MXene-based 3D printing filament, electrode and preparation method
The method of preparing MXene-based 3D-printed filaments combined with multi-wall carbon nanotubes through solution mixing method solves the problem of insufficient conductivity in the prior art, achieves efficient electrochemical performance improvement and cost reduction, and is suitable for supercapacitor electrodes rapid large-scale preparation.
Patent Information
- Application Number
- CN202411423042.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-12
- Publication Date
- 2025-01-10
AI Technical Summary
In the existing 3D printing technology, there are limited types of conductive fillers, which cannot meet the requirements of future energy storage devices, resulting in insufficient conductivity and difficulty in achieving high-performance supercapacitor electrodes.
MXene-based 3D printed filaments were prepared by solution mixing method, combining multi-wall carbon nanotubes and thermoplastic polyurethane materials, forming a uniform dispersion liquid through ultrasound and stirring. Then, conductive filaments were prepared in a single screw extruder and printed through an FDM printer. The electrodes are sintered at high temperature to form a stable frame structure to improve conductivity.
It achieves efficient electrochemical performance improvement, reduces preparation costs, and can quickly and large-scale preparation of supercapacitor electrodes. The material has a stable structure at high temperatures, avoiding material waste.
Smart Images
Figure CN119286234A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to a MXene-based 3D printing filament, an electrode and a preparation method thereof, and belongs to the technical field of new energy storage. Background Art
[0002] In recent years, printing technology has shown great potential in the preparation of high-performance energy storage devices. Printing technology can easily control the geometry, position, film thickness and conductivity of the electrode, thus greatly improving the design flexibility and the performance of the energy storage device. To date, a variety of printing technologies have been used to manufacture SC electrodes, among which additive manufacturing (AM), also known as three-dimensional (3D) printing, a manufacturing method that sequentially adds 2D layers on existing layers to build a 3D structure, has attracted great attention in industry and academia. Compared with traditional methods, additive manufacturing has the advantages of being able to control electrode thickness and geometry, prepare high area energy and power density devices, low cost and low environmental impact. Fused deposition modeling (FDM) has become one of the promising 3D printing technologies due to its low cost and ability to control the amount of materials. In FDM printing technology, the raw materials are generally thermoplastics, such as acrylonitrile butadiene styrene (ABS), polylactic acid (PLA), etc. Since pure thermoplastic filaments do not have other special properties, their role is only in the construction of the structure. The conductivity of the filament requires the addition of carbon-based conductive fillers, such as carbon black, graphene, multi-walled carbon nanotubes, etc., to the thermoplastic polymer, and the charge transfer is established by electron hopping or tunneling between the conductive fillers. A large number of researchers have made great efforts to prepare FDM printable composite filaments in order to obtain conductive filaments that meet printing requirements. However, the current types of conductive fillers are limited, and filaments prepared from carbon-based conductive fillers cannot meet the requirements of future energy storage devices. Therefore, it is very necessary to develop new printing filaments for desktop 3D printing devices to achieve better energy storage effects. Summary of the invention
[0003] The purpose of the present invention is to provide a MXene-based 3D printing filament, an electrode and a preparation method. The MXene-based 3D printing filament is prepared by a solution mixing method, and the preparation process is simple and the cost is low.
[0004] In order to achieve the above objectives / solve the above technical problems, the present invention is implemented by adopting the following technical solutions.
[0005] In a first aspect, the present invention provides a method for preparing a MXene-based 3D printing filament, comprising the following steps: Weigh 0.5-1 portion of freeze-dried MXene material and disperse it in 50-100 ml of NN dimethylformamide, and continue ultrasonication until the MXene is completely dispersed in DMF to form a MXene dispersion; N-methylpyrrolidone (NMP) dispersion of multi-walled carbon nanotubes, 10 parts of polyurethane, 0.5-1 parts of polyvinylpyrrolidone and 0.1-0.2 parts of fluorine surfactant were added to the MXene dispersion for preliminary stirring, and the mixture after preliminary stirring was sealed and stirred and mixed for a second time in an oil bath pot; The mixture after secondary stirring is ventilated and dried, and the ventilated and dried mixture is cut into blocks and put into a single-screw extruder to extrude into MXene-based printing filaments.
[0006] Furthermore, the ultrasound time is 3 to 5 hours.
[0007] Furthermore, the NMP dispersion of multi-walled carbon nanotubes contains 4% multi-walled carbon nanotubes.
[0008] Furthermore, the initial stirring speed was 30 rad / s for 30 min, the secondary stirring time was 24 h, and the temperature of the oil bath was set to 90 °C.
[0009] Furthermore, the ventilation drying is specifically as follows: placing the mixture after the secondary stirring in a forced air drying oven for 24 hours, with the temperature set to 90°C.
[0010] Furthermore, the extrusion temperature of the single-screw extruder is set to 160-175° C., and the extrusion diameter of the single-screw extruder is set to 1.75 mm.
[0011] In a second aspect, the present invention provides a MXene-based 3D printing filament prepared by the preparation method of the above-mentioned MXene-based 3D printing filament, comprising: 4.4 wt% multi-walled carbon nanotubes, 4.4 wt% MXene material, and 91.2 wt% thermoplastic polyurethane (TPU) elastomer material; the interaction between the MXene material and the multi-walled carbon nanotubes in the electrode forms a stable framework structure, making the basic structure of the printed electrode more stable.
[0012] In a third aspect, the present invention provides a method for preparing a 3D electrode based on the above-mentioned MXene-based printed 3D filament, comprising the following steps: printing out an electrode by passing the MXene-based 3D printed filament through an FDM printer at 180-210°C, 50-60% speed, and a hot bed at 60°C; The electrode was placed in a tubular furnace, the temperature was raised by 1 °C every 2 min, and sintered at 500 °C~900 °C for 1 h under argon protection to remove the polymer on the electrode surface.
[0013] In a fourth aspect, the present invention provides a 3D electrode prepared based on the above-mentioned 3D electrode preparation method, comprising: the 3D electrode has a thickness of 0.8 mm, a diameter of 15 mm, and a circular shape, the MXene material in the electrode is oxidized into titanium dioxide, the TPU material forms carbon under high temperature, the MXene material interacts with multi-walled carbon nanotubes (MWCNTs), stabilizes the structure of the electrode, and keeps the electrode structure stable at high temperatures, in addition, this interaction also includes the effects of improving the conductivity of the electrode, increasing the surface area of the electrode, and promoting electron transport, and the electrode prepared with MXene material and multi-walled carbon nanotubes (MWCNTs) can expose more active sites, which is beneficial to the diffusion of electrode ions and has better electrochemical properties.
[0014] Compared with the prior art, the present invention has the following beneficial effects: the present invention provides a method for preparing printing filaments by solution mixing, which has a simple preparation process and low cost; The present invention provides a 3D printing filament based on a novel material MXene. The 3D printing filament is a mixture of novel MXene material and carbon-based material multi-walled carbon nanotubes. The synergistic effect of the two different nanofillers can construct a good conductive network. At the same time, the mutual entanglement of the two conductive fillers can stabilize the electrode structure after heat treatment.
[0015] The present invention utilizes a new material MXene as a conductive filler for 3D printing filaments, and uses the 3D printing filaments to prepare supercapacitor electrodes. In the subsequent heat treatment process, MXene is oxidized into titanium dioxide, which can effectively improve the electrochemical properties of the printed electrodes without causing waste of materials, thereby further reducing the preparation cost and enabling large-scale preparation of supercapacitor electrodes in a short time. BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Figure 1 This is a SEM diagram of the electrode printed with 4.4 wt% MWCNT, 4.4 wt% MXene, and 91.2 wt% TPU filament after high-temperature sintering at 700°C under argon protection.
[0017] Figure 2 Comparison of cyclic voltammograms of electrodes printed with 4.4 wt% MWCNT, 4.4 wt% MXene, and 91.2 wt% TPU filaments after high-temperature sintering at 700°C and 900°C under argon protection.
[0018] Figure 3This is a constant current charge and discharge comparison chart of electrodes printed with 4.4 wt% MWCNT, 4.4 wt% MXene, and 91.2 wt% TPU filaments after high-temperature sintering at 700°C and 900°C under argon protection.
[0019] Figure 4 The cyclic voltammograms at different currents of the electrodes printed with 9 wt% MWCNT, 4.2 wt% MXene, and 86.8 wt% TPU filaments, which were assembled into supercapacitors after high-temperature sintering at 900°C under argon protection. DETAILED DESCRIPTION
[0020] The technical solution of the present invention is described in detail below through the accompanying drawings and specific embodiments. It should be understood that the embodiments of the present invention and the specific features in the embodiments are detailed descriptions of the technical solution of the present invention, rather than limitations on the technical solution of the present invention. The embodiments of the present invention and the technical features in the embodiments may be combined with each other unless there is a conflict.
[0021] The term "and / or" is only a description of the association relationship between related objects, indicating that there can be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. In addition, the character " / " generally indicates that the related objects are in an "or" relationship. Example 1
[0022] like Figure 1 An embodiment 1 shown in the figure provides a method for preparing a MXene-based 3D printing filament, comprising the following steps: Weigh 0.55 g of freeze-dried MXene and disperse it in 50 mL DMF (NN dimethylformamide). Continue ultrasonication for 5 h until the MXene is completely dispersed in DMF. Add NMP dispersion of multi-walled carbon nanotubes (0.55 g of multi-walled carbon nanotubes), 10 g of TPU (polyurethane), 1 g of polyvinyl pyrrolidone, and 0.2 g of fluorine surfactant to the MXene dispersion. Stir at 30 rad / s for 30 min, seal the mixture, and stir in a 90 °C oil bath for 24 h. After stirring, the mixture is mixed evenly, introduced into a square plate, and dried in a forced air drying oven at 90 °C for 24 h. The dried mixture film is cut into small pieces and put into a single-screw extruder and extruded at 165 °C to form a fused deposition modeling 3D printing filament with an average diameter of 1.75 mm. The 3D printing filament contains 4.4 wt% MWCNT, 4.4 wt% MXene, and 91.2 wt% TPU materials. Example 2
[0023] This embodiment 2 provides a method for preparing a 3D electrode, comprising the following steps: The 3D printing wire prepared by the preparation method of the MXene-based 3D printing filament in Example 1 was used to print a circular electrode with a thickness of 0.8 mm and a diameter of 15 mm by an FDM printer at 190°C, 50% speed, and a hot bed of 60°C.
[0024] The circular electrode was placed in a tube furnace, the temperature was raised by 1 °C every 2 min, and it was sintered at 700 °C for 1 h under argon protection to remove the polymer on the electrode surface.
[0025] like Figure 1 As shown in the figure, after sintering, the electrode surface was subjected to corresponding electrochemical tests 1, and the morphology of the 3D printed electrode was characterized using a GeminiSEM300 scanning electron microscope (SEM). From the SEM image, it can be seen that after the 3D printed MXene / MWCNT / TPU electrode is heat-treated, the polymer on the electrode surface will gradually decompose at high temperature, leaving holes on the electrode surface. The gas produced by TPU during the decomposition process will react with MXene to produce titanium dioxide. The synergistic effect of titanium dioxide and multi-walled carbon nanotubes can effectively provide a fast channel for ion transmission, thereby greatly reducing the transmission resistance and improving the electrochemical performance of the electrode; in addition, because the unique two-dimensional sheet structure of MXene and the tubular structure of CNT are intertwined, the shape of the electrode remains stable in a high temperature environment. Example 3
[0026] This embodiment 3 provides a method for preparing a 3D electrode. In addition to the technical solution described in embodiment 2, this embodiment adopts high-temperature sintering at 900°C under argon protection for 1 h to remove the polymer on the surface of the electrode.
[0027] like Figure 2~3 As shown, the electrodes prepared in Example 2 and Example 3 were subjected to electrochemical test 2 using a three-electrode system; wherein the MXene / MWCNT / TPU electrode was used as the working electrode, silver chloride was used as the reference electrode, the glass slide electrode was used as the counter electrode, and 1 M H2SO4 was used as the electrolyte. The electrochemical properties of the three-dimensional printed electrode were characterized by cyclic voltammetry (CV) and charge-discharge curves (CP), and the area capacitance of the electrode was calculated by analysis of the cyclic voltammetry curves, and the difference in electrochemical performance of the electrode heat-treated at 700°C and 900°C was compared; the test conditions were: the voltage window was 0 0.8V.
[0028] According to the cyclic voltammetry (CV) and charge-discharge curves (CP), it can be seen that the prepared electrode has better electrochemical properties after heat treatment at 900°C. On the one hand, it shows that heat treatment can effectively remove the polymer material on the surface of the electrode, and the synergistic effect of titanium dioxide and multi-walled carbon nanotubes can effectively improve the capacitance performance of the electrode. The carbonization of some polymer materials at high temperature also improves the energy storage capacity of the electrode; on the other hand, at a high temperature of 900°C, the shape of the electrode will be significantly reduced due to the decomposition of the polymer, but the structural stability is mainly due to the mutual entanglement of the MXene material and MWCNT. Example 4
[0029] This embodiment 4 provides a method for preparing a MXene-based 3D printing filament, comprising the following steps: Weigh 1.17 g of freeze-dried MXene and disperse it in 50 mL DMF (NN dimethylformamide). Continue ultrasonication for 5 h until the MXene is completely dispersed in DMF. Add NMP dispersion of multi-walled carbon nanotubes (0.55 g of multi-walled carbon nanotubes), 10 g of TPU (polyurethane), 1 g of polyvinyl pyrrolidone, and 0.2 g of fluorine surfactant to the MXene dispersion; stir at 30 rad / s for 30 min, seal the mixture, and stir and mix in a 90 °C oil bath for 24 h; After stirring, the mixture was mixed evenly, introduced into a square plate, and dried in a blast drying oven at 90 °C for 24 h; the dried mixture film was cut into small pieces and put into a single screw extruder at 165 °C to form a fused deposition modeling 3D printing filament with an average diameter of 1.75 mm. The prepared 3D printing filament contained 9 wt% MWCNT, 4.4 wt% MXene, and 91.2 wt% TPU material; Then, the printing filament was used to print circular electrodes with a thickness of 0.8 mm and a diameter of 15 mm using an FDM printer at 190 ℃, 50% speed, and a hot bed of 60 ℃. The circular electrodes were placed in a tubular furnace, the temperature was raised by 1 ℃ every 2 min, and they were sintered at 900 ℃ under argon protection for 1 h to remove the polymer on the electrode surface. Two circular electrodes were assembled with a diaphragm in a tee to prepare a supercapacitor with 1 M H2SO4 as the electrolyte. Performance tests were carried out 3, and the capacitance behavior of the supercapacitor was calculated at different scan rates in a voltage window of 0-0.8 V.
[0030] like Figure 4 As shown in Figure 2, at a scan rate of 2 mV / s, the maximum area capacitance of the supercapacitor can reach 1.25 F / cm -2 .
[0031] The present invention provides a 3D printing filament based on a new material MXene. The 3D printing filament is mixed with a new material MXene and a carbon-based material multi-walled carbon nanotube. The synergistic effect of the two different nanofillers can construct a good conductive network. At the same time, the mutual entanglement of the two conductive fillers can stabilize the electrode structure after heat treatment.
[0032] The present invention utilizes a new material MXene as a conductive filler for 3D printing filaments, and uses the 3D printing filaments to prepare supercapacitor electrodes. In the subsequent heat treatment process, MXene is oxidized into titanium dioxide, which can effectively improve the electrochemical properties of the printed electrodes without causing waste of materials, thereby further reducing the preparation cost and enabling large-scale preparation of supercapacitor electrodes in a short time.
[0033] The embodiments of the present invention are described above in conjunction with the accompanying drawings, but the present invention is not limited to the above-mentioned specific implementation methods. The above-mentioned specific implementation methods are merely illustrative and not restrictive. Under the enlightenment of the present invention, ordinary technicians in this field can also make many forms without departing from the scope of protection of the purpose of the present invention and the claims, which all fall within the protection of the present invention.
Claims
1. A method for preparing MXene-based 3D printing filaments, characterized in that: The following steps are involved: Take 0.5~1 portion of freeze-dried MXene material and disperse it in 50~100 ml of NN dimethylformamide, and continue ultrasonication until the MXene is completely dispersed in DMF to form a MXene dispersion; N-methylpyrrolidone dispersion of multi-walled carbon nanotubes, 10 parts of polyurethane, 0.5-1 parts of polyvinylpyrrolidone and 0.1-0.2 parts of fluorine surfactant were added to the MXene dispersion for preliminary stirring, and the mixture after preliminary stirring was sealed and stirred and mixed for a second time in an oil bath; The mixture after secondary stirring is ventilated and dried, and the ventilated and dried mixture is cut into blocks and put into a single-screw extruder to extrude into MXene-based printing filaments.
2. The method for preparing MXene-based 3D printing filament according to claim 1, characterized in that: The ultrasound time is: 3~5 h.
3. The method for preparing MXene-based 3D printing filament according to claim 1, characterized in that: The NMP dispersion of multi-walled carbon nanotubes contains 4% multi-walled carbon nanotubes.
4. The method for preparing MXene-based 3D printing filament according to claim 1, characterized in that: The initial stirring speed was 30 rad / s and the time was 30 min; The secondary stirring time was 24 h, and the temperature of the oil bath was set at 90 °C.
5. The method for preparing MXene-based 3D printing filament according to claim 1, characterized in that: The ventilation drying is specifically as follows: placing the mixture after the secondary stirring in a forced air drying oven for 24 hours, with the temperature set at 90°C.
6. The method for preparing MXene-based 3D printing filament according to claim 1, characterized in that: The extrusion temperature of the single screw extruder is set to 160-175° C., and the extrusion diameter of the single screw extruder is set to 1.75 mm.
7. The MXene-based 3D printing filament prepared by the method for preparing a MXene-based 3D printing filament according to any one of claims 1 to 6, characterized in that: include: Contains 4.4 wt% multi-walled carbon nanotubes, 4.4 wt% MXene materials, and 91.2wt% thermoplastic polyurethane elastomer materials.
8. The method for preparing a 3D electrode based on the MXene-based printed 3D filament according to claim 7, characterized in that: The following steps are involved: The MXene-based 3D printing filament is passed through an FDM printer at 180-210°C, 50-60% speed, and a hot bed at 60°C to print out an electrode; The electrode was placed in a tubular furnace, the temperature was raised by 1 °C every 2 min, and sintered at 500 °C-900 °C for 1 h under argon protection to remove the polymer on the electrode surface.
9. A 3D electrode prepared by the 3D electrode preparation method according to claim 8, characterized in that: include: The 3D electrode has a thickness of 0.8 mm, a diameter of 15 mm, and a circular shape.