Multifunctional wearable composite fiber membrane as well as preparation method and application thereof

Abstract

The invention belongs to the field of intelligent wearing, and discloses a multifunctional wearable composite fiber membrane and a preparation method and application thereof. The multifunctional wearable composite fiber membrane is of a sandwich structure, the upper layer is a fullerene hybridized phosphorene modified polyacrylonitrile membrane, the lower layer is a polyurethane membrane, and the middle layer is a silver nanowire layer. The preparation method comprises the following steps: firstly, preparing fullerene hybridized phosphorene nanosheets, dispersing the fullerene hybridized phosphorene nanosheets into a solvent to obtain fullerene hybridized phosphorene dispersion liquid, adding the fullerene hybridized phosphorene dispersion liquid into a polyacrylonitrile solution, stirring to obtain a fullerene hybridized phosphorene / polyacrylonitrile spinning solution, and carrying out electrostatic spinning to obtain the fullerene hybridized phosphorene modified polyacrylonitrile fiber membrane. And then rolling or spraying a silver nanowire layer, covering one side of the silver nanowire layer with a polyurethane fiber membrane, drying and pressing to obtain the composite material. The composite fiber membrane prepared by the invention has good mechanical properties, air permeability, one-way moisture conduction performance, antibacterial performance, heat dissipation performance, electromagnetic shielding performance and flame retardant performance, and has a wide application prospect in the field of flexible wearable intelligent equipment.

Description

Technical Field

[0001] The present invention belongs to the field of smart wearables, and relates to a multifunctional wearable composite fiber membrane, a preparation method thereof and an application thereof. Background Art

[0002] The development of fibers and textiles has spanned the entire history of human scientific civilization. With the development of technology, single-functional textiles can no longer meet people's growing needs for a better life, and multifunctional integrated smart textiles have gradually emerged in application fields such as mobile electronic devices, electromagnetic protection devices, and human motion detection. The nanofiber membrane with a Janus structure is a special structure composed of two or more components with different physical properties, and this double-sided structure can endow the nanofiber membrane with more excellent multifunctionality. Thermoplastic polyurethane uses water as a solvent and has the advantages of water resistance, pollution-free, safety and reliability, excellent mechanical properties, good compatibility, and easy modification. The properties of polyacrylonitrile fiber are similar to those of wool, so it is often called artificial wool and has good hydrophilicity, skin-friendly property, elasticity, heat preservation property and weather resistance. However, neither of them has conductivity, which brings the problem of low conductivity while endowing the flexible material with excellent mechanical properties. At the same time, polyacrylonitrile fibers and textiles are extremely easy to be ignited at high temperatures, and the long-term operation of integrated wearable electronic devices will further increase the fire risk. For example, CN117005107A endows the MXene@PDA-PU fiber membrane with hydrophilicity by adding MXene, and the PU nanofiber membrane is used as a hydrophobic layer to make the Janus fiber membrane have unidirectional water permeability. At the same time, the addition of MXene also makes the Janus fiber membrane have good photothermal conversion property, heat collection property, cyclic heat response property, mechanical properties and flame retardancy, but does not pay attention to problems such as the antibacterial property of the fiber membrane. Another example is that CN116278243A relates to a wearable aerogel film fabric with both heat and moisture management functions, which is assembled from thermoplastic polyurethane nanowires doped with zinc oxide nanoparticles and a biomass cellulose aerogel film, but does not pay attention to problems such as the flame retardancy of wearable film materials.

[0003] Phosphorene is an emerging two-dimensional material after graphene and has been widely studied due to its high specific surface area, excellent optoelectronic properties and mechanical properties. Phosphorene is composed of phosphorus elements and has the advantages of less smoke, low toxicity and pollution-free of phosphorus-based flame retardants, and has the potential to become the next-generation commercial flame retardant. However, due to the presence of lone pair electrons on the surface, phosphorene is easily oxidized in air and difficult to preserve. Functional modification of phosphorene will effectively avoid its easy oxidation problem, but the process is complex and the operation is cumbersome. Therefore, researching wearable fabrics with functions such as skin-friendly, breathable, sweat-absorbing, and antibacterial, and designing multifunctional wearable devices with good mechanical properties, electrochemical properties, electromagnetic shielding properties, etc. are the future development directions. Summary of the Invention

[0004] In order to overcome the disadvantages and deficiencies of the prior art, the primary object of the present invention is to provide a multifunctional wearable composite fiber membrane.

[0005] Another object of the present invention is to provide a method for preparing a multifunctional wearable composite fiber membrane. This method obtains a polyacrylonitrile fiber membrane modified with fullerene hybridized phosphorene nanosheets through electrospinning, and after surface rolling with silver nanowires, polyurethane electrospinning is carried out thereon for encapsulation. The obtained sandwich-structured composite material has good mechanical properties, electromagnetic shielding properties, air permeability, antibacterial properties, directional sweat discharge properties, heat dissipation properties, and flame retardant properties, and has broad prospects in the field of flexible wearable devices.

[0006] Another object of the present invention is to provide the application of the above-mentioned multifunctional wearable composite fiber membrane.

[0007] The object of the present invention is achieved by the following technical solutions:

[0008] A multifunctional wearable composite fiber membrane, the multifunctional wearable composite fiber membrane has a sandwich structure, the upper layer is a polyacrylonitrile membrane modified with fullerene hybridized phosphorene, the lower layer is a polyurethane membrane, and the middle layer is a silver nanowire layer;

[0009] The modification is physical modification blending.

[0010] Preferably, the polyacrylonitrile membrane modified with fullerene hybridized phosphorene is an electrospun membrane, and the polyurethane membrane is an electrospun membrane.

[0011] Preferably, the fullerene hybridized phosphorene is fullerene hybridized phosphorene nanosheets, and the mass ratio of fullerene to phosphorene nanosheets is 2:1 to 4:1.

[0012] Preferably, the mass ratio of fullerene hybridized phosphorene to polyacrylonitrile is 0.6:10 to 1:10.

[0013] Preferably, the mass ratio of polyacrylonitrile to polyurethane is 0.4:1 to 1:1.

[0014] Preferably, the silver nanowires have a diameter of 90 nanometers and a length of 20 - 60 micrometers.

[0015] A method for preparing a multifunctional wearable composite fiber membrane, comprising the following steps:

[0016] (1) Using black phosphorus crystals and fullerene as raw materials, prepare fullerene hybridized phosphorene by mechanical ball milling;

[0017] (2) Disperse the fullerene hybridized phosphorene into a solvent to obtain a fullerene hybridized phosphorene dispersion, add the fullerene hybridized phosphorene dispersion into a polyacrylonitrile solution, stir to obtain a fullerene hybridized phosphorene / polyacrylonitrile spinning solution, and prepare a polyacrylonitrile fiber membrane modified with fullerene hybridized phosphorene by electrospinning;

[0018] (3) Roll coat or spray a silver nanowire layer on the polyacrylonitrile fiber membrane modified with fullerene hybridized phosphorene, and then cover a polyurethane fiber membrane on one side of the silver nanowire layer, and obtain a multifunctional wearable composite fiber membrane after drying and pressing.

[0019] Preferably, the specific steps of step (1) are as follows: Take an appropriate amount of black phosphorus crystal and add it to an appropriate amount of polar solvent at room temperature, place it together with 50 g of ZrO2 beads with a diameter of 3 mm in a planetary ball mill at 500 - 800 r / min for ball milling for 6 - 10 h; After the ball milling is completed, centrifuge the reactants at 1000 r / min for 30 - 60 min to remove the large pieces of black phosphorus in the lower layer; Take the upper suspension and centrifuge it at 5000 r / min for 30 - 60 min, and take the lower precipitate for vacuum drying to obtain phosphorene nanosheets; Take an appropriate amount of fullerene and mix it with the phosphorene nanosheets, place it together with 50 g of ZrO2 beads with a diameter of 3 mm in a planetary ball mill at 500 - 800 r / min for ball milling for 12 - 24 h; After the ball milling is completed, screen the mixture to remove the zirconium beads, and perform Soxhlet extraction of the collected powder with carbon disulfide for 12 - 24 h; Finally, vacuum dry the sample for 12 - 24 h to obtain fullerene hybridized phosphorene.

[0020] Preferably, in the specific steps of step (1), the polar solvent is at least one of ethanol, acetone, isopropanol, and water;

[0021] In the specific steps of step (1), the addition ratio of black phosphorus crystal to polar solvent is 500 mg - 1 g:200 mL, and more preferably 1 g:200 mL.

[0022] Preferably, the concentration of the polyacrylonitrile solution in step (2) is 0.3 - 0.5 g / mL in g / mL.

[0023] Preferably, the dispersion in step (2) is ultrasonic dispersion, the ultrasonic power is 200 - 400 W, and the ultrasonic time is 60 - 90 min.

[0024] Preferably, the voltage of the electrospinning in step (2) is 18 kv - 20 kv, the spinning speed is 1 mL / h - 1.5 mL / h, and the receiving distance is 10 - 30 cm.

[0025] Preferably, the solvent in step (2) is at least one of N,N - dimethylformamide, N,N - dimethylacetamide, and N - methylpyrrolidone;

[0026] Preferably, the method for covering the polyurethane fiber membrane in step (3) is electrospinning;

[0027] Preferably, for the method of covering the polyurethane fiber membrane in step (3) by electrospinning, the voltage is 18 kv to 20 kv, the spinning speed is 1 mL / h to 1.5 mL / h, the receiving distance is 10 - 30 cm, and the concentration of the polyurethane solution is 0.1 - 0.2 g / mL, more preferably 0.15 g / mL.

[0028] Preferably, the polyurethane fiber membrane in step (3) is an aqueous polyurethane fiber membrane or a thermoplastic polyurethane fiber membrane.

[0029] The drying in step (3) is vacuum drying, the drying temperature is 30°C to 50°C, and the time is 12 h to 24 h;

[0030] The pressing in step (3) is normal temperature pressing, and the pressing time is 6 - 8 h.

[0031] Application of the above - mentioned multifunctional wearable composite fiber membrane in flexible intelligent wearable devices.

[0032] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0033] (1) The present invention designs a full - nanofiber Janus - type structure fabric. Its through - hole structure realizes good air / water permeability. By utilizing the hydrophobicity difference between the fullerene - phosphorene / polyacrylonitrile fiber membrane and the polyurethane fiber membrane, the unidirectional moisture - guiding function is achieved; meanwhile, the fabric is a multi - layer fiber membrane structure. By using the interaction and complementarity between layers, stress can be effectively dispersed, avoiding excessive load on a single layer, thereby improving the overall mechanical properties;

[0034] (2) The present invention introduces a silver nanowire layer between the fiber membranes, which has an antibacterial effect and simultaneously improves the thermal conductivity, electrical conductivity, and electromagnetic shielding performance of the fabric;

[0035] (3) The present invention uses the mechanical ball - milling method to exfoliate phosphorene and carry out fullerene - phosphorene hybridization, reducing the aggregation effect of phosphorene and fullerene; Fullerene is attached to the activated surface of the phosphorene nanosheet by P - C covalent bonds rather than physical blending, preventing the oxidation of phosphorene. At the same time, fullerene has ultra - high free - radical scavenging ability and has a certain flame - retardant property. It acts synergistically with phosphorene on the flame - retardant effect of the material and further improves the thermal conductivity of the fabric and enhances the electromagnetic shielding performance;

[0036] (4) The composite fiber membrane prepared by the present invention has excellent properties, including good mechanical properties, air permeability, unidirectional moisture conduction property, antibacterial property, heat dissipation property, electromagnetic shielding property and flame retardancy. The elongation at break is higher than 430%, the thermal conductivity is higher than 1.2 W / (m·K), the electromagnetic shielding level is Class B or Class C, the flame retardancy level is V-0, and the safety factor is high, showing broad prospects in the field of flexible wearable devices. Description of the Drawings

[0037] Figure 1 It is the SEM image of fullerene hybridized phosphorene in Example 1.

[0038] Figure 2 It is the surface SEM image of the polyacrylonitrile fiber membrane in Comparative Example 1.

[0039] Figure 3 It is the SEM image of the polyacrylonitrile fiber membrane modified by fullerene hybridized phosphorene in Example 1.

[0040] Figure 4 It is the microcalorimetric test result of the polyacrylonitrile / phosphorene composite fiber membrane and the multifunctional wearable composite fiber membrane prepared in Example 1. PAN / BP represents the phosphorene-modified polyacrylonitrile composite fiber membrane, and PAN / C 60 -BP represents the composite fiber membrane modified by fullerene hybridized phosphorene, demonstrating that the flame retardancy effect of fullerene hybridized phosphorene is superior to that of unhybridized phosphorene. Detailed Embodiments

[0041] The present invention will be further described in detail below in conjunction with the embodiments and the drawings, but the embodiments of the present invention are not limited thereto. The raw materials involved in the present invention can be directly purchased from the market. For the process parameters not specifically mentioned, conventional techniques can be referred to.

[0042] Fullerene is commercially available fullerene C 60 .

[0043] Black phosphorus crystal: Purchased from Kunming Black Phosphorus Technology Service Co., Ltd.

[0044] Silver nanowires: Purchased from Macklin Reagent, with a diameter of 90 nm and a length of 20 - 60 μm.

[0045] Polyurethane: Thermoplastic polyurethane with a molecular weight of 90k, purchased from Risheng Chemical Co., Ltd., Taiwan Province, China.

[0046] Example 1

[0047] (1) Take 1 g of black phosphorus crystals and add them to 200 mL of isopropanol at room temperature. Place them together with 50 g of ZrO₂ beads with a diameter of 3 mm in a planetary ball mill at 500 r / min and ball mill for 6 h. After the ball milling is completed, centrifuge the reactants at 1000 r / min for 30 min to remove the large pieces of black phosphorus in the lower layer. Take the upper suspension and centrifuge it at 5000 r / min for 60 min. Take the precipitate in the lower layer and dry it in vacuum to obtain phosphorene nanosheets. Take 0.6 g of fullerene and mix it with 0.3 g of phosphorene nanosheets. Place them together with 50 g of ZrO₂ beads with a diameter of 3 mm in a planetary ball mill at 500 r / min and ball mill for 24 h. After the ball milling is completed, screen the mixture to remove the zirconium beads. Extract the collected powder with carbon disulfide by Soxhlet extraction for 24 h to remove the unhybridized free fullerene. Finally, dry the sample in vacuum for 12 h to obtain fullerene hybridized phosphorene. As Figure 1 shown, fullerenes aggregate at the edges of phosphorene nanosheets, proving the successful preparation of fullerene hybridized phosphorene. Take 0.3 g of fullerene hybridized phosphorene and disperse it in 10 mL of N,N-dimethylacetamide. Ultrasonicate it at a power of 200 W for 90 min to obtain a fullerene hybridized phosphorene dispersion;

[0048] (2) Dissolve 3 g of polyacrylonitrile in 10 mL of N,N-dimethylacetamide and stir magnetically for 4 h to obtain a polyacrylonitrile solution. Add the fullerene hybridized phosphorene dispersion to the polyacrylonitrile solution and stir magnetically at room temperature for 6 - 8 h to obtain a fullerene hybridized phosphorene / polyacrylonitrile spinning solution. Electrospin the spinning solution at a voltage of 18 kV and a spinning speed of 1.5 mL / h at room temperature, with a receiving distance of 20 cm. After the electrospinning is completed, dry the collected fiber membrane in vacuum at 50 °C for 12 h to obtain a polyacrylonitrile fiber membrane modified with fullerene hybridized phosphorene. As Figure 3 shown, it is more uniformly dispersed and has a higher straightness at this scale. Fullerene hybridized phosphorene is more evenly distributed in the polyacrylonitrile fibers, and the surface roughness of the fibers is improved compared with Comparative Example 1, and the hydrophobic property is better;

[0049] (3) Roll coat a 100 ml ethanol solution of silver nanowires with a diameter of 90 nm and a length of 20 - 60 μm (10 mg / ml) on the surface of the polyacrylonitrile fiber membrane obtained in step (2), and air dry it;

[0050] (4) Dissolve 3 g of polyurethane particles in 20 mL of N,N-dimethylacetamide and stir at room temperature for 4 h to obtain a polyurethane solution. Electrospin the polyurethane solution at a voltage of 18 kV and a spinning speed of 1.5 mL / h at room temperature on the side of the silver nanowires of the fiber membrane obtained in step (3), with a receiving distance of 20 cm. Dry the collected fiber membrane in vacuum at 50 °C for 12 h and press it at room temperature for 6 h to obtain a flat multifunctional wearable composite fiber membrane;

[0051] (5) Cut the composite fiber membrane obtained in step (4) into small pieces of 3 cm × 3 cm, named FM-1, for subsequent characterization.

[0052] Example 2

[0053] (1) Take 1 g of black phosphorus crystals and add them to 400 mL of isopropanol at room temperature. Place them together with 50 g of ZrO2 beads with a diameter of 3 mm in a planetary ball mill at 500 r / min for ball milling for 6 h; after the ball milling is completed, centrifuge the reactants at 1000 r / min for 30 min to remove the large pieces of black phosphorus in the lower layer; take the upper suspension and centrifuge it at 5000 r / min for 60 min, and take the precipitate in the lower layer for vacuum drying to obtain phosphorene nanosheets; take 0.6 g of fullerene and mix it with 0.3 g of phosphorene nanosheets, and place them together with 50 g of ZrO2 beads with a diameter of 3 mm in a planetary ball mill at 500 r / min for ball milling for 24 h; after the ball milling is completed, sieve the mixture to remove the zirconium beads, and extract the collected powder with carbon disulfide by Soxhlet extraction for 24 h to remove the unhybridized free fullerene; finally, vacuum dry the sample for 12 h to obtain fullerene hybridized phosphorene; take 0.3 g of fullerene hybridized phosphorene and disperse it in 10 mL of N,N-dimethylacetamide, and ultrasonicate it at a power of 200 W for 90 min to obtain a fullerene hybridized phosphorene dispersion;

[0054] (2) Dissolve 3 g of polyacrylonitrile in 10 mL of N,N-dimethylacetamide and stir magnetically for 4 h to obtain a polyacrylonitrile solution; add the fullerene hybridized phosphorene dispersion to the polyacrylonitrile solution and stir magnetically at room temperature for 6 - 8 h to obtain a fullerene hybridized phosphorene / polyacrylonitrile spinning solution; electrospin the spinning solution at a voltage of 18 kV and a spinning speed of 1.5 mL / h at room temperature, and the receiving distance is 20 cm; after the electrospinning is completed, vacuum dry the collected fiber membrane at 50 °C for 12 h to obtain a polyacrylonitrile fiber membrane modified with fullerene hybridized phosphorene;

[0055] (3) Roll coat a 100 ml ethanol solution (10 mg / ml) of silver nanowires with a diameter of 90 nm and a length of 20 - 60 μm on the surface of the polyacrylonitrile fiber membrane obtained in step (2), and air dry it;

[0056] (4) Dissolve 3 g of polyurethane particles in 20 mL of N,N-dimethylacetamide and stir at room temperature for 4 h to obtain a polyurethane solution. Electrospin the polyurethane solution at a voltage of 18 kV and a spinning speed of 1.5 mL / h at room temperature on the silver nanowire side of the fiber membrane in step (3), and the receiving distance is 20 cm. Vacuum dry the collected fiber membrane at 50 °C for 12 h and press it at room temperature for 6 h to obtain a flat multifunctional wearable composite fiber membrane;

[0057] (5) Cut the composite fiber membrane obtained in step (4) into small pieces of 3 cm × 3 cm, named FM-2, for subsequent characterization.

[0058] Example 3

[0059] (1) Take 1 g of black phosphorus crystals and add them to 200 mL of isopropanol at room temperature. Place them together with 50 g of ZrO2 beads with a diameter of 3 mm in a planetary ball mill at 500 r / min for ball milling for 6 h. After the ball milling is completed, centrifuge the reactants at 1000 r / min for 30 min to remove the large pieces of black phosphorus in the lower layer. Take the upper suspension and centrifuge it at 5000 r / min for 60 min, and take the precipitate in the lower layer for vacuum drying to obtain phosphorus nanosheets. Take 0.8 g of fullerene and mix it with 0.2 g of phosphorus nanosheets, and place them together with 50 g of ZrO2 beads with a diameter of 3 mm in a planetary ball mill at 500 r / min for ball milling for 24 h. After the ball milling is completed, screen the mixture to remove the zirconium beads, and subject the collected powder to Soxhlet extraction with carbon disulfide for 24 h to remove the unhybridized free fullerene. Finally, vacuum dry the sample for 12 h to obtain fullerene hybridized phosphorus; take 0.3 g of fullerene hybridized phosphorus and disperse it in 10 mL of N,N-dimethylacetamide, and ultrasonicate it at a power of 200 W for 90 min to obtain a fullerene hybridized phosphorus dispersion;

[0060] (2) Dissolve 3 g of polyacrylonitrile in 10 mL of N,N-dimethylacetamide and stir magnetically for 4 h to obtain a polyacrylonitrile solution. Add the fullerene-phosphorus dispersion to the polyacrylonitrile solution and stir magnetically at room temperature for 6 - 8 h to obtain a fullerene hybridized phosphorus / polyacrylonitrile spinning solution. Electrospin the spinning solution at a voltage of 18 kV and a spinning speed of 1.5 mL / h at room temperature, and the receiving distance is 20 cm. After the electrospinning is completed, vacuum dry the collected fiber membrane at 50 °C for 12 h to obtain a polyacrylonitrile fiber membrane modified with fullerene hybridized phosphorus;

[0061] (3) Roll coat a 100 ml ethanol solution of silver nanowires with a diameter of 90 nm and a length of 20 - 60 μm (10 mg / ml) on the surface of the polyacrylonitrile fiber membrane obtained in step (2), and air dry it;

[0062] (4) Dissolve 3 g of polyurethane particles in 20 mL of N,N-dimethylacetamide and stir at room temperature for 4 h to obtain a polyurethane solution. Electrospin the polyurethane solution at a voltage of 18 kV and a spinning speed of 1.5 mL / h at room temperature on the side of the silver nanowires of the fiber membrane in step (3), and the receiving distance is 20 cm. Vacuum dry the collected fiber membrane at 50 °C for 12 h and press it at room temperature for 6 h to obtain a flat multifunctional wearable composite fiber membrane;

[0063] (5) Cut the composite fiber membrane obtained in step (4) into small pieces of 3 cm × 3 cm, named FM-3, for subsequent characterization.

[0064] Example 4

[0065] (1) Add 1 g of black phosphorus crystals to 200 mL of isopropanol at room temperature, and place them together with 50 g of ZrO2 beads with a diameter of 3 mm in a planetary ball mill at 500 r / min for ball milling for 6 h; after the ball milling is completed, centrifuge the reactants at 1000 r / min for 30 min to remove the large pieces of black phosphorus in the lower layer; take the upper suspension and centrifuge it at 5000 r / min for 60 min, and take the lower precipitate for vacuum drying to obtain phosphorus nanosheets; take 0.6 g of fullerene and 0.3 g of phosphorus nanosheets and mix them, and place them together with 50 g of ZrO2 beads with a diameter of 3 mm in a planetary ball mill at 500 r / min for ball milling for 24 h; after the ball milling is completed, sieve the mixture to remove the zirconium beads, and extract the collected powder with carbon disulfide by Soxhlet extraction for 24 h to remove the unhybridized free fullerene; finally, vacuum dry the sample for 12 h to obtain fullerene hybridized phosphorus; take 0.3 g of fullerene hybridized phosphorus and disperse it in 10 mL of N,N-dimethylacetamide, and ultrasonicate it at a power of 200 W for 90 min to obtain a fullerene hybridized phosphorus dispersion;

[0066] (2) Dissolve 5 g of polyacrylonitrile in 10 mL of N,N-dimethylacetamide and stir magnetically for 4 h to obtain a polyacrylonitrile solution; add the fullerene hybridized phosphorus dispersion to the polyacrylonitrile solution and stir magnetically at room temperature for 6 - 8 h to obtain a fullerene hybridized phosphorus / polyacrylonitrile spinning solution; electrospin the spinning solution at a voltage of 18 kV and a spinning speed of 1.5 mL / h at room temperature, and the receiving distance is 20 cm; after the electrospinning is completed, vacuum dry the collected fiber membrane at 50 °C for 12 h to obtain a polyacrylonitrile fiber membrane modified with fullerene hybridized phosphorus;

[0067] (3) Roll coat a 100 ml ethanol solution (10 mg / ml) of silver nanowires with a diameter of 90 nm and a length of 20 - 60 μm on the surface of the polyacrylonitrile fiber membrane obtained in step (2), and air dry it;

[0068] (4) Dissolve 3 g of polyurethane particles in 20 mL of N,N-dimethylacetamide and stir at room temperature for 4 h to obtain a polyurethane solution. Electrospin the polyurethane solution at a voltage of 18 kV and a spinning speed of 1.5 mL / h at room temperature on the side of the silver nanowires of the fiber membrane obtained in step (3), and the receiving distance is 20 cm. Vacuum dry the collected fiber membrane at 50 °C for 12 h and press it at room temperature for 6 h to obtain a flat multifunctional wearable composite fiber membrane;

[0069] (5) Cut the composite fiber membrane obtained in step (4) into small pieces of 3 cm × 3 cm, named FM-4, for subsequent characterization.

[0070] Example 5

[0071] (1) Take 1 g of black phosphorus crystals and add them to 200 mL of isopropanol at room temperature. Place them together with 50 g of ZrO₂ beads with a diameter of 3 mm in a planetary ball mill at 500 r / min and mill for 6 h. After the ball milling is completed, centrifuge the reactants at 1000 r / min for 30 min to remove the large pieces of black phosphorus in the lower layer. Take the upper suspension and centrifuge it at 5000 r / min for 60 min. Take the lower precipitate and dry it in vacuo to obtain phosphorene nanosheets. Take 0.6 g of fullerene and mix it with 0.3 g of phosphorene nanosheets. Place them together with 50 g of ZrO₂ beads with a diameter of 3 mm in a planetary ball mill at 500 r / min and mill for 24 h. After the ball milling is completed, sieve the mixture to remove the zirconium beads. Extract the collected powder with carbon disulfide in a Soxhlet extractor for 24 h to remove the unhybridized free fullerene. Finally, dry the sample in vacuo for 12 h to obtain fullerene hybridized phosphorene. Take 0.18 g of fullerene hybridized phosphorene and disperse it in 10 mL of N,N-dimethylacetamide. Ultrasonicate it at a power of 200 W for 90 min to obtain a fullerene hybridized phosphorene dispersion;

[0072] (2) Dissolve 3 g of polyacrylonitrile in 10 mL of N,N-dimethylacetamide and stir magnetically for 4 h to obtain a polyacrylonitrile solution. Add the fullerene hybridized phosphorene dispersion to the polyacrylonitrile solution and stir magnetically at room temperature for 6 - 8 h to obtain a fullerene hybridized phosphorene / polyacrylonitrile spinning solution. Electrospin the spinning solution at a voltage of 18 kV and a spinning speed of 1.5 mL / h at room temperature, with a receiving distance of 20 cm. After the electrospinning is completed, dry the collected fiber membrane in vacuo at 50 °C for 12 h to obtain a polyacrylonitrile fiber membrane modified with fullerene hybridized phosphorene;

[0073] (3) Roll coat a 100 ml ethanol solution of silver nanowires with a diameter of 90 nm and a length of 20 - 60 μm (10 mg / ml) on the surface of the polyacrylonitrile fiber membrane obtained in step (2), and air dry it;

[0074] (4) Dissolve 3 g of polyurethane particles in 20 mL of N,N-dimethylacetamide and stir at room temperature for 4 h to obtain a polyurethane solution. Electrospin the polyurethane solution at a voltage of 18 kV and a spinning speed of 1.5 mL / h at room temperature on the side of the silver nanowires of the fiber membrane obtained in step (3), with a receiving distance of 20 cm. Dry the collected fiber membrane in vacuo at 50 °C for 12 h and press it at room temperature for 6 h to obtain a flat multifunctional wearable composite fiber membrane;

[0075] (5) Cut the composite fiber membrane obtained in step (4) into small pieces of 3 cm × 3 cm and name it FM-5 for subsequent characterization.

[0076] Example 6

[0077] (1) Add 1 g of black phosphorus crystals to 200 mL of isopropanol at room temperature, and place them together with 50 g of ZrO₂ beads with a diameter of 3 mm in a planetary ball mill at 500 r / min for ball milling for 6 h; after the ball milling is completed, centrifuge the reactants at 1000 r / min for 30 min to remove the large pieces of black phosphorus in the lower layer; take the upper suspension and centrifuge it at 5000 r / min for 60 min, and take the precipitate in the lower layer for vacuum drying to obtain phosphorene nanosheets; take 0.6 g of fullerene and 0.3 g of phosphorene nanosheets and mix them, and place them together with 50 g of ZrO₂ beads with a diameter of 3 mm in a planetary ball mill at 500 r / min for ball milling for 24 h; after the ball milling is completed, sieve the mixture to remove the zirconium beads, and extract the collected powder with carbon disulfide by Soxhlet extraction for 24 h to remove the unhybridized free fullerene; finally, vacuum dry the sample for 12 h to obtain fullerene hybridized phosphorene; take 0.3 g of fullerene hybridized phosphorene and disperse it in 10 mL of N,N-dimethylacetamide, and ultrasonicate it at a power of 200 W for 90 min to obtain a fullerene hybridized phosphorene dispersion;

[0078] (2) Dissolve 3 g of polyacrylonitrile in 10 mL of N,N-dimethylacetamide and stir magnetically for 4 h to obtain a polyacrylonitrile solution; add the fullerene hybridized phosphorene dispersion to the polyacrylonitrile solution and stir magnetically at room temperature for 6 - 8 h to obtain a fullerene hybridized phosphorene / polyacrylonitrile spinning solution; electrospin the spinning solution at a voltage of 18 kV and a spinning speed of 1.5 mL / h at room temperature, and the receiving distance is 20 cm; after the electrospinning is completed, vacuum dry the collected fiber membrane at 50 °C for 12 h to obtain a polyacrylonitrile fiber membrane modified with fullerene hybridized phosphorene;

[0079] (3) Roll coat a 100 ml ethanol solution of silver nanowires with a diameter of 90 nm and a length of 20 - 60 μm (10 mg / ml) on the surface of the polyacrylonitrile fiber membrane obtained in step (2), and air dry it;

[0080] (4) Electrospin 7.5 g of 40% wt aqueous polyurethane solution at a voltage of 18 kV and a spinning speed of 1.5 mL / h at room temperature on the side of the silver nanowires of the fiber membrane obtained in step (3), and the receiving distance is 20 cm. Vacuum dry the collected fiber membrane at 50 °C for 12 h and press it at room temperature for 6 h to obtain a flat multifunctional wearable composite fiber membrane;

[0081] (5) Cut the composite fiber membrane obtained in step (4) into small pieces of 3 cm × 3 cm and name it FM-6 for subsequent characterization.

[0082] Comparative Example 1

[0083] (1) Dissolve 3 g of polyacrylonitrile in 10 mL of N,N-dimethylacetamide and stir magnetically for 4 h to obtain a polyacrylonitrile solution. Electrospin the solution at a spinning speed of 1.5 mL / h at a voltage of 18 kV at room temperature with a receiving distance of 20 cm. After electrospinning, dry the collected fiber membrane in a vacuum at 50 °C for 12 h to obtain a polyacrylonitrile fiber membrane, as shown in SEM Figure 2 as follows;

[0084] (3) Dissolve 3 g of polyurethane particles in 20 mL of N,N-dimethylacetamide and stir at room temperature for 4 h to obtain a polyurethane solution. Electrospin the polyurethane solution at a spinning speed of 1.5 mL / h at a voltage of 18 kV at room temperature onto the fiber membrane in step (2) with a receiving distance of 20 cm. Dry the collected fiber membrane in a vacuum at 50 °C for 12 h and press it at room temperature for 6 h to obtain a flat composite fiber membrane;

[0085] (5) Cut the composite fiber membrane obtained in step (4) into small pieces of 3 cm × 3 cm and name it FM-1’ for subsequent characterization.

[0086] Comparative Example 2

[0087] (1) Take 1 g of black phosphorus crystals and add them to 200 mL of isopropanol at room temperature. Place them together with 50 g of ZrO2 beads with a diameter of 3 mm in a planetary ball mill at 500 r / min for ball milling for 6 h. After ball milling, centrifuge the reactants at 1000 r / min for 30 min to remove the large pieces of black phosphorus in the lower layer. Take the upper suspension and centrifuge it at 5000 r / min for 60 min, and take the precipitate in the lower layer and dry it in a vacuum to obtain phosphorene nanosheets. Take 0.3 g of phosphorene nanosheets and disperse them in 10 mL of N,N-dimethylacetamide, and ultrasonicate them at a power of 200 W for 90 min to obtain a phosphorene dispersion;

[0088] (2) Dissolve 3 g of polyacrylonitrile in 10 mL of N,N-dimethylacetamide and stir magnetically for 4 h to obtain a polyacrylonitrile solution. Add the phosphorene dispersion to the polyacrylonitrile solution and stir magnetically at room temperature for 6 - 8 h to obtain a phosphorene / polyacrylonitrile spinning solution. Electrospin the spinning solution at a spinning speed of 1.5 mL / h at a voltage of 18 kV at room temperature with a receiving distance of 20 cm. After electrospinning, dry the collected fiber membrane in a vacuum at 50 °C for 12 h to obtain a phosphorene / polyacrylonitrile fiber membrane;

[0089] (3) Roll coat a 100 ml ethanol solution of silver nanowires with a diameter of 90 nm and a length of 20 - 60 μm (10 mg / ml) on the surface of the polyacrylonitrile fiber membrane in step (2) and air dry it;

[0090] (4) Dissolve 3 g of polyurethane particles in 20 mL of N,N-dimethylacetamide, stir at room temperature for 4 h to obtain a polyurethane solution. Electrospin the polyurethane solution at a spinning speed of 1.5 mL / h under a voltage of 18 kV at room temperature onto the side of the silver nanowires of the fiber membrane in step (3), with a receiving distance of 20 cm. Vacuum dry the collected fiber membrane at 50 °C for 12 h and press it at room temperature for 6 h to obtain a flat multifunctional wearable composite fiber membrane;

[0091] (5) Cut the composite fiber membrane obtained in step (4) into small pieces of 3 cm × 3 cm and name it FM-2’ for subsequent characterization.

[0092] Comparative Example 3

[0093] (1) Take 0.3 g of fullerene and disperse it in 10 mL of N,N-dimethylacetamide, ultrasonicate for 90 min at a power of 200 W to obtain a fullerene dispersion;

[0094] (2) Dissolve 3 g of polyacrylonitrile in 10 mL of N,N-dimethylacetamide, stir magnetically for 4 h to obtain a polyacrylonitrile solution; add the fullerene dispersion to the polyacrylonitrile solution, stir magnetically at room temperature for 6 - 8 h to obtain a fullerene / polyacrylonitrile spinning solution; electrospin the spinning solution at a spinning speed of 1.5 mL / h under a voltage of 18 kV at room temperature, with a receiving distance of 20 cm; after electrospinning, vacuum dry the collected fiber membrane at 50 °C for 12 h to obtain a fullerene / polyacrylonitrile fiber membrane;

[0095] (3) Roll coat the surface of the polyacrylonitrile fiber membrane in step (2) with 100 ml of an ethanol solution of silver nanowires (10 mg / ml) with a diameter of 90 nm and a length of 20 - 60 μm, and air dry it;

[0096] (4) Dissolve 3 g of polyurethane particles in 20 mL of N,N-dimethylacetamide, stir at room temperature for 4 h to obtain a polyurethane solution. Electrospin the polyurethane solution at a spinning speed of 1.5 mL / h under a voltage of 18 kV at room temperature onto the side of the silver nanowires of the fiber membrane in step (3), with a receiving distance of 20 cm. Vacuum dry the collected fiber membrane at 50 °C for 12 h and press it at room temperature for 6 h to obtain a flat multifunctional wearable composite fiber membrane;

[0097] (5) Cut the composite fiber membrane obtained in step (4) into small pieces of 3 cm × 3 cm and name it FM-3’ for subsequent characterization.

[0098] Comparative Example 4

[0099] (1) Take 1 g of black phosphorus crystals and add them to 200 mL of isopropanol at room temperature. Place them together with 50 g of ZrO2 beads with a diameter of 3 mm in a planetary ball mill at 500 r / min for ball milling for 6 h. After the ball milling is completed, centrifuge the reactants at 1000 r / min for 30 min to remove the large pieces of black phosphorus in the lower layer. Take the upper suspension and centrifuge it at 5000 r / min for 60 min. Take the precipitate in the lower layer and dry it in vacuum to obtain phosphorene nanosheets. Take 0.3 g of fullerene and mix it with 0.3 g of phosphorene nanosheets. Place them together with 50 g of ZrO2 beads with a diameter of 3 mm in a planetary ball mill at 500 r / min for ball milling for 24 h. After the ball milling is completed, screen the mixture to remove the zirconium beads. Soxhlet extract the collected powder with carbon disulfide for 24 h to remove the unhybridized free fullerene. Finally, dry the sample in vacuum for 12 h to obtain fullerene hybridized phosphorene. Take 0.3 g of fullerene hybridized phosphorene and disperse it in 10 mL of N,N-dimethylacetamide. Ultrasonicate it at a power of 200 W for 90 min to obtain a fullerene hybridized phosphorene dispersion;

[0100] (2) Dissolve 3 g of polyacrylonitrile in 10 mL of N,N-dimethylacetamide and stir magnetically for 4 h to obtain a polyacrylonitrile solution. Add the fullerene hybridized phosphorene dispersion to the polyacrylonitrile solution and stir magnetically at room temperature for 6 - 8 h to obtain a fullerene hybridized phosphorene / polyacrylonitrile spinning solution. Electrospin the spinning solution at a voltage of 18 kV and a spinning speed of 1.5 mL / h at room temperature, with a receiving distance of 20 cm. After the electrospinning is completed, dry the collected fiber membrane in vacuum at 50 °C for 12 h to obtain a polyacrylonitrile fiber membrane modified with fullerene hybridized phosphorene;

[0101] (3) Roll coat a 100 ml ethanol solution of silver nanowires with a diameter of 90 nm and a length of 20 - 60 μm (10 mg / ml) on the surface of the polyacrylonitrile fiber membrane obtained in step (2) and air dry it;

[0102] (4) Dissolve 3 g of polyurethane particles in 20 mL of N,N-dimethylacetamide and stir at room temperature for 4 h to obtain a polyurethane solution. Electrospin the polyurethane solution at a voltage of 18 kV and a spinning speed of 1.5 mL / h at room temperature on the side of the silver nanowires of the fiber membrane obtained in step (3), with a receiving distance of 20 cm. Dry the collected fiber membrane in vacuum at 50 °C for 12 h and press it at room temperature for 6 h to obtain a flat multifunctional wearable composite fiber membrane;

[0103] (5) Cut the composite fiber membrane obtained in step (4) into small pieces of 3 cm × 3 cm and name it FM-4' for subsequent characterization.

[0104] Comparative Example 5

[0105] (1) Take 1 g of black phosphorus crystals and add them to 200 mL of isopropanol at room temperature. Place them together with 50 g of ZrO2 beads with a diameter of 3 mm in a planetary ball mill at 500 r / min and ball mill for 6 h. After the ball milling is completed, centrifuge the reactants at 1000 r / min for 30 min to remove the large pieces of black phosphorus in the lower layer. Take the upper suspension and centrifuge it at 5000 r / min for 60 min. Take the precipitate in the lower layer and dry it in vacuo to obtain phosphorene nanosheets. Take 0.6 g of fullerene and mix it with 0.1 g of phosphorene nanosheets. Place them together with 50 g of ZrO2 beads with a diameter of 3 mm in a planetary ball mill at 500 r / min and ball mill for 24 h. After the ball milling is completed, sieve the mixture to remove the zirconium beads. Soxhlet extract the collected powder with carbon disulfide for 24 h. Finally, dry the sample in vacuo for 12 h to obtain fullerene hybridized phosphorene. Take 0.3 g of fullerene hybridized phosphorene and disperse it in 10 mL of N,N-dimethylacetamide. Ultrasonic it at a power of 200 W for 90 min to obtain a fullerene hybridized phosphorene dispersion;

[0106] (2) Dissolve 3 g of polyacrylonitrile in 10 mL of N,N-dimethylacetamide and stir magnetically for 4 h to obtain a polyacrylonitrile solution. Add the fullerene hybridized phosphorene dispersion to the polyacrylonitrile solution and stir magnetically at room temperature for 6 - 8 h to obtain a fullerene hybridized phosphorene / polyacrylonitrile spinning solution. Electrospin the spinning solution at a voltage of 18 kV and a spinning speed of 1.5 mL / h at room temperature, and the receiving distance is 20 cm. After the electrospinning is completed, dry the collected fiber membrane in vacuo at 50 °C for 12 h to obtain a polyacrylonitrile fiber membrane modified with fullerene hybridized phosphorene;

[0107] (3) Roll coat a 100 ml ethanol solution of silver nanowires with a diameter of 90 nm and a length of 20 - 60 μm (10 mg / ml) on the surface of the polyacrylonitrile fiber membrane obtained in step (2), and air dry it;

[0108] (4) Dissolve 3 g of polyurethane particles in 20 mL of N,N-dimethylacetamide and stir at room temperature for 4 h to obtain a polyurethane solution. Electrospin the polyurethane solution at a voltage of 18 kV and a spinning speed of 1.5 mL / h at room temperature on the side of the silver nanowires of the fiber membrane obtained in step (3), and the receiving distance is 20 cm. Dry the collected fiber membrane in vacuo at 50 °C for 12 h and press it at room temperature for 6 h to obtain a flat multifunctional wearable composite fiber membrane;

[0109] (5) Cut the composite fiber membrane obtained in step (4) into small pieces of 3 cm × 3 cm, named FM-5', for subsequent characterization.

[0110] Comparative Example 6

[0111] (1) Take 1 g of black phosphorus crystals and add them to 200 mL of isopropanol at room temperature. Place them together with 50 g of ZrO₂ beads with a diameter of 3 mm in a planetary ball mill at 500 r / min and mill for 6 h. After the milling is completed, centrifuge the reactants at 1000 r / min for 30 min to remove the large pieces of black phosphorus in the lower layer. Take the upper suspension and centrifuge it at 5000 r / min for 60 min. Take the precipitate in the lower layer and dry it in vacuo to obtain phosphorene nanosheets. Take 0.6 g of fullerene and mix it with 0.3 g of phosphorene nanosheets. Place them together with 50 g of ZrO₂ beads with a diameter of 3 mm in a planetary ball mill at 500 r / min and mill for 24 h. After the milling is completed, sieve the mixture to remove the zirconium beads. Soxhlet extract the collected powder with carbon disulfide for 24 h. Finally, dry the sample in vacuo for 12 h to obtain fullerene hybridized phosphorene. Take 0.3 g of fullerene hybridized phosphorene and disperse it in 10 mL of N,N-dimethylacetamide. Ultrasonic it at a power of 200 W for 90 min to obtain a fullerene hybridized phosphorene dispersion;

[0112] (2) Dissolve 3 g of polyacrylonitrile in 10 mL of N,N-dimethylacetamide and stir magnetically for 4 h to obtain a polyacrylonitrile solution. Add the fullerene hybridized phosphorene dispersion to the polyacrylonitrile solution and stir magnetically at room temperature for 6 - 8 h to obtain a fullerene hybridized phosphorene / polyacrylonitrile spinning solution. Electrospin the spinning solution at a voltage of 18 V and a spinning speed of 1.5 mL / h at room temperature, with a receiving distance of 20 cm. After the electrospinning is completed, dry the collected fiber membrane in vacuo at 50 °C for 12 h to obtain a polyacrylonitrile fiber membrane modified with fullerene hybridized phosphorene;

[0113] (3) Dissolve 3 g of polyurethane particles in 20 mL of N,N-dimethylacetamide and stir at room temperature for 4 h to obtain a polyurethane solution. Electrospin the polyurethane solution at a voltage of 18 kV and a spinning speed of 1.5 mL / h at room temperature on one side of the fiber membrane in step (2), with a receiving distance of 20 cm. Dry the collected fiber membrane in vacuo at 50 °C for 12 h and press it at room temperature for 6 h to obtain a flat multifunctional wearable composite fiber membrane;

[0114] (5) Cut the composite fiber membrane obtained in step (4) into small pieces of 3 cm × 3 cm and name it FM-6’ for subsequent characterization.

[0115] Test Example

[0116] Characterize the mechanical properties and thermal conductivity of the products prepared in each comparative example and example. The characterization methods and results are as follows:

[0117] I. Mechanical Properties

[0118] According to the test method of GB / T 1447-2005, the measured tensile strength and elongation at break of the fiber membrane were detected using a CMT4303 SANS universal testing machine (MTS system, Shenzhen, China).

[0119] Table 1 Tensile test results of each comparative example and example

[0120]

[0121] II. Thermal conductivity

[0122] According to the test method of GB / T 11205-2009, the thermal conductivity was tested using a portable thermal conductivity meter (TC 3000, Xi'an Xiaxi Electronic Technology Co., Ltd.).

[0123] Table 2 Thermal conductivity test results of each comparative example and example

[0124]

[0125] III. Antibacterial property

[0126] According to the test method of GB / T 21510-2008, the antibacterial properties against Escherichia coli and Staphylococcus aureus were tested for each comparative example and example.

[0127] Table 3 Antibacterial property test results of each comparative example and example

[0128]

[0129] IV. Flame retardant property

[0130] According to the flame retardant standard UL 94, the vertical burning test was carried out on each comparative example and example using a vertical burning tester.

[0131] Table 4 Vertical burning test results of each comparative example and example

[0132]

[0133] V. Electromagnetic shielding property

[0134] According to the international standard MIL-STD-285 and its subsequent standard MIL-STD-188-125, it is divided into five grades: A, B, C, D, and E, where grade A has the best shielding effect and grade E has the worst shielding effect.

[0135] Table 5 Electromagnetic shielding test results of each comparative example and example

[0136]

[0137] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. A multifunctional wearable composite fiber membrane, characterized in that, The multifunctional wearable composite fiber membrane has a sandwich structure, with the upper layer being a polyacrylonitrile membrane modified by fullerene hybridized phosphorene, the lower layer being a polyurethane membrane, and the middle layer being a silver nanowire layer; The modification is physical modification.

2. The multifunctional wearable composite fiber membrane according to claim 1, wherein, The fullerene hybridized phosphorene is a fullerene hybridized phosphorene nanosheet, and the mass ratio of fullerene to phosphorene nanosheet is 2:1 to 4:

1.

3. The multifunctional wearable composite fiber membrane according to claim 1, characterized in that, The mass ratio of the fullerene hybridized phosphorene to polyacrylonitrile is 0.6:10 to 1:

10.

4. The multifunctional wearable composite fiber membrane according to claim 1, wherein The mass ratio of polyacrylonitrile to polyurethane is 0.4:1 to 1:

1.

5. The multifunctional wearable composite fiber membrane according to claim 1, wherein The polyacrylonitrile membrane modified by fullerene hybridized phosphorene is an electrospun membrane, and the polyurethane membrane is an electrospun membrane.

6. A method for preparing the multifunctional wearable composite fiber membrane according to any one of claims 1 to 5, characterized in that, It includes the following steps: (1) Prepare fullerene hybridized phosphorene nanosheets, i.e., fullerene hybridized phosphorene, by mechanical ball milling; (2) Disperse the fullerene hybridized phosphorene into a solvent to obtain a fullerene hybridized phosphorene dispersion, add the fullerene hybridized phosphorene dispersion to a polyacrylonitrile solution, stir to obtain a fullerene hybridized phosphorene / polyacrylonitrile spinning solution, and prepare a polyacrylonitrile fiber membrane modified by fullerene hybridized phosphorene by electrospinning; (3) Roll coat or spray a silver nanowire layer on the polyacrylonitrile fiber membrane modified by fullerene hybridized phosphorene, and then cover a polyurethane fiber membrane on one side of the silver nanowire layer, and obtain a multifunctional wearable composite fiber membrane through drying and pressing.

7. The preparation method of the multifunctional wearable composite fiber membrane according to claim 6, wherein In step (2), the voltage of the electrospinning is 18 kv to 20 kv, the spinning speed is 1 mL / h to 1.5 mL / h, and the receiving distance is 10 - 30 cm.

8. The preparation method of the multifunctional wearable composite fiber membrane according to claim 6, characterized in that, The solvent in step (2) is at least one of N,N - dimethylformamide, N,N - dimethylacetamide, and N - methylpyrrolidone.

9. The preparation method of the multifunctional wearable composite fiber membrane according to claim 6, characterized in that, The method of covering the polyurethane fiber membrane in step (3) is electrospinning; The drying in step (3) is vacuum drying, the drying temperature is 30°C to 50°C, and the time is 12 h to 24 h; The pressing is normal temperature pressing, and the pressing time is 6 - 8 h.

10. Application of the multifunctional wearable composite fiber membrane according to any one of claims 1 to 5 in a flexible intelligent wearable device.

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