Preparation method and device of micro-nanofiber material

Abstract

The application discloses a kind of preparation method and device of micro-nanofiber material, including fixed frame, feed assembly and spinning assembly, feed assembly is installed in fixed frame, spinning assembly is rotatably installed below feed assembly;Spinning assembly includes inner disc and multiple solid spinning needle heads, inner disc is rotatably arranged below feed assembly, multiple solid spinning needle heads are evenly protrudingly installed in the side wall of inner disc, and the distance between the movable end of adjacent two solid spinning needle heads is 0.5-2mm;Liquid outlet of feed assembly is arranged above solid spinning needle head, and liquid outlet faces solid spinning needle head, and feed assembly transports spinning solution to solid spinning needle head by liquid outlet.The preparation device of micro-nanofiber material proposed in the application can effectively avoid that spinning solution blocks spinning needle head, improve spinning efficiency, and has simple and reasonable structure and low cost, to overcome the deficiencies in the prior art.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of micro-nano fiber material, and particularly relates to a preparation method and device of micro-nano fiber material. BACKGROUND

[0002] The micro-nano fiber material is a solid linear micro-nano material with a length-diameter ratio greater than 1000:1. Due to the advantages of high pore volume, low density, low mass ratio and extremely high specific surface area, the micro-nano fiber material has a wide application in energy storage, electronics, biotechnology, medical treatment, textile and filtration.

[0003] At present, the electrospinning technology is the most commonly used spinning technology for preparing the micro-nano fiber material, and has the characteristics of simple device, wide material application range and stable fiber quality. However, the electrospinning technology needs a high-voltage electrostatic field, and has a high requirement for the polarity of the spinning solution and the receiving device. In addition, the production efficiency of the electrospinning technology is low, which limits the large-scale development and application of the electrospinning technology.

[0004] In order to overcome the defects of the electrospinning technology, the centrifugal spinning technology is generally used to prepare the micro-nano fiber material. The hollow spinning needle is used as a spinning nozzle in the centrifugal spinning technology. When the applied centrifugal force reaches a critical value, the centrifugal force overcomes the gravity of the spinning solution to generate a sol flow jet. The sol flow jet is stretched and refined into continuous nanofibers under the synergistic action of the centrifugal force and solvent evaporation. The nanofibers are freely stacked to obtain a two-dimensional or three-dimensional micro-nano fiber material. However, in the process of preparing the micro-nano fiber material, the number of the spinning needles is generally only 2 or 4, and the spinning efficiency is slow. In addition, the spinning needle in the prior art is hollow. In the spinning process, the spinning solution flows out from the channel with an internal aperture of 0.1 mm in the hollow needle, and the spinning solution is sprayed to form the micro-nano fiber. However, due to the small internal aperture of the hollow needle and the high molecular solution of the spinning solution, the spinning solution is easily blocked in the hollow spinning needle, which leads to the failure of spinning. If the hollow needle is replaced to solve the blocking problem, the machine needs to be frequently stopped, which seriously affects the spinning efficiency, and also easily causes the increase of equipment maintenance cost and the waste of human resources.

[0005] Therefore, it is necessary to develop a spinning method and device with simple structure, high production efficiency and low cost, so as to realize the industrialized production and application of the micro-nano fiber material. SUMMARY

[0006] The present application aims to provide a preparation device of micro-nano fiber material, which can effectively avoid the blocking of the spinning solution in the spinning needle, improve the spinning efficiency, has a simple and reasonable structure and low cost, and overcomes the defects in the prior art.

[0007] Another object of the present application is to provide a preparation method of micro-nano fiber material, which is matched with the preparation device of micro-nano fiber material, can effectively improve the technical problems of easy clogging of spinning needle and low spinning efficiency in the preparation process of micro-nano fiber material, and is beneficial to ensure the spinning quality of micro-nano fiber material.

[0008] To achieve this object, the present application adopts the following technical solutions:

[0009] A preparation device of micro-nano fiber material, comprising a fixing frame, a feeding assembly and a spinning assembly; the feeding assembly is installed on the fixing frame, and the spinning assembly is rotatably installed below the feeding assembly; the feeding assembly is used to provide spinning solution to the spinning assembly, and the spinning assembly is used to stretch and thin the spinning solution provided by the feeding assembly into continuous micro-nano fibers, and the micro-nano fibers are free to stack or free to stack after sintering to obtain micro-nano fiber material;

[0010] The spinning assembly comprises an inner disc and a plurality of solid spinning needles; the inner disc is rotatably arranged below the feeding assembly, and a plurality of solid spinning needles are arranged around the outside of the inner disc, and the distance between the movable ends of adjacent two solid spinning needles is 0.5-2mm;

[0011] The liquid outlet of the feeding assembly is arranged above the solid spinning needle, and the liquid outlet faces the solid spinning needle; the feeding assembly transports the spinning solution to the solid spinning needle through the liquid outlet.

[0012] Further, the spinning assembly further comprises an outer disc, which is a hollow structure with an open top; the outer disc is coaxial with the inner disc, and the inner disc is installed inside the outer disc; the inner disc and the outer disc jointly form a liquid storage cavity for storing spinning solution;

[0013] A plurality of through holes are formed in the side wall of the outer disc, and the through holes and the liquid storage cavity are in communication with each other;

[0014] The solid spinning needle is provided in multiple rows, and the solid spinning needles in multiple rows are arranged in up-down direction and protrude from the side wall of the outer disc;

[0015] The number of solid spinning needles in one row is multiple, one solid spinning needle in each row protrudes from one through hole, and the fixed end of the solid spinning needle is in interference fit with the through hole, and a liquid passing gap is left between the fixed end of the solid spinning needle and the through hole.

[0016] Further, the length of the solid spinning needle is 10-50mm, and the diameter of the movable end of the solid spinning needle is 0.02-0.12mm.

[0017] Further, a power device is installed on the fixed frame, and an output end of the power device is connected to the inner disc, and the power device is used to drive the rotation of the inner disc.

[0018] Further, a conversion piece is arranged between the power device and the spinning assembly, and the spinning assembly is detachably installed on the bottom of the power device through the conversion piece.

[0019] One end of the conversion piece is connected to the connecting rod, and the other end of the conversion piece is connected to the output end of the power device.

[0020] Further, the feeding assembly comprises a storage tank and a guide pipe connected in sequence, the storage tank is installed on the edge of the fixed frame, and the guide pipe is installed on the middle of the fixed frame, the storage tank is used to store the spinning solution, and the guide pipe is used to transport the spinning solution.

[0021] The end of the guide pipe is provided with a liquid outlet, the liquid outlet is located above the liquid storage cavity, the liquid outlet faces the liquid storage cavity, and the guide pipe transports the spinning solution into the liquid storage cavity through the liquid outlet.

[0022] A preparation method of a micro-nano fiber material, using the nanofiber material preparation device as described above, comprising the following steps:

[0023] A. preparing a spinning solution with spinnability;

[0024] B. transporting the spinning solution to the solid spinning needle through the feeding assembly, and obtaining organic micro-nano fibers through centrifugal spinning of the solid spinning needle through the rotation of the inner disc;

[0025] C. freely stacking the organic micro-nano fibers to obtain an organic micro-nano fiber material;

[0026] or calcining the organic micro-nano fibers to obtain inorganic micro-nano fibers, and freely stacking the inorganic micro-nano fibers to obtain an inorganic micro-nano fiber material.

[0027] Further, the spinning solution comprises 3-15 parts of a polymer and 85-97 parts of a solvent by weight;

[0028] or the spinning solution comprises 3-15 parts of a polymer, 85-97 parts of a solvent, 0.001-0.005 parts of a catalyst, and 20-35 parts of an inorganic precursor by weight.

[0029] Further, in step B, the rotating speed of the inner disc is 1400-2500 r / min, and the feeding speed of the feeding assembly is 1-5 ml / min.

[0030] Further, in step C, the temperature of the calcination treatment is increased to 750-1500 °C at a temperature increasing speed of 5-8 °C / min, and then the temperature is decreased to room temperature after 0-24 hours of heat preservation.

[0031] In step C, the stacking thickness of the free stacking process is 3-5 mm.

[0032] The technical scheme provided by the embodiment of the application can have the following beneficial effects:

[0033] 1. The technical scheme adopts the solid spinning needle instead of the hollow spinning needle in the prior art, avoids the spinning solution from blocking the hollow spinning needle, and the need for frequent shutdown and replacement of the hollow spinning needle, which seriously affects the spinning efficiency, further ensures the spinning efficiency, and also avoids the high equipment maintenance cost and the waste of human resources caused by the replacement of the hollow spinning needle, and reduces the maintenance cost of the equipment.

[0034] 2. In the process of preparing the micro-nano fiber material in the prior art, the number of spinning needles is generally only 2 or 4, and the spinning efficiency is slow. In the technical scheme, the number of solid spinning needles is multiple, preferably 30-50, and can be adjusted according to actual needs, which speeds up the spinning efficiency.

[0035] 3. In the technical scheme, the feeding assembly is arranged above the solid spinning needle, and the spinning solution is attached to the surface of the solid spinning needle and is jetted from the movable end of the solid spinning needle to the air, so that the technical scheme does not need to consider the sealing and fastening of the connection between the feeding assembly and the solid spinning needle, and also does not need to consider the fluid design requirement between the feeding assembly and the solid spinning needle, so that the device structure of the technical scheme is simpler and the manufacturing cost is lower. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 is a structural schematic view of a preparation device for a micro-nano fiber material.

[0037] Figure 2 is a partial structural schematic view of a preparation device for a micro-nano fiber material.

[0038] Figure 3 is a preparation device for a micro-nano fiber material Figure 2 of the application.

[0039] Figure 4 is another partial structural schematic view of a preparation device for a micro-nano fiber material.

[0040] Figure 5 is another partial structure schematic view of the preparation device of the micro-nano fiber material.

[0041] Figure 6 is the SEM diagram of the micro-nano fiber material prepared by using the technical solution.

[0042] Among them: fixed frame 1, feed assembly 2, storage tank 21, material guide pipe 22, liquid outlet 23, spinning assembly 3, inner disc 31, solid spinning needle 32, outer disc 33, through hole 331, connecting rod 34, liquid storage cavity 301, power device 4, conversion piece 5. DETAILED DESCRIPTION

[0043] The embodiments of the present application are described in detail below, examples of which are shown in the drawings, wherein the same or similar reference signs represent the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the drawings are exemplary and are only used to explain the present application, and cannot be understood as a limitation of the present application.

[0044] The technical solution provides a preparation device of micro-nano fiber material, which comprises a fixed frame 1, a feed assembly 2 and a spinning assembly 3; the feed assembly 2 is installed on the fixed frame 1, and the spinning assembly 3 is rotatably installed below the feed assembly 2; the feed assembly 2 is used to provide spinning solution to the spinning assembly 3, and the spinning assembly 3 is used to stretch and refine the spinning solution provided by the feed assembly 2 into continuous micro-nano fibers, and the micro-nano fibers are freely stacked or sintered to obtain a micro-nano fiber material;

[0045] The spinning assembly 3 comprises an inner disc 31 and a plurality of solid spinning needles 32, the inner disc 31 is rotatably arranged below the feed assembly 2, and a plurality of solid spinning needles 32 are arranged around the outside of the inner disc 31, and the distance between the movable ends of two adjacent solid spinning needles 32 is 0.5-2mm;

[0046] The liquid outlet 23 of the feed assembly 2 is arranged above the solid spinning needle 32, and the liquid outlet 23 faces the solid spinning needle 32, and the feed assembly 2 transports the spinning solution to the solid spinning needle 32 through the liquid outlet 23.

[0047] In order to overcome the technical problems that the spinning needle is easy to be blocked and the spinning efficiency is low in the prior art, the technical solution provides a preparation device of micro-nano fiber material, as shown in Figures 1-4As shown, it includes a fixing frame 1, a feeding component 2, and a spinning component 3; the feeding component 2 provides a spinning solution to the spinning component 3, and the spinning component 3 stretches and refines the spinning solution into continuous nanofibers. The micro-nanofibers are freely stacked or sintered and then freely stacked to obtain two-dimensional or three-dimensional micro-nanofiber materials.

[0048] Specifically, the spinning assembly 3 includes an inner disc 31 and a plurality of solid spinning needles 32. The feeding assembly 2 supplies spinning solution to the solid spinning needles 32 through the liquid outlet 23. Since the distance between the movable ends of the solid spinning needles 32 is 0.5-2mm (e.g., ... Figure 3 As shown in m), the gaps between the solid spinning needles 32 are small, allowing the spinning solution to be rapidly and uniformly dispersed among the multiple solid spinning needles 32, and to flow and adhere to the surface of the solid spinning needles 32. The rotation of the solid spinning needles 32 is driven by the inner disc 31, thereby generating centrifugal force. Under the action of centrifugal force and the adhesion between the spinning solution and the surface of the solid spinning needles 32, the spinning solution adhering to the surface of the solid spinning needles 32 is jetted from the movable end of the solid spinning needles 32 into the air, forming a sol jet with a diameter equivalent to that of the movable end of the solid spinning needles 32. During the jetting process, the sol jet is rapidly stretched and thinned. At the same time, the solvent in the spinning solution evaporates rapidly in the sol jet with a high specific surface area, causing the sol jet to dry into a gel, forming micro-nanofibers. The micro-nanofibers can be freely stacked or sintered and then freely stacked to obtain two-dimensional or three-dimensional micro-nanofiber materials. It should be noted that free stacking refers to the natural stacking of micro and nanofibers as they fall under the influence of gravity.

[0049] In existing technologies for preparing micro / nanofiber materials, the number of spinning needles is typically only two or four, resulting in slow spinning efficiency. In contrast, this technical solution uses multiple solid spinning needles 32, preferably 30 to 50, which can be adjusted according to actual needs, thus accelerating the spinning process.

[0050] Furthermore, in existing technologies, the spinning needle is hollow. During the spinning process, the spinning solution flows out from a channel with an internal aperture of 0.1 mm inside the hollow needle, spraying out the spinning solution and forming micro / nanofibers. However, because the internal aperture of the hollow needle is too small, and the spinning solution is a polymer solution, the spinning solution easily gets clogged inside the hollow spinning needle, preventing spinning. If the clogging problem is solved by replacing the hollow needle, frequent machine shutdowns are required, severely affecting spinning efficiency and also increasing equipment maintenance costs and wasting human resources.

[0051] The solid spinning needle 32 is used to replace the hollow spinning needle in the prior art, so that the spinning solution is prevented from blocking the hollow spinning needle, frequent shutdown for replacing the hollow spinning needle is avoided, the spinning efficiency is ensured, the high equipment maintenance cost and the waste of human resources caused by replacing the hollow spinning needle are avoided, and the equipment maintenance cost is reduced.

[0052] Further, in the existing centrifugal spinning technology, the spinning solution enters the hollow spinning needle from the feeding assembly 2, and is then sprayed from the inside of the hollow spinning needle, so that the sealing requirement of the connection between the feeding assembly 2 and the hollow spinning needle is high, the fluid design requirement in the process of entering the hollow spinning needle from the feeding assembly 2 is high, and the assembly and fastening of the feeding assembly 2 and the hollow spinning needle are also considered, so that the existing micro-nano fiber material preparation device is complex in design.

[0053] In the technical solution, the feeding assembly 2 is arranged above the solid spinning needle 32, and the spinning solution is attached to the surface of the solid spinning needle 32 and is sprayed from the movable end of the solid spinning needle 32, so that the sealing and fastening of the connection between the feeding assembly 2 and the solid spinning needle 32 are not considered, and the fluid design requirement between the feeding assembly 2 and the solid spinning needle 32 is not considered, so that the device structure of the technical solution is simpler, and the manufacturing cost is lower.

[0054] Further, although the spinning solution attached to the surface of the solid spinning needle 32 can only spread along the surface to the periphery under the action of the centrifugal force, when the spacing between the solid spinning needles 32 is too large, the spinning solution can flow away from the gap between the solid spinning needles 32, so that the surface of part of the solid spinning needles 32 cannot adhere to the spinning solution, and the spinning efficiency is affected; when the spacing between the solid spinning needles 32 is too small, the spinning solution is easy to adhere together, and cannot be sprayed from the movable end of the solid spinning needle 32 to the air for spinning under the action of the centrifugal force. Therefore, the spacing between the movable ends of the solid spinning needles 32 is limited to 0.5-2 mm in the technical solution, so as to ensure the smooth spinning.

[0055] Preferably, the material of the solid spinning needle 32 is copper.

[0056] Since the metal copper has a certain hardness and a relatively poor activity, it is not easy to be oxidized and deteriorated, and thus cannot be used. Therefore, in one preferred embodiment of the technical solution, the material of the solid spinning needle 32 is copper, so as to ensure the use performance of the solid spinning needle 32.

[0057] Further, the spinning assembly 3 further comprises an outer disc 33, which is a hollow structure with an open top, the outer disc 33 is coaxial with the inner disc 31, and the inner disc 31 is installed inside the outer disc 33; the inner disc 31 and the outer disc 32 jointly form a liquid storage cavity 301 for storing the spinning solution.

[0058] The side wall of the outer disc 33 is provided with a plurality of through holes 331, which are in communication with the liquid storage cavity 301.

[0059] The solid spinning needle 32 is provided in multiple rows, and the solid spinning needles 32 in multiple rows are arranged in up and down directions and protrude from the side wall of the outer disc 33.

[0060] The number of solid spinning needles 32 in one row is multiple, one solid spinning needle 32 in each row protrudes from one through hole 331, and the fixed end of the solid spinning needle 32 is in interference fit with the through hole 331, and a liquid passing gap is left between the fixed end of the solid spinning needle 32 and the through hole 331.

[0061] In a preferred embodiment of the present technical solution, the solid spinning needle 32 is provided in multiple rows, and when the inner disc 31 rotates at high speed, the solid spinning needle 32 installed on the side wall of the inner disc 31 also rotates at high speed, which gives the spinning solution adhered to the surface of the solid spinning needle 32 a large centrifugal force, so that the spinning solution adhered to the surface of the solid spinning needle 32 can only spread to a limited height, generally only 1-3 rows. Therefore, in order to further improve the spinning efficiency, the present technical solution increases the number of rows of solid spinning needles 32 while increasing the number of outer discs 33, uses the inner disc 31 and the outer disc 33 to jointly form a liquid storage cavity 301, and uses the liquid storage cavity 301 to store the spinning solution, so that the surface of all solid spinning needles 32 can uniformly adhere to the spinning solution, thereby further increasing the spinning efficiency.

[0062] Further, the side wall of the outer disc 33 is provided with a plurality of through holes 331, which are in communication with the liquid storage cavity 301, at this time, the solid spinning needle 32 needs to be installed on the side wall of the outer disc 33 to avoid the direct spraying of the spinning solution from the through hole 331, and the rapid spraying of a large amount of spinning solution affects the formation of the spinning fiber, and ensures the smooth spinning.

[0063] Further, the length of the solid spinning needle 32 is 10-50 mm, and the diameter of the movable end of the solid spinning needle 32 is 0.02-0.12 mm.

[0064] The diameter of the micro-nano fiber in the commonly used micro-nano fiber material is 100 nm-1 um, and the diameter of the micro-nano fiber obtained by centrifugal spinning is related to the length of the solid spinning needle 32 and the diameter of the movable end. Therefore, in one preferred embodiment of the technical solution, by limiting the length of the solid spinning needle 32 and the diameter of the movable end, the quality of the micro-nano fiber is ensured, so that the obtained micro-nano fiber material meets the use requirements.

[0065] Further, the power device 4 is installed on the fixed frame 1, the output end of the power device 4 is connected with the inner disc 31, and the power device 4 is used to drive the rotation of the inner disc 31.

[0066] In one preferred embodiment of the technical solution, the power device 4 is provided, and the inner disc 1 is driven to rotate by the power device 4, and the transmission mode is simple.

[0067] Further, the conversion piece 5 is arranged between the power device 4 and the spinning assembly 3, and the spinning assembly 3 is detachably installed at the bottom of the power device 4 through the conversion piece 5.

[0068] The end of the spinning assembly 3 close to the conversion piece 5 is provided with a connecting rod 34, one end of the conversion piece 5 is connected with the connecting rod 34, and the other end of the conversion piece 5 is connected with the output end of the power device 4.

[0069] In one preferred embodiment of the technical solution, the conversion piece 5 is provided, so that the spinning assembly 3 is detachably connected, so that other types of spinning assemblies 3 can be replaced, and the use range of the micro-nano fiber material preparation device is improved.

[0070] Specifically, the end of the spinning assembly 3 close to the conversion piece 5 is provided with a connecting rod 34, one end of the conversion piece 5 is connected with the connecting rod 34, and the other end of the conversion piece 5 is connected with the output end of the power device 4. When the staff needs to spin other types of nano fiber materials, at this time the staff only needs to remove the conversion piece 5, so that the spinning assembly 3 is separated from the conversion piece 5, and then the spinning assembly 3 is pulled out outward, so that the disassembly of the spinning assembly 3 is completed, and then other types of spinning assemblies 3 are replaced.

[0071] It should be noted that the conversion piece 5 can be a shaft coupling, which is not limited here.

[0072] Further, the feeding assembly 2 comprises a storage tank 21 and a guide pipe 22 connected in sequence, the storage tank 21 is installed at the edge of the fixed frame 1, the guide pipe 22 is installed at the middle of the fixed frame 1, the storage tank 21 is used to store spinning solution, and the guide pipe 22 is used to transport spinning solution.

[0073] The end of the material guide pipe 22 is provided with a liquid outlet 23, the liquid outlet 23 is located above the liquid storage cavity 301, the liquid outlet 23 faces the liquid storage cavity 301, and the material guide pipe 22 transports the spinning solution into the liquid storage cavity 301 through the liquid outlet 23.

[0074] In a preferred embodiment of the technical solution, the feeding assembly 2 comprises the material storage tank 21 and the material guide pipe 22 connected end to end in sequence, the end of the material guide pipe 22 is provided with a liquid outlet 23, the liquid outlet 23 is located above the liquid storage cavity 301, the liquid outlet 23 faces the liquid storage cavity 301, and the material guide pipe 22 transports the spinning solution into the liquid storage cavity 301 through the liquid outlet 23, which facilitates smooth spinning of the solid spinning needle 32 and is simple and efficient.

[0075] In addition, by installing the material storage tank 21 on the edge of the fixed frame 1 and installing the material guide pipe 22 on the middle of the fixed frame 1, the installation stability of the feeding assembly 2 is improved.

[0076] A method for preparing a micro-nano fiber material using the above-mentioned device for preparing a nano fiber material, comprising the following steps:

[0077] A. preparing a spinning solution with spinnability;

[0078] B. transporting the spinning solution to the solid spinning needle 32 through the feeding assembly 2, and obtaining organic micro-nano fibers by centrifugal spinning of the solid spinning needle 32 through rotation of the inner disc 31;

[0079] C. freely stacking the organic micro-nano fibers to obtain an organic micro-nano fiber material;

[0080] or calcining the organic micro-nano fibers to obtain inorganic micro-nano fibers, and freely stacking the inorganic micro-nano fibers to obtain an inorganic micro-nano fiber material.

[0081] The present application also provides a method for preparing a micro-nano fiber material, which cooperates with the device for preparing a micro-nano fiber material to effectively improve the technical problems of easy clogging of the spinning needle and low spinning efficiency in the existing micro-nano fiber material preparation process, and is conducive to ensuring the spinning quality of the micro-nano fiber material.

[0082] Specifically, before spinning, a spinning solution with spinnability is first prepared, wherein the type of the spinning solution can be prepared according to actual needs, when inorganic micro-nano fiber material is needed, a spinning solution suitable for inorganic micro-nano fiber material can be prepared, when organic micro-nano fiber material is needed, a spinning solution suitable for organic micro-nano fiber material can be prepared, and the type of the spinning solution is not limited.

[0083] Secondly, the spinning solution is delivered to the solid spinning needle 32 through the feeding assembly 2, and the organic micro-nano fiber is obtained through centrifugal spinning by rotating the inner disc 31. In this process, by using the solid spinning needle 32 instead of the hollow spinning needle in the prior art, the spinning solution is prevented from blocking the hollow spinning needle, and the spinning efficiency is seriously affected. The situation of frequent shutdown and replacement of the hollow spinning needle is avoided, and the spinning efficiency is further ensured. At the same time, the high equipment maintenance cost and the waste of human resources caused by replacing the hollow spinning needle are avoided, and the maintenance cost of the equipment is reduced. In addition, in the technical solution, the number of solid spinning needles 32 is multiple, which further improves the spinning efficiency.

[0084] Finally, when preparing the organic micro-nano fiber material, the organic micro-nano fiber is freely stacked to obtain; when preparing the inorganic micro-nano fiber material, the inorganic micro-nano fiber is obtained by calcining treatment, and the inorganic micro-nano fiber material is obtained by freely stacking the inorganic micro-nano fiber, and the preparation method is simple.

[0085] Further, the spinning solution includes 3-15 parts of polymer and 85-97 parts of solvent by weight;

[0086] Or, the spinning solution includes 3-15 parts of polymer, 85-97 parts of solvent, 0.001-0.005 parts of catalyst and 20-35 parts of inorganic precursor by weight.

[0087] When preparing the organic spinning fiber material, the spinning solution includes polymer and solvent, the polymer is dissolved in the solvent, the spinning solution has a specific rheological property, the spinnability of the spinning solution is realized, and the micro-nano fiber material can be obtained.

[0088] Further, the spinning solution includes 3-15 parts of polymer and 85-97 parts of solvent by weight, which is more conducive to obtaining a uniformly dissolved spinning solution for preparing organic micro-nano fiber, and the above concentration of the spinning solution is conducive to subsequent jet spinning, and the obtained organic spinning fiber material has excellent compression and flexibility; if the polymer content is too low, the spinning solution concentration is too low, which affects the finished product efficiency of the micro-nano fiber material; if the polymer content is too high, on the one hand, the polymer is not easy to be completely dissolved, which increases the difficulty of polymer dissolution; on the other hand, the viscosity of the obtained spinning solution is too high, which increases the difficulty of spinning.

[0089] When the inorganic spun fiber material is prepared, the spinning solution comprises 3-15 parts of polymer, 85-97 parts of solvent, 0.001-0.005 parts of catalyst and 20-35 parts of inorganic precursor, the inorganic precursor is hydrolyzed to obtain oxide, and the inorganic micro-nano fiber is obtained through spinning and calcination treatment; the catalyst mainly plays a catalytic role, which can make the inorganic precursor quickly, effectively and more fully hydrolyzed into inorganic oxide, and then is conducive to obtaining inorganic micro-nano fiber with excellent performance.

[0090] Further, the spinning solution comprises 3-15 parts of polymer, 85-97 parts of solvent, 0.001-0.005 parts of catalyst and 20-35 parts of inorganic precursor, which is more conducive to obtaining a uniformly dissolved spinning solution that can be used to prepare inorganic micro-nano fiber, and the above-mentioned concentration of the spinning solution is conducive to subsequent jet spinning, and the inorganic spun fiber material with excellent performance such as compressibility and flexibility is obtained.

[0091] In order to obtain a fully dissolved spinning solution, the step of preparing the spinning solution comprises: adding polymer or polymer, catalyst and inorganic precursor into the solvent according to the ratio, and then stirring and dissolving at a stirring speed of 100-500 r / min under the condition of room temperature (25℃)-100℃ for 0.5-5 hours, so as to obtain a spinning solution with appropriate concentration. The specific amount of polymer and solvent and the specific process conditions can be set by the person skilled in the art according to the specific polymer and the selected solvent, which is not limited here, as long as the polymer is fully and quickly dissolved. The stirring can be completed by mechanical stirring or magnetic stirring.

[0092] Preferably, the polymer is at least one of polyvinyl alcohol, polyethylene glycol, polyimide, polyurethane, polyacrylonitrile, polyvinylpyrrolidone, cellulose, polyvinylidene fluoride, polymethyl methacrylate, polyacrylamide, polylactic acid, polyamide, polycaprolactone, polyvinyl butyral, polyethylene oxide, polyaniline and polycarbonate. Thus, the polymer material is widely available, easy to spin, and easy to remove in the subsequent calcination process.

[0093] The solvent is at least one of water, formic acid, acetic acid, acetonitrile, tetrahydrofuran, acetone, acetylacetone, butanone, n-hexane, cyclohexane, n-heptane, N-methyl pyrrolidone, 1,2-propanediol, chloroform, dichloromethane, 1,2-dichloroethane, methanol, ethanol, isopropyl alcohol, 1-methoxy-2-propanol, toluene, xylene, ethylenediamine, tert-butyl alcohol, n-butyl alcohol, n-propanol, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide and carbon tetrachloride.

[0094] The catalyst is at least one of phosphoric acid, hydrochloric acid, citric acid, urea and cetyltrimethylammonium bromide.

[0095] The inorganic precursor is at least one of zirconium oxychloride, zirconium acetate, zirconium n-propyl alcohol, zirconium n-butyl alcohol, zirconium hydroxide, zirconium acetylacetone, tetraethyl orthosilicate, methyl orthosilicate, aluminum isopropyl alcohol, aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum acetate, aluminum acetylacetone, hafnium tetrachloride, hafnium sulfate, hafnium n-butyl alcohol, hafnium ethyl alcohol, hafnium hydroxide, hafnium oxychloride, hafnium oxy nitrate, tetrabutyl titanate, potassium hexatitanate, potassium hydroxide, isobutyl titanate, barium acetate, tin chloride, tantalum pentachloride, cobalt acetate, zinc acetate, copper acetate, nickel acetate, titanium isopropyl alcohol, cerium nitrate, magnesium acetate, zinc nitrate, silver nitrate, tantalum isopropyl alcohol, niobium acetate, iron chloride, iron citrate, germanium isopropyl alcohol, manganese acetate, indium nitrate, polycarbosilane, chromium nitrate, chromium chloride, tungsten isopropyl alcohol, magnesium nitrate, iron nitrate, manganese chloride, cobalt nitrate, yttrium nitrate, and yttrium acetate.

[0096] Further, in step B, the rotating speed of the inner disc 31 is 1400-2500 r / min, and the feeding speed of the feeding assembly 2 is 1-5 ml / min.

[0097] When the rotating speed of the inner disc 31 is <1400 r / min, the rotating speed of the solid spinning needle 32 is too slow, so that the centrifugal force of the spinning solution applied to the surface of the solid spinning needle 32 is too low, the process of the spinning solution jetting from the active end of the solid spinning needle 32 to the air is hindered, and then the spinning efficiency is affected; when the rotating speed of the inner disc 31 is >2500 r / min, the centrifugal force of the spinning solution applied to the surface of the solid spinning needle 32 is too high, so that the spinning solution is sprayed too fast under the action of the centrifugal force, the obtained micro-nano fiber is too thick, and the quality of the nano fiber material is affected. Therefore, in one preferred embodiment of the present application, the rotating speed of the inner disc 31 is limited to 1400-2500 r / min, so as to ensure the spinning efficiency and the quality of the micro-nano fiber material. In addition, compared with the high rotating speed of 8000-20000 r / min of the prior art centrifugal spinning technology, the low rotating speed of 1400-2500 r / min of the present application can obtain high-quality micro-nano fiber material, on the one hand, the design requirement of the power device 4 is not high, and the manufacturing cost of the equipment is reduced; on the other hand, it is beneficial to reduce the moment of inertia, and effectively reduce the damage to the equipment when the power device 4 is out of balance.

[0098] Further, when the feeding speed of the feeding assembly 2 is too fast, too much spinning solution is attached to the surface of the solid spinning needle 32, which can easily lead to thickening of the nanofiber and affect the quality of the micro-nanofiber material; when the feeding speed of the feeding assembly 2 is too slow, on the one hand, the nanofiber is too thin; on the other hand, the feeding speed of the spinning solution cannot keep up with the spinning speed, which also affects the spinning efficiency. Therefore, in one preferred embodiment of the present technical solution, the feeding speed of the feeding assembly 2 is 1-5 ml / min, which also ensures the spinning efficiency and the quality of the micro-nanofiber material.

[0099] Further, in step C, the temperature of the calcination treatment is increased to 750-1500°C at a temperature increasing speed of 5-8°C / min, and then the temperature is decreased to room temperature after holding for 0-24 hours.

[0100] In step C, the stacking thickness of the free stacking process is 3-5 mm.

[0101] When the temperature increasing speed of the calcination treatment is <5°C / min, the temperature increasing speed is slow, which leads to slow calcination efficiency and reduces the preparation efficiency of the inorganic micro-nanofiber material; when the temperature increasing speed of the calcination treatment is >8°C / min, the temperature increasing speed is too fast, which leads to insufficient carbonization of the inorganic micro-nanofiber and affects the quality of the inorganic micro-nanofiber material. Therefore, in one preferred embodiment of the present technical solution, the temperature increasing speed of the calcination treatment is limited to 5-8°C / min, which ensures the quality of the obtained inorganic micro-nanofiber material.

[0102] Further, when the stacking thickness is <3 mm, the stacking thickness is too thin, and the stacked micro-nanofiber material needs to be frequently transported out, which can easily lead to inconvenience in production; when the stacking thickness is >5 mm, the stacking thickness is too thick, and the organic micro-nanofiber or the inorganic micro-nanofiber is not completely dried and solidified before being stacked together, which can easily affect the quality of the micro-nanofiber material. Therefore, in one preferred embodiment of the present technical solution, the stacking thickness of the free stacking process is limited to 3-5 mm, which ensures the quality of the micro-nanofiber material and guarantees the convenience of production.

[0103] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and / or "comprising," when used in this specification, specify the presence of stated features, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and / or groups thereof.

[0104] The foregoing is considered as illustrative only of the principles of the application. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the application to the exact construction and practice described. Accordingly, all such variations are intended to be included within the scope of the present application as defined in the following claims, along with full equivalents thereof.

[0105] In the description of the present application, it is to be understood that the orientation or positional relationships indicated by terms such as "front", "back", "up", "down", "left", "right", "lateral", "vertical", "horizontal", "top", "bottom", and the like are generally based on the orientation or positional relationships shown in the drawings, and are merely intended to facilitate the description and simplify the description, and do not indicate or imply that the device or element referred to must have a particular orientation or be constructed and operated in a particular orientation, and therefore cannot be construed as limiting the scope of protection of the present application. The orientation terms "inner", "outer" refer to the inner and outer relative to the contour of the components themselves.

[0106] For the convenience of description, spatial relative terms such as "over", "above", "upper surface", "upper", and the like can be used herein to describe the spatial positional relationship of one device or feature with respect to other devices or features as shown in the drawings. It should be understood that the spatial relative terms are intended to include different orientations in use or operation in addition to the orientation of the device as described in the drawings. For example, if the device in the drawings is inverted, the device described as "above" or "over" other devices or structures will be positioned "below" or "under" the other devices or structures. Thus, the exemplary term "above" can include both "above" and "below" orientations. The device can also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatial relative descriptions used herein are interpreted accordingly.

[0107] In addition, it should be noted that the use of the terms "first", "second", and the like do not have a special meaning, and are used only to facilitate the distinction between corresponding parts, and therefore cannot be construed as limiting the scope of protection of the present application.

[0108] It is to be noted that the terms "first", "second", and the like in the description and in the claims of the present application and in the above description of the drawings merely denote similar objects without necessarily requiring a specific order or sequence of these objects. It is to be understood that data used in these descriptions can be interchanged, where appropriate, so that the embodiments of the present application described herein can be carried out in other than the order shown or described herein.

[0109] The technical principles of the present application are described above in combination with specific embodiments. These descriptions are only for explaining the principles of the present application and cannot be interpreted in any way as a limitation on the scope of protection of the present application. Based on the explanations herein, other specific embodiments of the present application can be conceived by those skilled in the art without requiring creative efforts, and these embodiments will all fall within the scope of protection of the present application.

Claims

1. An apparatus for preparing micro / nanofiber materials, characterized in that, It includes a fixing frame, a feeding assembly, and a spinning assembly; the feeding assembly is mounted on the fixing frame, and the spinning assembly is rotatably mounted below the feeding assembly; the feeding assembly is used to provide a spinning solution to the spinning assembly, and the spinning assembly is used to stretch and refine the spinning solution provided by the feeding assembly into continuous micro / nanofibers, and the micro / nanofibers are freely stacked or sintered and then freely stacked to obtain a micro / nanofiber material; The spinning assembly includes an inner disc and a plurality of solid spinning needles. The inner disc is rotatably disposed below the feeding assembly. The plurality of solid spinning needles are arranged around the outside of the inner disc, and the distance between the movable ends of two adjacent solid spinning needles is 0.5 to 2 mm. The liquid outlet of the feeding assembly is located above the solid spinning needle and faces the solid spinning needle. The feeding assembly delivers spinning solution to the solid spinning needle through the liquid outlet. The spinning assembly also includes an outer disk, which is a hollow structure with an open top. The outer disk is coaxial with the inner disk, and the inner disk is installed inside the outer disk. The inner disk and the outer disk together form a liquid storage cavity, which is used to store the spinning solution. The outer disk has multiple through holes on its side wall, and the through holes are interconnected with the liquid storage cavity; The solid spinning needles are arranged in multiple rows, and the multiple rows of solid spinning needles are arranged vertically and protruding from the side wall of the outer disc. The number of solid spinning needles in a row is multiple, with one solid spinning needle in each row protruding from a through hole, and the fixed end of the solid spinning needle is interference-fitted with the through hole, with a liquid passage gap left between the fixed end of the solid spinning needle and the through hole.

2. The apparatus for preparing micro / nanofiber materials according to claim 1, characterized in that, The solid spinning needle has a length of 10–50 mm and a diameter of 0.02–0.12 mm at its movable end.

3. The apparatus for preparing micro / nanofiber materials according to claim 1, characterized in that, It also includes a power unit, which is mounted on the fixed frame. The output end of the power unit is connected to the inner disk, and the power unit is used to drive the rotation of the inner disk.

4. The apparatus for preparing micro / nanofiber materials according to claim 3, characterized in that, It also includes a conversion element disposed between the power unit and the spinning assembly, wherein the spinning assembly is detachably mounted to the bottom of the power unit via the conversion element; The spinning assembly has a connecting rod at one end near the conversion element, one end of the conversion element is connected to the connecting rod, and the other end of the conversion element is connected to the output end of the power device.

5. The apparatus for preparing micro / nanofiber materials according to claim 1, characterized in that, The feeding assembly includes a storage tank and a guide pipe connected end to end in sequence. The storage tank is installed on the edge of the fixed frame, and the guide pipe is installed in the middle of the fixed frame. The storage tank is used to store the spinning solution, and the guide pipe is used to transport the spinning solution. The feed tube has a liquid outlet at its end, which is located above the liquid storage chamber and faces the liquid storage chamber. The feed tube delivers the spinning solution into the liquid storage chamber through the liquid outlet.

6. A method for preparing micro / nanofiber materials, characterized in that, Using the apparatus for preparing nanofiber materials as described in any one of claims 1 to 5, the method includes the following steps: A. Prepare a spinning solution with spinnability; B. The spinning solution is fed to the solid spinning needle through the feeding assembly, and the solid spinning needle centrifugally spins organic micro and nanofibers by rotating the inner disk. C. The organic micro-nanofibers are freely stacked to obtain organic micro-nanofiber materials; Alternatively, the organic micro / nanofibers can be calcined to obtain inorganic micro / nanofibers, and the inorganic micro / nanofibers can be freely stacked to obtain inorganic micro / nanofiber materials.

7. The method for preparing a micro / nanofiber material according to claim 6, characterized in that, The spinning solution comprises 3 to 15 parts of polymer and 85 to 97 parts of solvent, calculated by weight. Alternatively, calculated by weight, the spinning solution comprises 3-15 parts polymer, 85-97 parts solvent, 0.001-0.005 parts catalyst, and 20-35 parts inorganic precursor.

8. The method for preparing a micro / nanofiber material according to claim 6, characterized in that, In step B, the rotational speed of the inner disc is 1400-2500 r / min, and the feeding speed of the feeding assembly is 1-5 ml / min.

9. The method for preparing a micro / nanofiber material according to claim 6, characterized in that, In step C, the calcination temperature is increased to 750℃ to 1500℃ at a heating rate of 5 to 8℃ / min, held at that temperature for 0 to 24 hours, and then cooled to room temperature. In step C, the stacking thickness of the free stacking process is 3-5 mm.

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