Ti3C2MXene / PEO composite micro-nano fiber and preparation method thereof
Through the controllable molding method of Ti3C2•MXene/PEO composite micro-nanofibers, the controllable size MXene micro-nanofibers are prepared under the action of electric field force by using electric direct writing technology, which solves the high cost and resolution in the existing technology. The problem of low and uncontrollable fiber size achieves efficient and low-cost MXene micro-nanofiber printing.
Patent Information
- Application Number
- CN202411499970.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-25
- Publication Date
- 2024-12-20
AI Technical Summary
The existing MXene micro-nanofiber printing technology has problems such as high cost, low resolution, poor fiber size and printing graphics controllability.
Using the controllable molding method of Ti3C2•MXene/PEO composite micro-nanofibers, 6% to 8% PEO-Ti3C2•MXene mixed inks were prepared, and the ink was pulled from the nozzle using electric field force during the electric direct writing printing process. Out, smooth straight or curved micro-nanofibers with sizes ranging from 200 nm to 20 um were prepared by program control of the receiving plate movement.
It realizes high-resolution, low-cost MXene micro-nanofiber printing, with controllable fiber size, avoiding material waste, simple processing technology, and improving production efficiency.
Smart Images
Figure CN119162697A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of micro-nano additive manufacturing, and specifically relates to a Ti3C2•MXene / PEO composite micro-nano fiber and a preparation method thereof. Background Art
[0002] MXene, or transition metal carbide, nitride or carbonitride, is an emerging class of two-dimensional materials with excellent electrochemical, electronic, optical and mechanical properties. It has been widely used in many fields, including energy storage, electronics, optoelectronics, biomedicine, sensors and catalysis. Compared with other two-dimensional materials, MXene has a series of unique properties, such as high metallic conductivity, excellent dispersion quality, negative surface charge and hydrophilicity, making it particularly suitable as printing ink. At present, the printing technology of MXene mainly includes inkjet printing, extrusion printing and laser-assisted printing. The graphics printed by these methods have low resolution, only at the micron level, and the processing equipment is expensive. Electrospinning technology can realize the manufacture of MXene nanofibers, but the morphology of the fibers is disordered and uncontrollable.
[0003] In summary, MXene micro-nanofiber printing technology still faces problems such as high cost, low resolution, and poor controllability of fiber size and printed graphics. Summary of the invention
[0004] In view of the problems of low resolution, high manufacturing cost and uncontrollable size in previous MXene printing technology, the present invention provides a Ti3C2•MXene / PEO composite micro-nano fiber and a preparation method thereof; the preparation method is a controllable molding method for preparing smooth straight or curved micro-nano fibers of Ti3C2•MXene / PEO composite functional materials with a size ranging from 200 nm to 20 um.
[0005] The present invention is implemented by the following technical solution: a method for preparing Ti3C2•MXene / PEO composite micro-nano fibers, comprising the following steps: (1) Preparation of Ti3C2•MXene / PEO composite functional material printing ink: polyethylene oxide (PEO) with a molecular weight of 300,000 was weighed in deionized water, and magnetic stirring was performed for 7 to 9 h to allow the polymer to fully dissolve until no bubbles appeared, and a PEO solution with a mass fraction of 6% to 8% was prepared; 0.01-0.05 g of Ti3C2•MXene was placed in 10 mL of deionized water and ultrasonically dispersed for 3-5 min to obtain a uniformly dispersed Ti3C2•MXene aqueous solution; 0.06-0.08 g of PEO solution was then weighed and added to the uniform solution and magnetically stirred for 4 h to uniformly mix the ink to obtain a mixed ink of 6%-8% PEO - 0.3%-0.7% Ti3C2•MXene; (2) Perform hydrophobic treatment on the printed substrate: During the electro-direct writing printing process, the substrate is ultrasonically cleaned in anhydrous ethanol for 20 to 30 minutes, then cleaned with deionized water for 2 to 3 times, and the cleaned substrate is dried at 60 °C for 20 to 30 minutes; (3) The mixed ink prepared in (1) is loaded into a syringe and a needle with an aperture size of 18 to 24 G is connected to the syringe; the external voltage is set to 2 to 4 kV, the current is set to 0.1 to 0.8 A, the electrode distance is set to <1 cm, the ink propulsion speed is set to 0.1 to 2 mL / h, the program-controlled slide drives the receiving plate to move, and the substrate movement speed is set to 2 to 8 mm / s, thereby preparing Ti3C2•MXene / PEO smooth straight or curved micro-nanofibers with a size ranging from 200 nm to 20 um and printing a preset shape at the same time.
[0006] The substrate is any one of a glass sheet, a silicon sheet, PET, PMMA or PI.
[0007] The present invention also provides a Ti3C2•MXene / PEO composite micro-nano fiber prepared by the method.
[0008] In the process of direct electrographic printing, since the deposition speed of the jet is fixed, when the program-controlled receiving plate movement speed is higher than the final jet speed, fibers of different diameters will be obtained. When the receiving plate speed is too high, the lines will be broken. On the contrary, if the receiving plate speed is lower than the final jet deposition speed, fibers with different degrees of curvature will be printed. At the same time, the flatness of the printing platform is also very critical to the deposition of the fibers. When the receiving plate is not flat, fibers with different degrees of curvature will appear.
[0009] Beneficial effects of the present invention: The method of the present invention uses the electric field force generated by the electric field to "pull" the material out of the nozzle, and in a non-contact manner, by changing the size of the charged nozzle and the distance between it and the collecting substrate, the cone jet is controlled to be deposited on the base material with the motion platform, and the Ti3C2•MXene / PEO composite functional material with a size of 200 nm to 20 um is obtained. The method can avoid material waste, and the processing technology is simple. The obtained fiber material has the advantages of high resolution and controllable size.
[0010] The present invention adopts a low-cost electric direct writing printing Ti3C2•MXene / PEO micro-nano fiber controllable molding method, by preparing a certain concentration of Ti3C2•MXene / PEO composite ink, under the action of electric field force, the ink is pulled out from the nozzle, and the movement of the receiving substrate is controlled by program to obtain Ti3C2•MXene / PEO micro-nano fibers with different patterns ranging from 200 nm to 20 um in size. The method of the present invention is used to print Ti3C2•MXene / PEO ink, which has the characteristics of simple operation, low price and high production efficiency. BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The present invention will be further described below in conjunction with the accompanying drawings: Figure 1 Process flow chart for preparing Ti3C2•MXene / PEO composite ink; Figure 2 A process flow chart for preparing a receiving substrate; Figure 3 A diagram of the electrical direct writing device used in the present invention; Figure 4 This is an electron microscope image of Ti3C2•MXene / PEO composite ink micron fiber under a specific implementation method; Figure 5 Microscope images of fibers printed by 7% PEO-0.3% Ti3C2•MXene composite ink under different applied voltages in a specific embodiment; Figure 6 It is a microscopic image of fibers printed by 7% PEO-0.3% Ti3C2•MXene composite ink at different substrate moving speeds in a specific embodiment; Figure 7 Microscope images of fibers printed at different flow rates using 7% PEO-0.3% Ti3C2•MXene composite ink in a specific embodiment; Figure 8 Microscope images of fibers printed at different printing distances using 7% PEO-0.3% Ti3C2•MXene composite ink in a specific embodiment; Fig. 9 The effect of different printing parameters on the fiber diameter of 7% PEO-0.3% Ti3C2•MXene composite ink in a specific implementation method; in the figure: (a) is the applied voltage; (b) is the substrate movement speed; (c) is the liquid supply flow rate; (d) is the printing distance In the figure: 1-beaker; 2-PEO; 3-multilayer / single-layer Ti3C2•MXene; 4-ultrasonic cell crusher soundproof box; 5-anhydrous ethanol; 6-ultrasonic cleaner; 7-glass sheet; 8-deionized water; 9-drying box; 10-computer; 11-high-speed camera; 12-motion control; 13-flow pump; Figure 5-8 The center scale is 10 microns. DETAILED DESCRIPTION
[0012] In order to make the purpose, 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 part of the embodiments of the present invention, rather than all the embodiments; based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.
[0013] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and the disclosure and materials cited therein are hereby incorporated by reference.
[0014] Technical equivalents to the specific embodiments described that are apparent to those skilled in the art using no more than routine experimentation are intended to be encompassed by this application.
[0015] The experimental methods in the following examples are all conventional methods unless otherwise specified. The instruments and equipment used in the following examples are all conventional laboratory instruments and equipment unless otherwise specified; the experimental materials used in the following examples are all purchased from conventional biochemical reagent stores unless otherwise specified.
[0016] like Figure 1 As shown, the production process steps of Ti3C2•MXene / PEO composite ink are as follows: (a) A small amount of polyethylene oxide (PEO) was dispersed in deionized water and stirred with a magnetic stirrer for 8 hours to fully and evenly dissolve it until no bubbles appeared to prevent it from affecting the continuity of printing, thereby obtaining a PEO solution with a mass fraction of 7%, which was then allowed to stand for 2 hours.
[0017] (b) 0.01-0.05 g of Ti3C2•MXene was respectively placed in 10 mL of deionized water and ultrasonically dispersed for 3-5 min to obtain a uniformly dispersed Ti3C2•MXene aqueous solution; the solution was slowly added to the prepared polyethylene oxide solution under the action of a magnetic stirrer. Since Ti3C2•MXene is difficult to disperse in water, a magnetic stirrer cannot be used to assist in the dissolution of the material. In order to fully mix the Ti3C2•MXene, the Ti3C2•MXene and PEO mixed solution was ultrasonically treated in a soundproof box for 3 min to accelerate the uniform mixing of the ink, thereby obtaining the target solution of 7% PEO-0.3% Ti3C2•MXene mixed ink.
[0018] like Figure 2 As shown, the steps of the production process of the receiving substrate are as follows: In the process of direct electro-writing printing, in order to prevent the material printed on the substrate from being contaminated and the spreading phenomenon from being different from the expected effect, the substrate needs to be hydrophobic. The glass slide was ultrasonically cleaned in anhydrous ethanol for 20 minutes, then washed with deionized water for 3 times, and the cleaned substrate was placed in a drying oven at 60 °C for 20 minutes.
[0019] like Figure 3 As shown, the steps of the direct writing printing process are as follows: The target solution was directly loaded into the syringe, and a high-voltage DC power supply was connected to form a strong electric field. The strong electric field force formed between the nozzle and the conductive substrate was used to pull the liquid out of the nozzle to form the Taylor cone liquid electrospinning method to form Ti3C2•MXene / PEO micro-nano fibers on the glass slide, thereby realizing MXene high-resolution graphics. The direct writing printing voltage was set to 3.6 kV, the current was 0.03 A, the receiving distance was 0.15 mm, the syringe solution was pushed at a speed of 0.2 mL / h, and a 21G needle was used. Under program-controlled movement of the receiving substrate, Ti3C2•MXene / PEO straight fibers with a size of 2.56±0.32 μm and a grid pattern were obtained, as shown in FIG. Figure 4 shown.
[0020] like Figure 5-9 As shown in the figure, the influence of printing parameters on fiber diameter is as follows: the fiber width decreases with increasing voltage, decreases with increasing substrate movement speed, increases with increasing injection pump flow rate, and increases with increasing printing distance. Therefore, by increasing the applied voltage, increasing substrate movement speed, reducing liquid supply flow rate, and shortening printing distance, the width of the deposited fiber can be reduced and the accuracy of the deposited pattern can be improved. Based on this feature, the key parameters in the electrojet printing process can be precisely controlled to achieve controllable manufacturing of Ti3C2•MXene / PEO composite fibers.
[0021] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, a person skilled in the art should understand that the technical solutions described in the aforementioned embodiments can still be modified, or some or all of the technical features can be replaced by equivalents to achieve substantially the same technical effects. These modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present invention and are all covered by the protection scope of the present invention.
Claims
1. A method for preparing Ti3C2•MXene / PEO composite micro-nano fibers, characterized in that: The steps include: (1) Preparation of Ti3C2•MXene / PEO composite functional material printing ink: polyethylene oxide (PEO) with a molecular weight of 300,000 was weighed in deionized water, and magnetic stirring was performed for 7 to 9 h to allow the polymer to fully dissolve until no bubbles appeared, and a PEO solution with a mass fraction of 6% to 8% was prepared; 0.01-0.05 g Ti3C2•MXene was placed in 10 mL deionized water and ultrasonically dispersed for 3-5 min to obtain a uniformly dispersed Ti3C2•MXene aqueous solution; 0.06-0.08 g PEO solution was weighed and added to the uniform solution and magnetically stirred for 4 h to make the ink uniformly mixed to obtain a mixed ink of 6%-8% PEO - 0.3%-0.7% Ti3C2•MXene; (2) Perform hydrophobic treatment on the printed substrate: During the electro-direct writing printing process, the substrate is ultrasonically cleaned in anhydrous ethanol for 20 to 30 minutes, then cleaned with deionized water for 2 to 3 times, and the cleaned substrate is dried at 60 °C for 20 to 30 minutes; (3) Printing Ti3C2•MXene micro-nanofibers by direct electrowriting: Load the mixed ink prepared in (1) into a syringe and connect a needle with an aperture size of 18 to 24 G to the syringe; set the external voltage to 2 to 4 kV, the current to 0.1 to 0.8 A, the electrode distance to <1 cm, the ink propulsion speed to 0.1 to 2 mL / h, and the program-controlled slide to drive the receiving plate to move at a substrate movement speed of 2 to 8 mm / s to prepare Ti3C2•MXene / PEO smooth straight or curved micro-nanofibers with a size of 200 nm to 20 um, and print the preset shape at the same time.
2. The method for preparing Ti3C2•MXene / PEO composite micro-nano fibers according to claim 1, characterized in that: The substrate is any one of a glass sheet, a silicon sheet, PET, PMMA or PI.
3. A Ti3C2•MXene / PEO composite micro-nanofiber prepared by the method described in claim 1 or 2.