A bubble-assisted wet spinning device, wet power fiber material, preparation method and application

Abstract

The application provides a bubble-assisted wet spinning device, a wet power fiber material, a preparation method and application, and belongs to the technical field of material preparation and application. The bubble-assisted wet spinning device comprises a spinning needle, a spinning liquid injection part and a gas injection part. The spinning needle comprises an inner channel and an outer channel. The inner channel is used for inserting a metal wire. The spinning liquid injection part and the gas injection part are communicated with the outer channel through the outer wall of the outer channel. The spinning liquid injection part is used for controlling the advancing speed of the spinning liquid. The gas injection part is used for controlling the gas pressure entering the bubble-assisted wet spinning device, so as to obtain fiber materials with different morphological structures. The bubble-assisted wet spinning device provided by the application can obtain fiber materials with various morphological structures by only changing the pressure or flow of the entering gas, so as to meet different use requirements.

Description

Technical Field

[0001] This invention relates to the field of material preparation and application technology, and in particular to a bubble-assisted wet spinning device, a wet power-generating fiber material, its preparation method, and its application. Background Technology

[0002] Nature has nurtured a variety of water-related materials, such as spider silk, pitcher plants, cactus spines, nerve fibers, and muscle fibers, possessing a range of functions including safety, hunting, water collection, sensing, and adaptive actuation. Spider silk is known for its remarkable ability to collect moisture from humid air; the serrated structures on the surfaces of pitcher plants and cactus spines facilitate the collection and transfer of water; and the electrical properties of nerve and muscle fibers in aquatic environments have increasingly fascinated scientists about the conversion of water into electricity, inspiring the design of materials with unique wettability for power generation. Inspired by these natural materials, various spinning techniques have been used to create a large number of biomimetic fibers with customizable intelligent functions. However, because water-powered materials typically require layered structural designs, their geometric properties are often limited, making it difficult to design structures that match the morphology of natural biological materials. While functionalized structures can be matched through material microfabrication techniques (such as 3D printing), the production of large quantities of fiber materials remains relatively scarce, which is even a more serious problem limiting their application.

[0003] Recently, hydroelectric power generation technology, especially evaporation-induced power generation (WEG) and moisture-induced power generation (MEG), has attracted much attention due to its spontaneous DC output (see: Liu X, Gao H, Ward JE, et al. Power generation from ambient humidity using protein nanowires. Nature. 2020; 578(7796):550-554.). Many functional materials, such as graphene oxide films with heterogeneous oxygen content, polymer films, and bacterial protein nanowires, have been shown to generate electricity upon contact with humid air. In recent years, transition metal dichalcogenides (TMDCs) have attracted widespread attention as representative two-dimensional (2D) van der Waals (vdW) semiconductor materials due to their excellent electronic and optoelectronic properties and ultra-thin 2D characteristics, making them strong contenders for emerging electronic applications. In particular, molybdenum disulfide (MoS2) has been extensively studied in various research fields. It not only has excellent performance of MoS2-based devices, but also has strong spin-orbit coupling and valence electron properties (see reference: Acerce M, Voiry D, Chhowalla M. Metallic 1T phaseMoS2 nanosheets as supercapacitor electrode materials. Nature Nanotech. 2015; 10(4):313-318.).

[0004] Textiles can serve as an ideal carrier for hydroelectric technology. Firstly, fabrics have wide applications in all aspects of our lives; soft, lightweight, and sustainable energy harvesting fabrics for photovoltaics and thermoelectric applications are considered to have enormous application potential. Secondly, fabric structures made of fibers can be easily designed with controllable moisture conductivity, such as single-moisture-wicking fabrics, which is beneficial for the structural design of water diffusion in hydroelectric power generation. Currently, artificial spinning technologies, including dry spinning, wet spinning, electrospinning, microfluidic spinning, thermal stretching, and 3D printing, have been used to manufacture fibers with various structures and functions. Among them, wet spinning is a spinning method in which spinning solution is flowed into a pre-designed needle and then sprayed into a coagulation bath to form core-sheath fibers with different structures. However, the needle manufacturing process of existing wet spinning methods is complex, and usually a single needle can only produce fibers with one type of morphology. Summary of the Invention

[0005] To address one or more technical problems existing in the prior art, this invention provides a bubble-assisted wet spinning device, a wet power-generating fiber material, a preparation method, and applications. The bubble-assisted wet spinning device provided by this invention can obtain fibers with various morphologies simply by changing the pressure or flow rate of the introduced gas, thereby meeting different application requirements.

[0006] The present invention provides a bubble-assisted wet spinning apparatus in a first aspect, the bubble-assisted wet spinning apparatus comprising a spinning needle, a spinning solution injection component and a gas injection component;

[0007] The spinning needle includes an inner channel and an outer channel; the inner channel is used to insert a metal wire.

[0008] The spinning solution injection component and the gas injection component are connected to the outer channel through the outer wall of the outer channel;

[0009] The spinning solution injection component is used to control the propulsion speed of the spinning solution;

[0010] The gas injection component is used to control the gas pressure introduced into the bubble-assisted wet spinning device to obtain fiber materials with different morphological structures.

[0011] Preferably, the diameter of the inner channel is 0.1–0.2 mm; and / or

[0012] The diameter of the outer channel is 1.0 to 3.5 mm.

[0013] Preferably, the gas injection component includes a gas needle, a gas controller, and a gas reservoir;

[0014] The diameter of the air needle is 0.05–0.12 mm; and / or

[0015] The distance between the outlet of the air needle and the outlet of the spinning needle is 5-20 mm.

[0016] In a second aspect, the present invention provides a wet power generation fiber material, the wet power generation fiber material comprising fiber material prepared using the bubble-assisted wet spinning apparatus described in the first aspect.

[0017] Preferably, the morphology of the fiber material is one or more of the following: cylindrical, hollow spindle structure, solid spindle structure, ratchet structure, and hybrid spindle structure; and / or

[0018] The fiber material is a core-sheath fiber, and the core layer of the core-sheath fiber is a metal wire.

[0019] Preferably, the sheath of the core-sheath fiber comprises a sodium alginate / molybdenum disulfide intercalated composite material;

[0020] Preferably, the mass ratio of sodium alginate to molybdenum disulfide nanosheets in the skin layer is 1:0.1 to 2;

[0021] Preferably, the molybdenum disulfide nanosheets have a size of 100–600 nm and a thickness of 1.0–3.0 nm.

[0022] Preferably, the wet power generation fiber material further includes carbon nanotube fibers coated on the surface of the fiber material.

[0023] In a third aspect, the present invention provides a method for preparing the wet-generating fiber material described in the second aspect, the method comprising:

[0024] Metal wires are inserted into the inner channel of a bubble-assisted wet spinning device, and the propulsion speed of the spinning solution and the pressure of the introduced gas are controlled to perform wet spinning and obtain fiber materials.

[0025] Carbon nanotube fibers are composited onto the surface of the fiber material to obtain a wet power generation fiber material.

[0026] Preferably, the spinning solution is obtained by mixing molybdenum disulfide nanosheets, sodium alginate, and a solvent;

[0027] The propulsion speed of the spinning solution is 0.5–10 mL / min; and / or

[0028] The pressure of the introduced gas is 0–100 kPa.

[0029] The present invention provides, in a fourth aspect, the application of the wet power generation fiber material described in the second aspect for use in the field of wet power generation.

[0030] Compared with the prior art, the present invention has at least the following beneficial effects:

[0031] The bubble-assisted wet spinning device provided by this invention includes a gas injection component connected to the spinning needle. Compressed gas is introduced into the outer channel of the spinning needle through this component. Depending on the gas pressure distribution, single continuous small bubbles, continuous long bubbles, and bubble jets are generated. These bubbles affect fiber formation after the spinning solution enters the coagulation bath from the needle, resulting in fibers with different surface structures. The bubble-assisted wet spinning device provided by this invention can change the morphology of the formed fibers simply by altering the pressure or flow rate of the introduced gas, obtaining fiber materials with different morphologies (cylindrical, hollow spindle structure, solid spindle structure, ratchet structure, and mixed spindle structure). This overcomes the problem in existing wet spinning devices where a single-structure needle can only form fibers with one morphology, thus meeting diverse application requirements.

[0032] This invention achieves targeted design of special surface morphology of fibers through a specially designed spinning device, and innovatively combines fibers with wet power generation materials to obtain wet power generation fiber materials with different morphological structures. Based on the different moisture absorption and release effects of these wet power generation fiber materials with varying morphological structures, different wet power generation effects can be achieved, expanding the application prospects of fiber materials in multiple fields. Attached Figure Description

[0033] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0034] Figure 1 This is a schematic diagram of the structure of the bubble-assisted wet spinning device provided by the present invention;

[0035] Figure 2 These are transmission electron microscope images of the cross-section of the sodium alginate / molybdenum disulfide intercalated composite material prepared in Example 1 of this invention, obtained by laser ion beam cutting.

[0036] Figure 3 These are physical images of five different morphological structures of fiber materials prepared under different air pressures according to Example 1 of the present invention;

[0037] Figure 4 These are scanning electron microscope images of five different morphological structures of fiber materials prepared under different air pressures according to Example 1 of the present invention;

[0038] Figure 5 This is a time-voltage diagram of the hollow spindle wet power generation fiber material provided in Embodiment 1 of the present invention under humidity changes;

[0039] Figure 6 This is a time-voltage diagram of the ratchet wet-powered fiber material provided in Embodiment 1 of the present invention under humidity changes;

[0040] Figure 7 This is a graph showing the effect of different mass ratios of sodium alginate and molybdenum disulfide nanosheets on the wet power generation voltage.

[0041] Reference numerals: 11-spinning needle; 111-inner channel; 112-outer channel; 12-spinning solution injection component; 13-gas injection component; 131-gas needle; 132-gas controller; 133-gas storage device. Detailed Implementation

[0042] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0043] The present invention provides a bubble-assisted wet spinning apparatus in a first aspect, the bubble-assisted wet spinning apparatus comprising a spinning needle 11, a spinning solution injection component 12 and a gas injection component 13;

[0044] The spinning needle 11 includes an inner channel 111 and an outer channel 112; the inner channel 111 is used to insert a metal wire.

[0045] The spinning solution injection component 12 and the gas injection component 13 are connected to the outer channel 112 through the outer wall of the outer channel 112;

[0046] The spinning solution injection component 12 is used to control the propulsion speed of the spinning solution;

[0047] The gas injection component 13 is used to control the gas pressure introduced into the bubble-assisted wet spinning device to obtain fiber materials with different morphological structures.

[0048] The bubble-assisted wet spinning device provided by this invention includes a gas injection component connected to the spinning needle. Compressed gas is introduced into the outer channel of the spinning needle through this component. Depending on the gas pressure distribution, single continuous small bubbles, continuous long bubbles, and bubble jets are generated. These bubbles affect fiber formation after the spinning solution enters the coagulation bath from the needle, resulting in fibers with different surface structures. This bubble-assisted wet spinning device can change the morphology (surface geometry) of the formed fibers simply by changing the pressure or flow rate of the introduced gas, obtaining fiber materials with different morphologies (cylindrical, hollow spindle, solid spindle, ratchet, and mixed spindle structures). This overcomes the problem in existing wet spinning devices where a single-structure needle can only form fibers with one morphology, thus meeting diverse application needs. For example, wet-powered power generation fibers prepared using "hollow spindle" fiber materials can be used as self-powered power generation fibers to supply power to external devices, while wet-powered power generation fibers prepared using "ratchet" fiber materials can be used as electronic fibers for precise humidity sensing.

[0049] In some preferred embodiments of the present invention, the diameter of the inner channel is 0.1–0.2 mm; and / or

[0050] The diameter of the outer channel is 1.0 to 3.5 mm.

[0051] In some preferred embodiments of the present invention, the gas injection component includes a gas needle, a gas controller, and a gas reservoir. The gas injection component is used to inject gas into the spinning apparatus and control the gas pressure and flow rate entering the spinning apparatus; wherein, the gas reservoir stores gas, for example, it can be a gas cylinder; the gas controller is used to precisely control the gas pressure, for example, it can be a precision pressure controller; and the gas needle is used to pass gas into the spinning apparatus.

[0052] In some preferred embodiments of the present invention, the spinning solution injection component is a syringe used to control the propulsion speed of the spinning solution.

[0053] In the actual spinning process, the following steps are taken: immersing the spinning needle of the above-mentioned spinning device into the coagulation bath, controlling the propulsion speed of the spinning liquid through the spinning liquid injection component and injecting the spinning liquid into the spinning device, and controlling the gas pressure through the gas injection component and introducing the gas into the spinning device, thereby forming fibers with different morphological structures, and then collecting them through the fiber collection device.

[0054] In some preferred embodiments of the present invention, the diameter of the air needle is 0.05 to 0.12 mm.

[0055] In some preferred embodiments of the present invention, the distance between the outlet of the air needle and the outlet of the spinning needle is 5–20 mm. Controlling the distance between the outlet of the air needle and the outlet of the spinning needle within this range ensures that, during the spinning process, as the air pressure increases, the fiber morphology can change from cylindrical → hollow spindle structure → solid spindle structure → ratchet structure → mixed spindle structure.

[0056] In some preferred embodiments of the present invention, a bubble-assisted wet spinning device includes a spinning needle 11, a spinning solution injection component 12, and a gas injection component 13. The spinning needle 11 includes an inner channel 111 and an outer channel 112. The inner channel 111 is used to insert a metal wire, and the inner diameter of the inner channel 111 is 0.1–0.2 mm. The diameter of the outer channel is 1.0–3.5 mm. The spinning solution injection component 12 and the gas injection component 13 are connected to the outer channel 112 through the outer wall of the outer channel 112. The gas injection component 13 includes a gas needle 131, a gas controller 132, and a gas reservoir 133; the diameter of the gas needle is 0.05-0.12 mm, and the distance between the outlet of the gas needle and the outlet of the spinning needle is 5-20 mm; wherein, the gas controller 132 is a precision pressure regulating valve, and the gas reservoir 133 is a nitrogen cylinder; the spinning solution injection component 12 is used to control the propulsion speed of the spinning solution; the gas injection component 13 is used to control the gas pressure entering the outer layer channel 112 to obtain fiber materials with different morphological structures.

[0057] In a second aspect, the present invention provides a wet power generation fiber material, the wet power generation fiber material comprising fiber material prepared using the bubble-assisted wet spinning apparatus described in the first aspect.

[0058] This invention achieves targeted design of special surface morphology of fibers through a specially designed spinning device, and innovatively combines fibers with wet power generation materials to obtain wet power generation fiber materials with different morphological structures. Based on the different moisture absorption and release effects of these wet power generation fiber materials with varying morphological structures, different wet power generation effects can be achieved, expanding the application prospects of fiber materials in multiple fields.

[0059] In some preferred embodiments of the present invention, the morphology of the fiber material is one or more of the following: cylindrical, hollow spindle structure, solid spindle structure, ratchet structure, and hybrid spindle structure. It should be noted that the hollow spindle structure is a beaded structure comprising multiple uniformly sized hollow spindle structural units; the solid spindle structure is a beaded structure comprising multiple uniformly sized solid spindle structural units; the ratchet structure is a continuous structure comprising multiple uniformly sized ratchet-like units; and the hybrid spindle structure is a beaded structure comprising multiple non-uniformly sized spindle-shaped units.

[0060] In some preferred embodiments of the present invention, the fiber material is a core-sheath fiber, and the core layer of the core-sheath fiber is a metal wire. The internal metal wire core layer of the fiber material (core-sheath fiber) in the fiber-based wet power generation material serves as the negative electrode, while the externally coated (e.g., wound) carbon nanotube fibers serve as the positive electrode, making it applicable to the field of wet power generation.

[0061] In some preferred embodiments of the present invention, the sheath of the core-sheath fiber comprises a sodium alginate / molybdenum disulfide intercalated composite material; preferably, the mass ratio of sodium alginate to molybdenum disulfide nanosheets in the sheath is 1:0.1 to 2 (for example, it can be 1:0.1, 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.6, 1:1.8, or 1:2); preferably, the size of the molybdenum disulfide nanosheets is 100 to 600 nm, and the thickness is 1.0 to 3.0 nm. The sheath of the fiber material, comprising a sodium alginate / molybdenum disulfide intercalated composite material (an organic / inorganic composite material of sodium alginate intercalated two-dimensional molybdenum disulfide nanosheets), can serve as a basic material for wet power generation. Fibers formed from this material can specifically act on moisture in the air, causing the fiber to generate an electric current under humid conditions through the movement of water molecules and the migration and jumping of protons between layers. Constructing transition metal disulfide / sodium alginate materials with a three-dimensional microchannel structure at the microscale ensures superior moisture and electrical conductivity; simultaneously, the macroscopic fiber structure exhibits tunable moisture absorption, thereby improving power generation performance. For example... Figure 7As shown, under the same conditions, by controlling the mass ratio of sodium alginate to molybdenum disulfide nanosheets within the above-mentioned range, the resulting fibers can be ensured to have excellent power generation performance. The inventors discovered that if the sodium alginate content is too high, the power generation performance is poor; if the sodium alginate content is too low, it is detrimental to fiber formation. It should be noted that... Figure 7 The curves in the figure correspond to the time-voltage curves under different mass ratios of sodium alginate and molybdenum disulfide nanosheets.

[0062] In some preferred embodiments of the present invention, the wet power generation fiber material further includes carbon nanotube fibers coated on the surface of the fiber material.

[0063] In a third aspect, the present invention provides a method for preparing the wet-generating fiber material described in the second aspect, the method comprising:

[0064] Metal wires are inserted into the inner channel of a bubble-assisted wet spinning device, and the propulsion speed of the spinning solution and the pressure of the introduced gas are controlled to perform wet spinning and obtain fiber materials.

[0065] Carbon nanotube fibers are composited onto the surface of the fiber material to obtain a wet power generation fiber material.

[0066] The wet power generation fiber material provided by this invention has the advantages of simple and quick preparation process and high yield, which is conducive to industrial production and application in the field of flexible intelligent textiles.

[0067] In some preferred embodiments of the present invention, the spinning solution is obtained by mixing molybdenum disulfide nanosheets, sodium alginate and solvent.

[0068] In some preferred embodiments of the present invention, the method for preparing molybdenum disulfide nanosheets includes:

[0069] (i) Pyrene and lithium are dissolved in dimethyl ether to obtain 10-20 mL of a 0.2-0.8 M pyrene-lithium (Py-Li) solution, wherein the molar ratio of pyrene to lithium is 1:0.5-2.0; (ii) 0.3-1.0 g of commercial MoS2 powder is added to the pyrene-lithium (Py-Li) solution and stirred for 1-10 hours. The mixture is centrifuged, the supernatant is discarded, and the mixture is washed several times with dimethyl ether and then dried under vacuum to obtain the intercalated compound; (iii) The intercalated compound is dissolved in water to form an intercalated compound solution with a concentration of 0.1-0.5 g / mL, and ultrasonic treatment is performed. The suspension obtained after ultrasonic treatment is centrifuged and dried to obtain molybdenum disulfide nanosheets. Preferably, the ultrasonic treatment is performed at 50-250 watts for 5-50 minutes to achieve exfoliation; the centrifugation is performed at 500-6000 rpm for 10-50 minutes to remove residual coarse particles. To improve the quality of molybdenum disulfide nanosheets, the suspension obtained after ultrasonic treatment was centrifuged at least three times.

[0070] In some preferred embodiments of the present invention, the propulsion speed of the spinning solution is 0.5–10 mL / min (for example, it can be 0.5 mL / min, 1 mL / min, 1.5 mL / min, 2 mL / min, 2.5 mL / min, 3 mL / min, 3.5 mL / min, 4 mL / min, 4.5 mL / min, 5 mL / min, 5.5 mL / min, 6 mL / min, 6.5 mL / min, 7 mL / min, 7.5 mL / min, 8 mL / min, 8.5 mL / min, 9 mL / min, etc.). (mL / min, 9.5mL / min or 10mL / min); The propulsion speed of the spinning solution has a certain influence on the morphology of the fiber. The inventors found that if the propulsion speed of the spinning solution is too high or too low, the variety of fiber structural morphologies decreases as the air pressure increases during the spinning process. That is, it is impossible to achieve all the morphological changes of the fiber structure from cylindrical → hollow spindle structure → solid spindle structure → ratchet structure → mixed spindle structure. If the propulsion speed of the spinning solution is too high, the first part of the morphology cannot be obtained. If the propulsion speed of the spinning solution is too low, the second part of the morphology cannot be obtained.

[0071] In some preferred embodiments of the present invention, the pressure of the introduced gas is 0–100 kPa (for example, it can be 0 kPa, 1 kPa, 10 kPa, 15 kPa, 16 kPa, 20 kPa, 25 kPa, 26 kPa, 30 kPa, 32 kPa, 35 kPa, 39 kPa, 40 kPa, 41 kPa, 44 kPa, 50 kPa, 55 kPa, 58 kPa, 60 kPa, 70 kPa, 80 kPa, 90 kPa, or 100 kPa). Controlling the introduced gas pressure within the above range allows for all morphological changes in the fiber structure from cylindrical to hollow spindle structure to solid spindle structure to ratchet structure to mixed spindle structure. It should be noted that when the gas pressure is 0 kPa, the fiber is cylindrical; as the gas pressure continues to increase, it sequentially forms a hollow spindle structure, a solid spindle structure, a ratchet structure, and a mixed spindle structure.

[0072] The present invention provides, in a fourth aspect, the application of the wet power generation fiber material described in the second aspect for use in the field of wet power generation.

[0073] To more clearly illustrate the technical solution and advantages of the present invention, the present invention will be further described below in conjunction with embodiments.

[0074] Example 1

[0075] S1. Pyrene and lithium in a molar ratio of 1:0.5 were dissolved in dimethyl ether to prepare 10 mL of 0.2 M pyrene-lithium (Py-Li) solution. 0.3 g of commercial MoS2 powder was added and stirred for 1 hour. The mixture was centrifuged at 6000 rpm, the supernatant was discarded, and the mixture was washed 5 times with dimethyl ether and then dried under vacuum to obtain the intercalated compound. The intercalated compound was then dissolved in water to form a 0.1 g / mL solution, and sonicated (50 W) for 5 minutes to achieve exfoliation. The resulting suspension was centrifuged at 500 rpm for 10 minutes to remove residual coarse particles, and the suspension was purified by drying to obtain MoS2 nanosheets. To further improve the quality of the nanosheets, the exfoliated suspension was centrifuged at 8000 rpm for 2 minutes, and this process was repeated more than three times to remove excess impurities and some thick, unexfoliated MoS2. Finally, a 5% sodium alginate aqueous solution (where the M:G component is 1:0.5) was prepared, and after being fully dissolved, molybdenum disulfide nanosheets were added at a mass ratio of sodium alginate to molybdenum disulfide of 1:0.1. The solution was then uniformly dispersed for 10 hours under magnetic stirring at 100 r.pm to obtain a liquid crystal spinning solution.

[0076] S2. Insert the metal wire into the inner channel of the spinning needle in advance, then take 20 mL of 0.5% spinning solution into the syringe (spinning solution injection component). The advance speed of the syringe (spinning solution injection component) is 0.5 mL / min. The gas pressure is controlled by the gas injection component. The fiber is then drawn into the coagulation bath of 0.1% calcium chloride. When the gas pressure is 0 kPa, the fiber morphology is ordinary cylindrical (denoted as cylindrical fiber material). When the gas pressure is increased to 10 kPa, the fiber morphology changes from ordinary cylindrical (denoted as cylindrical fiber material) to "hollow spindle structure" (denoted as hollow spindle fiber material). After increasing the gas pressure to 15 kPa, the fiber morphology changes to "solid spindle structure" (denoted as solid spindle fiber material). Continuing to increase the gas pressure to 20 kPa, the fiber morphology changes to "ratchet structure" (denoted as ratchet fiber material). Finally, after increasing the gas pressure to 30 kPa, the fiber cross-section changes to "mixed spindle structure" (denoted as mixed spindle fiber material).

[0077] S3. A layer of carbon nanotube fibers is uniformly wound around the surface of the obtained cylindrical fiber material, hollow spindle fiber material, solid spindle fiber material, ratchet fiber material and mixed spindle fiber material to obtain cylindrical wet power generation fiber material, hollow spindle wet power generation fiber material, solid spindle wet power generation fiber material, ratchet wet power generation fiber material and mixed spindle wet power generation fiber material respectively; wherein the carbon nanotube fibers on the surface are used as positive electrodes and the internal metal wires are used as negative electrodes.

[0078] Transmission electron microscopy (TEM) images of the sodium alginate / molybdenum disulfide intercalated composite material prepared in this embodiment, obtained by laser ion beam cutting of the cross-section, are shown below. Figure 1 As shown, the interlayer spacing of molybdenum disulfide after intercalation is 0.90 nm, while the interlayer spacing of unintercalated layered molybdenum disulfide is 0.64 nm.

[0079] Depend on Figure 3-4 As can be seen, in this embodiment, as the gas pressure increases, the morphology and structure of the fiber material changes from cylindrical → hollow spindle structure → solid spindle structure → ratchet structure → mixed spindle structure.

[0080] The power generation capacity of the wet-generating fiber prepared in this embodiment under ambient humidity conditions and its real-time response to humidity were tested. Figure 5 and Figure 6 As shown, the hollow spindle-shaped wet-powered fiber material, approximately 5 cm long, provided in this embodiment can generate a voltage of approximately 0.4V at 60% relative humidity for more than 9 hours. The ratchet-shaped wet-powered fiber material can respond rapidly and linearly to gradient humidity changes. Figure 5 and Figure 6 The horizontal axis represents time, the left vertical axis represents voltage, and the right vertical axis represents relative humidity.

[0081] Example 2

[0082] S1. A 1:1 molar ratio of pyrene and lithium was dissolved in dimethyl ether to prepare 12 mL of a 0.4 M pyrene-lithium (Py-Li) solution. 0.5 g of commercial MoS2 powder was added and stirred for 3 hours. The mixture was centrifuged at 6000 rpm, the supernatant was discarded, and the mixture was washed five times with dimethyl ether and then vacuum dried to obtain the intercalated compound. The intercalated compound was then dissolved in water to form a 0.3 g / mL solution, and simultaneously sonicated (100 W) for 10 minutes to achieve exfoliation. The resulting suspension was centrifuged at 1000 rpm for 20 minutes to remove residual coarse particles, and the suspension was purified by drying to obtain MoS2 nanosheets. To further improve the quality of the nanosheets, the exfoliated suspension was centrifuged at 10000 rpm for 2 minutes, and this process was repeated more than three times to remove excess impurities and some thick, unexfoliated MoS2. Finally, a 2% sodium alginate aqueous solution (where the M:G component is 1:0.5) was prepared, and after being fully dissolved, molybdenum disulfide nanosheets were added at a mass ratio of sodium alginate to molybdenum disulfide of 1:0.2. The solution was then uniformly dispersed for 10 hours under magnetic stirring at 100 r.pm to obtain a liquid crystal spinning solution.

[0083] S2. Insert the metal wire into the inner channel of the spinning needle in advance, then take 20 mL of 2% spinning solution into the syringe (spinning solution injection component). The advance speed of the syringe (spinning solution injection component) is 1 mL / min. The gas pressure is controlled by the gas injection component. The fiber is then drawn into the coagulation bath of 2% calcium chloride. When the gas pressure is 0 kPa, the fiber morphology is ordinary cylindrical (denoted as cylindrical fiber material). When the gas pressure is increased to 15 kPa, the fiber morphology changes from ordinary cylindrical (denoted as cylindrical fiber material) to "hollow spindle structure" (denoted as hollow spindle fiber material). After increasing the gas pressure to 26 kPa, the fiber morphology changes to "solid spindle structure" (denoted as solid spindle fiber material). Continuing to increase the gas pressure to 32 kPa, the fiber morphology changes to "ratchet structure" (denoted as ratchet fiber material). Finally, after increasing the gas pressure to 44 kPa, the fiber cross-section changes to "mixed spindle structure" (denoted as mixed spindle fiber material).

[0084] S3. A layer of carbon nanotube fibers is uniformly wound around the surface of the obtained cylindrical fiber material, hollow spindle fiber material, solid spindle fiber material, ratchet fiber material and mixed spindle fiber material to obtain cylindrical wet power generation fiber material, hollow spindle wet power generation fiber material, solid spindle wet power generation fiber material, ratchet wet power generation fiber material and mixed spindle wet power generation fiber material respectively; wherein the carbon nanotube fibers on the surface are used as positive electrodes and the internal metal wires are used as negative electrodes.

[0085] Example 3

[0086] S1. Dissolve pyrene and lithium in dimethyl ether at a molar ratio of 1:2 to prepare 18 mL of 0.6 M pyrene-lithium (Py-Li) solution. Add 0.8 g of commercial MoS2 powder and stir for 4 hours. Centrifuge the mixture at 6000 rpm and discard the supernatant. Wash five times with dimethyl ether and then vacuum dry to obtain the intercalated compound. Dissolve the intercalated compound in water to form a 0.4 g / mL solution and sonicate (150 W) for 20 minutes to achieve exfoliation. Centrifuge the resulting suspension at 2000 rpm for 30 minutes to remove residual coarse particles, and then purify the suspension by drying to obtain MoS2 nanosheets. To further improve the quality of the nanosheets, centrifuge the exfoliated suspension at 11000 rpm for 2 minutes and repeat this process more than three times to remove excess impurities and some thick unexfoliated MoS2. Finally, a 3% sodium alginate aqueous solution (where the M:G component is 1:0.5) was prepared, and after being fully dissolved, molybdenum disulfide nanosheets were added at a mass ratio of sodium alginate to molybdenum disulfide of 1:0.6. The solution was then uniformly dispersed for 10 hours under magnetic stirring at 100 r.pm to obtain a liquid crystal spinning solution.

[0087] S2. Insert the metal wire into the inner channel of the spinning needle in advance, then take 20 mL of 3% spinning solution into the syringe (spinning solution injection component). The advance speed of the syringe (spinning solution injection component) is 2 mL / min. The gas pressure is controlled by the gas injection component. The fiber is then drawn into the coagulation bath of 3% calcium chloride. When the gas pressure is 0 kPa, the fiber morphology is ordinary cylindrical (denoted as cylindrical fiber material). When the gas pressure is increased to 16 kPa, the fiber morphology changes from ordinary cylindrical to "hollow spindle structure" (denoted as hollow spindle fiber material). After increasing the gas pressure to 26 kPa, the fiber morphology changes to "solid spindle structure" (denoted as solid spindle fiber material). Continuing to increase the gas pressure to 39 kPa, the fiber morphology changes to "ratchet structure" (denoted as ratchet fiber material). Finally, after increasing the gas pressure to 50 kPa, the fiber cross-section changes to "mixed spindle structure" (denoted as mixed spindle fiber material).

[0088] S3. A layer of carbon nanotube fibers is uniformly wound around the surface of the obtained cylindrical fiber material, hollow spindle fiber material, solid spindle fiber material, ratchet fiber material and mixed spindle fiber material to obtain cylindrical wet power generation fiber material, hollow spindle wet power generation fiber material, solid spindle wet power generation fiber material, ratchet wet power generation fiber material and mixed spindle wet power generation fiber material respectively; wherein the carbon nanotube fibers on the surface are used as positive electrodes and the internal metal wires are used as negative electrodes.

[0089] Example 4

[0090] S1. Dissolve pyrene and lithium in dimethyl ether at a molar ratio of 1:1 to prepare 10 mL of 0.2 M pyrene-lithium (Py-Li) solution. Add 0.3 g of commercial MoS2 powder and stir for 1 hour. Centrifuge the mixture at 6000 rpm and discard the supernatant. Wash five times with dimethyl ether and then vacuum dry to obtain the intercalated compound. Dissolve the intercalated compound in water to form a 0.5 g / mL solution and sonicate (200 W) for 10 minutes to achieve exfoliation. Centrifuge the resulting suspension at 1500 rpm for 40 minutes to remove residual coarse particles, and then purify the suspension by drying to obtain MoS2 nanosheets. To further improve the quality of the nanosheets, centrifuge the exfoliated suspension at 12000 rpm for 1 minute and repeat this process more than three times to remove excess impurities and some thick unexfoliated MoS2. Finally, a 4% sodium alginate aqueous solution (where the M:G component is 1:0.5) was prepared, and after being fully dissolved, molybdenum disulfide nanosheets were added at a mass ratio of sodium alginate to molybdenum disulfide of 1:1.2. The solution was then uniformly dispersed for 10 hours under magnetic stirring at 100 r.pm to obtain a liquid crystal spinning solution.

[0091] S2. Insert the metal wire into the inner channel of the spinning needle in advance, then take 20 mL of 4% spinning solution into the syringe (spinning solution injection component). The advance speed of the syringe (spinning solution injection component) is 3 mL / min. The gas pressure is controlled by the gas injection component. The fiber is then drawn into the coagulation bath of 4% calcium chloride. When the gas pressure is 0 kPa, the fiber morphology is ordinary cylindrical (denoted as cylindrical fiber material). When the gas pressure is increased to 28 kPa, the fiber morphology changes from ordinary cylindrical (denoted as cylindrical fiber material) to "hollow spindle structure" (denoted as hollow spindle fiber material). After increasing the gas pressure to 32 kPa, the fiber morphology changes to "solid spindle structure" (denoted as solid spindle fiber material). Continuing to increase the gas pressure to 41 kPa, the fiber morphology changes to "ratchet structure" (denoted as ratchet fiber material). Finally, after increasing the gas pressure to 58 kPa, the fiber cross-section changes to "mixed spindle structure" (denoted as mixed spindle fiber material).

[0092] S3. A layer of carbon nanotube fibers is uniformly wound around the surface of the obtained cylindrical fiber material, hollow spindle fiber material, solid spindle fiber material, ratchet fiber material and mixed spindle fiber material to obtain cylindrical wet power generation fiber material, hollow spindle wet power generation fiber material, solid spindle wet power generation fiber material, ratchet wet power generation fiber material and mixed spindle wet power generation fiber material respectively; wherein the carbon nanotube fibers on the surface are used as positive electrodes and the internal metal wires are used as negative electrodes.

[0093] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A wet-generating fiber material, characterized in that, The wet power generation fiber material includes fiber material prepared using a bubble-assisted wet spinning device; the bubble-assisted wet spinning device includes a spinning needle, a spinning solution injection component, and a gas injection component. The spinning needle includes an inner channel and an outer channel; the inner channel is used to insert a metal wire. The spinning solution injection component and the gas injection component are connected to the outer channel through the outer wall of the outer channel; The spinning solution injection component is used to control the propulsion speed of the spinning solution; The gas injection component is used to control the gas pressure introduced into the bubble-assisted wet spinning device in order to obtain fiber materials with different morphological structures. The fiber material is a core-sheath fiber, and the core layer of the core-sheath fiber is a metal wire; The sheath of the core-sheath fiber includes a sodium alginate / molybdenum disulfide intercalated composite material, which is an organic / inorganic composite material of sodium alginate intercalated with two-dimensional molybdenum disulfide nanosheets. The mass ratio of sodium alginate to molybdenum disulfide nanosheets in the cortex is 1:0.1~2; The molybdenum disulfide nanosheets have a size of 100~600nm and a thickness of 1.0~3.0nm; The wet power generation fiber material also includes carbon nanotube fibers coated on the surface of the fiber material.

2. The wet-generating fiber material according to claim 1, characterized in that, The morphology of the fiber material is one or more of the following: cylindrical, hollow spindle structure, solid spindle structure, ratchet structure, and mixed spindle structure.

3. The wet-generating fiber material according to claim 1, characterized in that, The diameter of the inner channel is 0.1~0.2 mm; and / or The diameter of the outer channel is 1.0~3.5mm.

4. The wet-generating fiber material according to claim 1, characterized in that, The gas injection component includes a gas needle, a gas controller, and a gas storage device; The diameter of the air needle is 0.05~0.12mm; and / or The distance between the outlet of the air needle and the outlet of the spinning needle is 5~20mm.

5. A method for preparing the wet-generating fiber material according to any one of claims 1-4, characterized in that, The preparation method includes: Metal wires are inserted into the inner channel of a bubble-assisted wet spinning device, and the propulsion speed of the spinning solution and the pressure of the introduced gas are controlled to perform wet spinning and obtain fiber materials; the spinning solution is obtained by mixing molybdenum disulfide nanosheets, sodium alginate and solvent. Carbon nanotube fibers are composited onto the surface of the fiber material to obtain a wet power generation fiber material.

6. The preparation method according to claim 5, characterized in that, The propulsion speed of the spinning solution is 0.5~10 mL / min; and / or The pressure of the introduced gas is 0~100kPa.

7. The application of the wet-generating fiber material according to any one of claims 1-4, characterized in that, Used in the field of wet power generation.

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