specific capacity and preparation method and application thereof
CN115602454A (en) * 2022-12-12 2023-01-13 深圳市今朝时代股份有限公司（Cn） Super capacitor pole piece and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012051641A1 (en) * 2010-10-22 2012-04-26 University Of Queensland Metal oxide particles
CN104591127A (en) * 2015-01-09 2015-05-06 中山大学 Ultrahigh-specific-area hollow carbon nano-spheres as well as preparation method and application thereof
CN106589362A (en) * 2016-12-22 2017-04-26 陕西科技大学 Polyaniline nano particle/two-dimensional layered titanium carbide composite material and low-temperature preparation method of polyaniline nano particle/two-dimensional layered titanium carbide composite material
CN106750277A (en) * 2016-12-05 2017-05-31 哈尔滨工业大学 A kind of MXene polyaniline composite materials and preparation method thereof
CN108689397A (en) * 2017-04-10 2018-10-23 中国科学院苏州纳米技术与纳米仿生研究所 A kind of carbon hollow ball aeroge, preparation method and application
CN109003836A (en) * 2018-08-13 2018-12-14 湖北汽车工业学院 A kind of preparation method based on MXene flexible fabric electrode and its application in supercapacitor
US10519580B2 (en) * 2011-06-10 2019-12-31 South Dakota Board Of Regents Titanium carbide (TiC) nano-fibrous felts

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012051641A1 (en) * 2010-10-22 2012-04-26 University Of Queensland Metal oxide particles
US10519580B2 (en) * 2011-06-10 2019-12-31 South Dakota Board Of Regents Titanium carbide (TiC) nano-fibrous felts
CN104591127A (en) * 2015-01-09 2015-05-06 中山大学 Ultrahigh-specific-area hollow carbon nano-spheres as well as preparation method and application thereof
CN106750277A (en) * 2016-12-05 2017-05-31 哈尔滨工业大学 A kind of MXene polyaniline composite materials and preparation method thereof
CN106589362A (en) * 2016-12-22 2017-04-26 陕西科技大学 Polyaniline nano particle/two-dimensional layered titanium carbide composite material and low-temperature preparation method of polyaniline nano particle/two-dimensional layered titanium carbide composite material
CN108689397A (en) * 2017-04-10 2018-10-23 中国科学院苏州纳米技术与纳米仿生研究所 A kind of carbon hollow ball aeroge, preparation method and application
CN109003836A (en) * 2018-08-13 2018-12-14 湖北汽车工业学院 A kind of preparation method based on MXene flexible fabric electrode and its application in supercapacitor

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112292015A (en) * 2020-11-10 2021-01-29 上海海事大学 MXene/PPy composite wave absorbing agent and preparation method thereof
CN112409657A (en) * 2020-12-04 2021-02-26 深圳市腾顺电子材料有限公司 Improved conductive rubber composition and method for making same
CN112409657B (en) * 2020-12-04 2021-08-24 深圳市腾顺电子材料有限公司 Improved conductive rubber composition and method for making same
CN114883115A (en) * 2022-04-14 2022-08-09 净海新能源科技创新(镇江)有限公司 Composite material with high specific capacity and preparation method and application thereof
CN115602454A (en) * 2022-12-12 2023-01-13 深圳市今朝时代股份有限公司（Cn） Super capacitor pole piece and preparation method thereof

Also Published As

Publication number Publication date
CN111627719B (en) 2022-06-21

Similar Documents

Publication Publication Date Title
CN111627719B (en) Conductive polymer hollow sphere PACP @ titanium carbide composite material and preparation method thereof
Peng et al. Low-cost and high energy density asymmetric supercapacitors based on polyaniline nanotubes and MoO 3 nanobelts
Xu et al. Facile preparation of hierarchical vanadium pentoxide (V2O5)/titanium dioxide (TiO2) heterojunction composite nano-arrays for high performance supercapacitor
CN111883366A (en) Polypyrrole nanosphere @ titanium carbide composite material and preparation method and application thereof
Wu et al. An aqueous 2.1 V pseudocapacitor with MXene and V-MnO2 electrodes
CN113012945B (en) Modified Ppy-MXene composite material, and preparation method and application thereof
Xu et al. Synthesis of heterostructure SnO2/graphitic carbon nitride composite for high-performance electrochemical supercapacitor
Yang et al. Realizing high-performance lithium ion hybrid capacitor with a 3D MXene-carbon nanotube composite anode
Alam et al. Binary composites of sonochemically synthesized cobalt phosphates/polyaniline for supercapattery devices
US20200283306A1 (en) Preparation method of hexagonal molybdenum oxide nanorod
CN110336002A (en) Nitrogen-doped carbon-coated zinc oxide composite nano material for lithium ion battery
CN107346711A (en) A kind of composite PANI/Ti3C2TxPreparation and application
CN114854030A (en) Preparation method of single-layer MXene nanosheet/ZIF-67 composite material
Ge et al. Electrochemical performance of MoO3-RuO2/Ti in H2SO4 electrolyte as anodes for asymmetric supercapacitors
Koventhan et al. Development of a polyaniline/CMK-3/hydroquinone composite supercapacitor system
CN110310838B (en) Hollow nano cage composite material and preparation method and application thereof
CN111063549B (en) Two-dimensional MOFs nanosheet-derived full-electrode material for hybrid capacitor
CN109473292B (en) Preparation method and application of niobium nitride/reduced graphene oxide nanocomposite
CN113929146B (en) MnO/Mn with core-shell structure 3 O 4 Preparation and application of electrode material
CN111599600B (en) Preparation method and application of graphene/iron oxyhydroxide/polyaniline supercapacitor positive electrode material
CN110745863B (en) Preparation method of zinc titanate/reduced graphene oxide nanocomposite and application of zinc titanate/reduced graphene oxide nanocomposite to lithium ion capacitor
CN110655112B (en) Manganese oxide positive electrode material of water-based battery and preparation method and application thereof
CN105731520B (en) A kind of preparation method by organic composite precursor synthesis height ratio capacity ZnO
Mehta et al. Microwave synthesis of plant-based supercapacitor electrodes for flexible electronics
Wu et al. Flexible asymmetric supercapacitor with crosslinked polyacrylate containing double ions as solid electrolyte

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