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CN-121991341-A - 1,5 Naphthalene disulfonic acid modified polypyrrole/MXene composite material and in-situ preparation method and application thereof

CN121991341ACN 121991341 ACN121991341 ACN 121991341ACN-121991341-A

Abstract

The invention discloses a1, 5 naphthalene disulfonic acid modified polypyrrole/MXene composite material, and an in-situ preparation method and application thereof. The pyrrole monomer, 1,5 naphthalene disulfonic acid and MXene colloidal solution are uniformly mixed and prepared by a one-step in-situ polymerization method. The specific capacitance of polypyrrole is 151F/g under the condition of 0.5A/g of current density, and the specific capacitance of the 1,5 naphthalene disulfonic acid modified polypyrrole/MXene composite material is up to 714F/g, and compared with the polypyrrole, the specific capacitance is improved by 4.7 times. The capacity retention rate of polypyrrole after 5000 times of circulation is only 33.5%, and the capacity retention rate of the symmetrical supercapacitor assembled by the composite material after 10000 times of circulation is as high as 99.8%, compared with polypyrrole, the composite material has excellent circulation stability, and the problems of low specific capacitance and poor circulation stability of the conventional conductive polymer are effectively solved.

Inventors

  • LI SHIYUN
  • YAN SHUAI
  • HAO QIANCHENG
  • YU ZHOU
  • HUANG LINGYAN

Assignees

  • 江苏科技大学

Dates

Publication Date
20260508
Application Date
20260206

Claims (10)

  1. 1. The preparation method for preparing the 1,5 naphthalene disulfonic acid modified polypyrrole/MXene composite material in situ is characterized by comprising the following steps of: and adding the MXene colloidal solution into a mixed solution containing pyrrole monomers and 1,5 naphthalene disulfonic acid, slowly dripping the solution into a ferric trichloride hexahydrate solution, performing in-situ polymerization under ice water bath, centrifugally separating, washing, and drying in vacuum to obtain the in-situ preparation 1,5 naphthalene disulfonic acid modified polypyrrole/MXene composite material.
  2. 2. The preparation method of claim 1, wherein the concentration of the MXene colloidal solution is 1-10 mg/mL, the molar ratio of the pyrrole monomer to the 1,5 naphthalene disulfonic acid is 1:0.03-1:0.1, and the mass of the MXene accounts for 0.5% -5% of the mass of the pyrrole monomer.
  3. 3. The preparation method according to claim 1, wherein the concentration of the ferric trichloride hexahydrate solution is 0.2-0.8 mmol/L, and the in-situ polymerization time is 3-6 hours.
  4. 4. The preparation method according to claim 1, wherein the time of vacuum drying is 12-24 hours and the temperature of vacuum drying is 20-60 ℃.
  5. 5. The 1,5 naphthalene disulfonic acid modified polypyrrole/MXene composite material obtained by the preparation method of any one of claims 1 to 4.
  6. 6. An electrode sheet prepared by using the polypyrrole/MXene composite material modified by 1,5 naphthalene disulfonic acid according to claim 5.
  7. 7. The electrode sheet according to claim 6, wherein the 1,5 naphthalene disulfonic acid modified polypyrrole/MXene composite material is mixed with acetylene black and polyvinylidene fluoride, and dissolved in N-methyl pyrrolidone to obtain a slurry, and the slurry is uniformly smeared on graphite paper, and vacuum-dried to obtain the electrode sheet.
  8. 8. The electrode sheet according to claim 7, wherein the mass ratio of the 1,5 naphthalene disulfonic acid modified polypyrrole/MXene composite material to the acetylene black and the polyvinylidene fluoride is 6-8:1-2:0.5-1.
  9. 9. A symmetrical supercapacitor comprising the electrode sheet of claim 5 or any one of claims 6 to 8.
  10. 10. The symmetrical supercapacitor according to claim 9, wherein the electrode plates comprising the 1,5 naphthalene disulfonic acid modified polypyrrole/MXene composite material are used as cathode and anode, respectively, and the H 2 SO 4 solution is used as electrolyte, to assemble the symmetrical supercapacitor.

Description

1,5 Naphthalene disulfonic acid modified polypyrrole/MXene composite material and in-situ preparation method and application thereof Technical Field The invention relates to a 1,5 naphthalene disulfonic acid modified polypyrrole/MXene composite material, and an in-situ preparation method and application thereof, and belongs to the field of composite materials. Background In recent years, with the rapid development of intelligent electronic technology, great commercial interest has been generated in flexible, portable and wearable devices. Extensive research is therefore being conducted to meet the increasing demands on next generation energy storage systems. Supercapacitors are a class of energy storage devices that hold great promise for excellent power density, significantly reduced charge times, and extremely long cycle life. The fundamental goal in developing such devices is to achieve both high energy and high power density. The current supercapacitors are still significantly deficient in energy density, limiting their wide application in situations where high energy output is required, while their relatively low energy density and low cycle efficiency limit further use. In addition, the polymer electrode material is easy to aggregate in the compounding process, so that the effective active area is reduced, and the charge transmission efficiency is influenced. The compatibility between the electrode and the electrolyte, the interfacial charge transfer kinetics, and the mechanical stability of the material during cycling are also critical issues to be addressed. Therefore, developing a composite electrode material with high energy density, excellent cycling stability and efficient interfacial charge transport is an important direction to promote the development of supercapacitor technology. The polypyrrole conductive polymer has excellent performance, can realize efficient reversible Faraday redox reaction, has excellent charge storage and transmission capacity and has the advantages of easy synthesis, sustainable environment, adjustable conductivity, obvious redox activity and the like, and is a powerful candidate material for the high-performance supercapacitor electrode. Polypyrrole has unique position in the field of super capacitors and is a typical conjugated conductive polymer. Polypyrrole has various oxidation states, and the oxidation states of the polypyrrole change in the doping and dedoping processes, so that charge storage and release are realized. The charge storage device can realize charge storage through rapid oxidation-reduction reaction, and further has excellent environmental stability, is relatively stable in air and is not easy to oxidize or degrade. Polypyrrole can be prepared by electrochemical or chemical oxidation polymerization of pyrrole monomers at present. However, polypyrrole has a relatively limited effective surface area, limits rapid transport of electrolyte ions, and reduces the availability of electroactive sites, which leads to their susceptibility to structural degradation and volumetric expansion during long-term cycling, resulting in poor cycling stability and specific capacity. Disclosure of Invention The first object of the invention is to provide a1, 5 naphthalene disulfonic acid modified polypyrrole/MXene composite material, which solves the problems of volume shrinkage and expansion, poor long-cycle stability and the like of the conductive polymer material at the present stage. The second object of the invention is to provide a preparation method for preparing the 1,5 naphthalene disulfonic acid modified polypyrrole/MXene electrode composite material in situ. The third object of the invention is to provide an electrode plate prepared by using the 1,5 naphthalene disulfonic acid modified polypyrrole/MXene composite material, and the last object of the invention is to provide the 1,5 naphthalene disulfonic acid modified polypyrrole/MXene composite material or the application of the electrode plate in a symmetrical super capacitor. The preparation method of the 1,5 naphthalene disulfonic acid modified polypyrrole/MXene composite material comprises the following steps: and adding the MXene colloidal solution into a mixed solution containing pyrrole monomers and 1,5 naphthalene disulfonic acid, slowly dripping the solution into a ferric trichloride hexahydrate solution, performing in-situ polymerization under ice water bath, centrifugally separating, washing, and drying in vacuum to obtain the in-situ preparation 1,5 naphthalene disulfonic acid modified polypyrrole/MXene composite material. Further, the concentration of the MXene colloidal solution is 1-10 mg/mL, the molar ratio of the pyrrole monomer to the 1,5 naphthalene disulfonic acid is 1:0.03-1:0.1, and the mass of the MXene accounts for 0.5% -5% of the mass of the pyrrole monomer. Preferably, the molar ratio of the pyrrole monomer to the 1,5 naphthalene disulfonic acid is 1:0.05-1:0.1, the mass of MXene ac