CN111627719B - 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 PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 86
- 239000000243 solution Substances 0.000 claims description 75
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- 239000006185 dispersion Substances 0.000 claims description 46
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 40
- 229910009819 Ti3C2 Inorganic materials 0.000 claims description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 35
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- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000002244 precipitate Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 25
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 20
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- 238000009210 therapy by ultrasound Methods 0.000 claims description 20
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- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 6
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- 239000003990 capacitor Substances 0.000 abstract description 8
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- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 15
- 239000002077 nanosphere Substances 0.000 description 7
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 241000446313 Lamella Species 0.000 description 4
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- 239000003575 carbonaceous material Substances 0.000 description 3
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- 230000009286 beneficial effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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
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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 super capacitor electrode is improved.
Description
[ 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 ] A method for producing a semiconductor device
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 shrinkage of polymers, so that the cycling stability of the material is influenced to a great extent, and the application of the material is limited.
[ 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 3, Ti obtained in the step 13C2Precooling after ultrasonic dispersion to obtain a dispersion liquid E; and mixing the reaction liquid D and the dispersion liquid E, stirring, standing to obtain a suspension F, carrying out suction filtration on the suspension F to obtain a precipitate, 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.
The invention is further improved in that:
preferably, the specific process of step 1 is: 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, the ratio of LiF to hydrochloric acid solution in the LiF dispersion 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.
The conductive polymer hollow sphere PACP @ titanium carbide composite material prepared by any one of the preparation methods is characterized in that the PACP is hollow sphere, the titanium carbide is in a lamellar shape, and the PACP hollow spheres are uniformly distributed on 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 material3C2The @ 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, the 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.
Further, in the step 2, ammonium persulfate is precooled, 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 the accumulation and self-assembly of pure PACP, and 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 made 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.
Weighing 2g of LiF and 20mL of 9M HCl (specifically, 15mL of concentrated HCl +5mL of water with a mass concentration of 36%) and adding the LiF and the HCl 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.
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 water bath on the obtained mixed solution for 30min respectively 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
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.
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 (2) is increased by 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 pt electrode 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
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.
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; adding the reaction solution D dropwise into the dispersionStirring the solution E for 30s, standing the solution 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
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.
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 washing the washed precipitateFreeze drying to obtain Ti3C2@PACP。
Example 4
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.
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 (2)
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；
The specific process of 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 Ti3C2Powder; in the LiF dispersion, the ratio of LiF to hydrochloric acid solution was 2 g: 20 mL; the vacuum oxygen discharge time is 2 hours, the ultrasonic treatment time is 1 hour, and the centrifugal treatment time is 1 hour;
step 2, adding aniline, pyrrole and TX-100 into deionized water, and sequentially stirring, performing ultrasonic treatment and 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;
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 is a mixed solution of 1.9g of ammonium persulfate and 15mL of deionized water;
in the step 2, precooling the ammonium persulfate solution to the temperature of less than 5 ℃; dropwise adding ammonium persulfate into the mixed solution C; adding ammonium persulfate into the mixed solution C, stirring for 30min, and reacting for 4h to obtain a reaction solution D;
step 3, Ti obtained in the step 13C2Precooling after ultrasonic dispersion to obtain a dispersion liquid E; mixing reaction solution D and dispersingStirring the solution E, standing to obtain a suspension F, performing suction filtration on the suspension F to obtain a precipitate, cleaning the precipitate with deionized water, and freeze-drying the cleaned precipitate to obtain a powdery conductive polymer hollow sphere PACP @ titanium carbide composite material;
in step 3, 80-95mg of Ti is taken3C2Adding the mixture into deionized water, carrying out ultrasonic dispersion, and precooling to obtain a dispersion liquid E;
in the step 3, when the reaction liquid D and the dispersion liquid E are mixed, dropwise adding the reaction liquid D into the dispersion liquid E, stirring for 30s, and standing for 8h to obtain a suspension F;
in the conductive polymer hollow sphere PACP @ titanium carbide composite material, the PACP is 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).
2. The conductive polymer hollow sphere PACP @ titanium carbide composite material prepared by the preparation method of claim 1, wherein the PACP is in the shape of a hollow sphere, the titanium carbide is in the shape of a sheet layer, and the PACP hollow spheres are uniformly distributed in Ti3C2The monolithic layer surface of (a).
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