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CN-122013441-A - Stretchable elastic carbon nanofiber membrane material and preparation method thereof

CN122013441ACN 122013441 ACN122013441 ACN 122013441ACN-122013441-A

Abstract

The invention discloses a stretchable elastic carbon nanofiber membrane material and a preparation method thereof. The preparation method comprises the following steps of respectively dissolving polystyrene and carbon precursor polymers to prepare spinning solutions, spinning according to a certain combination sequence to obtain a multi-layer carbon precursor nanofiber membrane, inducing the construction of a carbon precursor nanofiber membrane micro buckling structure by utilizing the thermal contraction effect of a polystyrene layer, dissolving and removing polystyrene by ethyl acetate to obtain a nanofiber membrane only retaining pure carbon precursor, and finally performing pre-oxidation and carbonization to obtain the stretchable elastic carbon nanofiber membrane. The elastic carbon nanofiber membrane prepared by the invention has excellent stretchable rebound performance, high conductivity and high specific surface area, and can be applied to the application fields of national defense and military industry, energy environment protection, aerospace, flexible electronics and the like.

Inventors

  • ZHONG ZHAOXIANG
  • He Wentai
  • ZENG YIQING
  • XING WEIHONG

Assignees

  • 南京工业大学
  • 南京工业大学苏州未来膜技术创新中心

Dates

Publication Date
20260512
Application Date
20260324

Claims (7)

  1. 1. The preparation method of the stretchable elastic carbon nanofiber membrane material is characterized by comprising the following steps of: S1, dissolving a carbon precursor polymer in a solvent, and uniformly stirring by magnetic force to obtain a carbon precursor solution A; S2, dissolving polystyrene in a solvent, and uniformly stirring by magnetic force to obtain spinning solution B; S3, carrying out electrostatic spinning on the solution A and the solution B according to a certain combination sequence, stripping the solution A and the solution B from the base material after a certain time, and then drying the base material in an oven for a certain time to obtain a multi-layer carbon precursor nanofiber membrane C; S4, heating the obtained multi-layer carbon precursor nanofiber membrane C to a certain temperature in an air atmosphere for pre-shrinking, keeping the temperature for a period of time, cooling, and then slowly stirring in a certain solvent for a certain time to dissolve and remove polystyrene, so as to obtain a single-layer pure carbon precursor nanofiber membrane D; S5, heating the single-layer pure carbon precursor nanofiber membrane D to a certain temperature in an air atmosphere for pre-oxidation, heating to a certain temperature at a certain heating rate in an inert atmosphere for carbonization, and cooling after heat preservation for a period of time to prepare the stretchable elastic carbon nanofiber membrane material.
  2. 2. The stretchable elastic carbon nanofiber membrane material and the preparation method thereof according to claim 1 are characterized in that in S1, the carbon precursor polymer is at least one of polyacrylonitrile, polyimide, polyvinylpyrrolidone and polyvinyl alcohol, the solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, acetone, dichloromethane, acetylacetone and toluene, and the concentration of the carbon precursor polymer in the carbon precursor solution A is 8-20wt%.
  3. 3. The stretchable elastic carbon nanofiber membrane material and the preparation method thereof according to claim 1 are characterized in that in the S2, the solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, acetone, methylene dichloride and toluene, and the concentration of polystyrene in the spinning solution B is 10-18wt%.
  4. 4. The stretchable elastic carbon nanofiber membrane material and the preparation method thereof according to claim 1 are characterized in that in the step S3, the combination sequence can be one of a polystyrene/carbon precursor nanofiber double-layer membrane, a polystyrene/carbon precursor-polystyrene/carbon precursor nanofiber sandwich membrane, a polystyrene/carbon precursor/polystyrene nanofiber sandwich membrane, a polystyrene/carbon precursor-polystyrene/polystyrene nanofiber sandwich membrane or a carbon precursor/polystyrene/carbon precursor nanofiber sandwich membrane, the process parameters of the electrostatic spinning process are that the environment temperature is 20-30 ℃, the humidity is 20% -60%, the injection speed is 1-2 mL/h, the positive voltage is 12-24 kV, the negative voltage is-1.0-2.0 kV, the receiving distance is 15-20 cm, the receiving speed is 50-100 r/min, the receiving substrate comprises one of silicone paper, release paper, non-woven fabric, tin foil paper and a metal copper mesh, the drying temperature is 50-70 ℃ and the drying time is 6-6 ℃.
  5. 5. The stretchable elastic carbon nanofiber membrane material and the preparation method thereof according to claim 1 are characterized in that in the step S4, the pre-shrinking temperature is raised to 120-150 ℃ from room temperature, the temperature raising rate is 5-10 ℃ per minute, the heat preservation time is 0.5-1 h, the solvent is ethyl acetate, the stirring speed is 100-200 rpm, and the stirring time is 8-24 h.
  6. 6. The stretchable elastic carbon nanofiber membrane material and the preparation method thereof according to claim 1 are characterized in that in the step S5, the pre-oxidation temperature is raised to 240-290 ℃ from room temperature, the temperature raising rate is 1-5 ℃ per minute, and the heat preservation time is 1-5 h.
  7. 7. The stretchable elastic carbon nanofiber membrane material and the preparation method thereof according to claim 1 are characterized in that in the step S5, the inert atmosphere is at least one of nitrogen and argon, the carbonization temperature is raised from room temperature to 600-900 ℃, the temperature raising rate is 1-5 ℃ per minute, and the heat preservation time is 1-5 h.

Description

Stretchable elastic carbon nanofiber membrane material and preparation method thereof Technical Field The invention belongs to the technical field of carbon nanofiber membranes, and particularly relates to a stretchable elastic carbon nanofiber membrane material and a preparation method thereof. Background Along with the rapid development of flexible wearable electronic equipment, intelligent strain sensing and novel flexible energy storage devices, urgent demands are made on flexible matrix materials with excellent mechanical flexibility, high conductivity and high electrochemical activity. Among the candidate materials, the carbon nanofiber membrane has a three-dimensional connected porous network structure, a high specific surface area, excellent electron conduction capacity and excellent physicochemical stability, and thus has a wide application prospect in the front field. The conventional carbon nanofiber membrane is generally prepared from a polymer precursor solution through electrostatic spinning and high-temperature carbonization treatment. For example, patent CN114318664B discloses a flexible carbon nanofiber membrane with an oriented structure and a method for preparing the same. According to the method, continuous electrostatic spinning is carried out through the cooperation of a high-speed rotating metal receiving roller and a plurality of spray heads, and then high-temperature carbonization is carried out in a high-purity nitrogen atmosphere. In the carbonization process, the high molecular chains undergo severe dehydrogenation, cyclization and crosslinking reactions to form a highly compact disordered graphite or graphite-like microcrystalline structure, and certain bending flexibility is given to the carbon nanofiber membrane. However, the maximum tensile strain that conventional pure carbon nanofiber membranes can withstand is usually only about 5%, and macroscopic properties of the film show extremely poor tensile deformation capability, and brittle fracture is extremely likely to occur under dynamic external forces such as large stretching or compression. This inherent defect severely restricts its practical application in strain sensing devices, safety protective articles, and wearable devices that are required to withstand dynamic large strains. In order to improve the stretchability of a carbon nanofiber membrane, patent CN119877184a discloses an ultrathin transparent carbon nanofiber membrane flexible strain sensor and a preparation method thereof, and the core strategy is to compound the carbon nanofiber membrane with an organic elastomer such as polyurethane. Although the organic polymer matrix is introduced to solve the problem of stretching the carbon nanofiber membrane to a certain extent, the intrinsic physicochemical advantages of high temperature resistance, corrosion resistance and the like of the pure carbon material are also seriously sacrificed, and the application scene of the composite material in severe environments such as extreme temperature, strong corrosive media and the like is greatly limited. Therefore, by reasonably designing the components of the precursor of the carbon nanofiber and precisely regulating and controlling the microstructure and morphology (such as the curling degree of the fiber, the flexibility of the crosslinking node and the multidimensional topological structure design of the film material), the inherent limitation of the traditional pure carbon material of being hard and brittle is broken through, and a pure carbon nanofiber film which has high conductivity, high porosity and intrinsic tensile elasticity is developed, so that the method becomes a key technical problem to be solved in the fields of material science and flexible electronics. Disclosure of Invention In view of the above, the invention provides a stretchable elastic carbon nanofiber membrane material and a preparation method thereof, which realize the preparation of the carbon nanofiber membrane material with stretchable elastic recovery performance, high conductivity and high air permeability, break the inherent cognition of the traditional carbon material of being hard and brittle, and greatly improve the application prospect of the carbon nanofiber membrane material in the fields of wearable equipment, strain sensing devices, air purification and the like. The invention is realized by the following technical scheme: S1, dissolving a carbon precursor polymer in a solvent, and uniformly stirring by magnetic force to obtain a carbon precursor solution A; S2, dissolving polystyrene in a solvent, and uniformly stirring by magnetic force to obtain spinning solution B; S3, carrying out electrostatic spinning on the solution A and the solution B according to a certain combination sequence, stripping the solution A and the solution B from the base material after a certain time, and then drying the base material in an oven for a certain time to obtain a multi-layer carbon precursor na