In-situ generated TiN-MXene aerogel material and preparation method thereof
By generating TiN in situ on the surface of MXene to form TiN-MXene aerogel material, the problem of easy oxidation of MXene at high temperature is solved, its antioxidant capacity and photothermal conversion performance are improved, and its application range is expanded.
Patent Information
- Application Number
- CN202511925728.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-19
- Publication Date
- 2026-02-10
AI Technical Summary
Existing MXene aerogel materials are prone to oxidation at high temperatures, which leads to a decline in performance and limits their application range.
Aerogels are formed by directional freeze-drying, and TiN is then generated in situ on the MXene surface to form TiN-MXene aerogel materials, thereby improving the antioxidant capacity.
It significantly improves the antioxidant capacity and photothermal conversion capacity of MXene aerogel, broadening its application range.
Smart Images
Figure CN121493984A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of aerogels, and in particular to an in-situ generated TiN-MXene aerogel material and its preparation method, wherein the TiN content is 1%-40% of the total mass of the aerogel. Background Technology
[0002] Aerogels, as a type of nanoscale porous solid material, are widely used in batteries, catalysis, thermal storage and other fields due to their ultra-low density (as low as 0.003 g / cm³), high porosity (up to 99.9%), nanoscale pore structure (20-50 nm), excellent elasticity and fatigue resistance.
[0003] Directional freezing is a technique that induces the directional growth of ice crystals by controlling a temperature gradient, thereby preparing materials with anisotropic structures. This method can precisely control the microstructure of materials, significantly improving their mechanical properties, thermal anisotropy, and mass transfer efficiency. It has wide applications in aerogels, tissue engineering scaffolds, battery separators, and biomimetic functional materials, and has unique advantages, especially in the preparation of high-strength, low-thermal-conductivity directional porous materials.
[0004] MXene is a two-dimensional transition metal carbide, nitride, or carbonitride with excellent electrical conductivity, hydrophilicity, and tunable surface chemistry. Its advantages include high thermal conductivity and high electrical conductivity (up to 10⁻⁶). 4 With its excellent mechanical properties, abundant surface functional groups (such as -OH, -O, -F), and tunable interlayer spacing and band gap, MXene exhibits great potential in fields such as supercapacitors, lithium-ion batteries, electromagnetic shielding, sensors, and catalysis. However, MXene is prone to oxidation, leading to the loss of its original properties, especially at high temperatures. This invention aims to enhance the oxidation resistance of MXene by preventing it from contacting oxygen in the air through in-situ growth of TiN on the surface of MXene aerogel. Simultaneously, TiN possesses a high melting point (3290℃), high hardness (Mohs hardness 8-9), excellent friction and wear resistance, good chemical stability, good thermal conductivity (29.1 W / (m·K)), electrical conductivity (resistivity approximately 20 µΩ·cm), and excellent light absorption properties. In-situ growth of TiN on the MXene surface can improve the mechanical properties and photothermal conversion capabilities of MXene aerogel while allowing it to retain its high thermal and electrical conductivity. Summary of the Invention
[0005] This application provides an in-situ generation method for TiN-MXene aerogel material, which involves forming an aerogel through directional freeze-drying and then generating the TiN-MXene aerogel material in situ. This method provides an aerogel material with a simple process, high reproducibility, and the ability to significantly improve the antioxidant capacity and photothermal conversion capacity of MXene.
[0006] On the other hand, this application provides a method for preparing in-situ TiN-MXene aerogel materials, comprising the following steps: (1) Weigh different masses of Ti3C2T X Nanosheets were dissolved in deionized water and stirred to obtain Ti3C2T at different concentrations. X Colloidal solutions; (2) The Ti3C2T samples obtained in step (1) at different concentrations X A colloidal solution was added to a polytetrafluoroethylene container with a copper block at the bottom. The container was then placed in liquid nitrogen and frozen into ice. The ice was separated from the container and then freeze-dried to obtain Ti3C2T. X Aerogel; (3) The freeze-dried Ti3C2T obtained in step (2) X MXene aerogel samples were placed in a tube furnace or muffle furnace. Under air atmosphere, the temperature was raised to 450℃ at a slow heating rate of 1℃ / min and held for 10-120 min to obtain Ti3C2T oxide. X Aerogel; (4) Take the Ti3C2T oxide obtained in step (3) X The aerogel was placed in a tube furnace and a mixture of argon and ammonia was introduced for 30 minutes. The temperature was then increased to 700-900℃ at a rate of 2-5℃ / min and held for 1-4 hours. It was then allowed to cool naturally to room temperature. (Ti3C2T) X The aerogel is transformed into an MXene aerogel with TiN coating on its surface.
[0007] Preferably, the Ti3C2T described in step (1) X The concentration of the colloidal solution was 10-16 mg / ml, and the stirring time was 30 min.
[0008] Preferably, the demolding step in step (2) includes: letting the frozen container stand at room temperature for 10–20 minutes, and then using a plastic tube to apply an impact force to separate the ice from the container.
[0009] Preferably, the ratio of the mixed gas of argon and ammonia introduced in step (4) is between 9:1 and 7:3, and the gas flow rate is 50-250 ml / min.
[0010] Beneficial effects.
[0011] This invention proposes an in-situ generation method for TiN-MXene aerogel, successfully growing TiN on the MXene surface, significantly improving the antioxidant capacity of MXene and meeting the application requirements of MXene aerogel at medium and high temperatures. This method not only broadens the application range of MXene aerogel but also provides a methodological reference for optimizing the antioxidant capacity and performance of MXene aerogel. Attached Figure Description
[0012] Appendix Figure 1 This is a scanning electron microscope (SEM) image of the pure MXene aerogel in Example 1.
[0013] Appendix Figure 2 This is a SEM image of the TiN-MXene aerogel in Example 1.
[0014] Appendix Figure 3 This is a SEM image of the TiN-MXene aerogel in Example 2.
[0015] Appendix Figure 4 This is the X-ray diffraction (XRD) pattern of the TiN-MXene aerogel in Example 1.
[0016] Appendix Figure 5 This is the Raman spectrum of the TiN-MXene aerogel in Example 1.
[0017] Appendix Figure 6 These are the photothermal effect temperature curves of TiN-MXene aerogel and MXene aerogel in Example 1. Detailed Implementation
[0018] To make the objectives, technical solutions, and beneficial effects of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the embodiments described in this specification are merely illustrative and not intended to limit the scope of the invention.
[0019] The above description of the invention is not intended to describe every disclosed embodiment or implementation of the invention. Instead, the following description provides more specific examples of exemplary embodiments. Throughout this application, guidance is provided through a series of embodiments that can be used in various combinations. The examples listed are representative only and should not be construed as exhaustive.
[0020] The following embodiments describe the disclosure of this application in more detail. These embodiments are merely illustrative, as various modifications and variations will be apparent to those skilled in the art within the scope of the disclosure of this application. All reagents used in the embodiments are commercially available or synthesized by conventional methods and can be used directly without further processing. Similarly, the instruments used in the embodiments are commercially available.
[0021] Example 1.
[0022] The steps for preparing the in-situ TiN-MXene aerogel material in this embodiment are as follows: (1) Weigh 180mg Ti3C2T X The nanosheets were dissolved in 15 ml of deionized water and stirred for 30 min to obtain 12 mg / ml Ti3C2T. X Colloidal solutions; (2) Take the 12 mg / ml Ti3C2T obtained in step (1) X A colloidal solution was added to a polytetrafluoroethylene container with a copper block at the bottom. The container was then placed in liquid nitrogen and frozen into ice. After standing at room temperature for 10 minutes, the ice was separated from the container by applying impact force through a plastic tube. The ice was then freeze-dried to obtain Ti3C2T. X Aerogel; (3) The freeze-dried Ti3C2T obtained in step (2) X MXene aerogel samples were placed in a tube furnace or muffle furnace. Under air atmosphere, the temperature was raised to 450℃ at a slow heating rate of 1℃ / min and held for 10 min to obtain Ti3C2T oxide. X Aerogel; (4) Take the Ti3C2T oxide obtained in step (3) X The aerogel was placed in a tube furnace and purged with a 9:1 mixture of argon and ammonia at a flow rate of 50 ml / min for 30 min. The temperature was then increased to 700℃ at a rate of 5℃ / min and held for 2 h, followed by natural cooling to room temperature. (Ti3C2T) X The aerogel is transformed into an MXene aerogel with TiN coating on its surface.
[0023] Elemental analysis of the TiN-MXene aerogel prepared in this embodiment showed that the TiN content in the aerogel was 1.2 wt%, and its SEM image is attached. Figure 1 As shown in the figure, the vertically arranged channels indicate that the orientation of MXene has been successfully achieved. Figure 2The image shows an SEM image of the in-situ generated TiN-MXene aerogel material prepared in this embodiment. As can be seen from the image, the TiN-MXene aerogel still maintains a vertical porous channel structure. Figure 4 The image shows the XRD pattern of the in-situ generated TiN-MXene aerogel material prepared in this embodiment. It can be seen from the image that TiN is present in the in-situ generated TiN-MXene aerogel material. Figure 5 The image shows the Raman spectrum of the in-situ generated TiN-MXene aerogel material prepared in this embodiment. The figure demonstrates successful in-situ growth of TiN. The prepared TiN-MXene aerogel material significantly improves its antioxidant capacity and mechanical properties. Figure 6 The image shows the photothermal effect temperature curve of the in-situ generated TiN-MXene aerogel material prepared in this embodiment. It can be seen that the photothermal conversion ability of MXene is enhanced after TiN is grown in situ on the MXene surface.
[0024] Example 2.
[0025] The steps for preparing the in-situ TiN-MXene aerogel material in this embodiment are as follows: (1) Weigh 240mg Ti3C2T X The nanosheets were dissolved in 15 ml of deionized water and stirred for 30 min to obtain 16 mg / ml Ti3C2T. X Colloidal solutions; (2) Take the 16 mg / ml Ti3C2T obtained in step (1) X A colloidal solution was added to a polytetrafluoroethylene container with a copper block at the bottom. The container was then placed in liquid nitrogen and frozen into ice. After standing at room temperature for 20 minutes, the ice was separated from the container by applying impact force through a plastic tube. The ice was then freeze-dried to obtain Ti3C2T. X Aerogel; (3) The freeze-dried Ti3C2T obtained in step (2) X MXene aerogel samples were placed in a tube furnace or muffle furnace. Under air atmosphere, the temperature was raised to 450℃ at a slow heating rate of 1℃ / min and held for 120 min to obtain Ti3C2T oxide. X Aerogel; (4) Take the Ti3C2T oxide obtained in step (3) X The aerogel was placed in a tube furnace and purged with a mixture of argon and ammonia in a 7:3 ratio for 30 min at a flow rate of 250 ml / min. The temperature was then increased to 900 °C at a rate of 2 °C / min and held for 4 h, followed by natural cooling to room temperature. (Ti3C2T) X The aerogel is transformed into an MXene aerogel with TiN coating on its surface.
[0026] Elemental analysis of the TiN-MXene aerogel prepared in this embodiment showed that the TiN content in the aerogel was 40.1 wt%, and its SEM image is attached. Figure 3 As shown, SEM tests indicate that TiN is generated in situ on the surface of MXene aerogel.
[0027] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any person skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope disclosed in this application, and these modifications or substitutions should all be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the rights and obligations stipulated herein. The scope of protection required shall prevail.
Claims
1. An in-situ generated TiN-MXene aerogel material, characterized in that, TiN is generated in situ on the surface of MXene aerogel, with a TiN content of 1%-40% of the total mass of the aerogel.
2. The method for preparing an in-situ TiN-MXene aerogel material as described in claim 1, characterized in that, Includes the following steps: (1) Weigh different masses of Ti3C2T X Nanosheets were dissolved in deionized water and stirred to obtain Ti3C2T at different concentrations. X Colloidal solutions; (2) The Ti3C2T samples obtained in step (1) at different concentrations X A colloidal solution was added to a polytetrafluoroethylene container with a copper block at the bottom. The container was then placed in liquid nitrogen to freeze and solidify. After demolding, ice blocks were obtained. The ice blocks were then freeze-dried to obtain Ti3C2T. X Aerogel; (3) The freeze-dried Ti3C2T obtained in step (2) X The MXene aerogel samples were placed in a tube furnace or muffle furnace. Under air atmosphere, the temperature was raised to 450℃ at a slow heating rate of 1℃ / min and held for 10-120 min. (4) Take the Ti3C2T obtained in step (3) X The aerogel was placed in a tube furnace and a mixture of argon and ammonia was introduced for 30 minutes. The temperature was then increased to 700-900℃ at a rate of 2-5℃ / min and held for 1-4 hours. It was then allowed to cool naturally to room temperature. (Ti3C2T) X The aerogel is transformed into an MXene aerogel with TiN coating on its surface.
3. The method for preparing an in-situ TiN-MXene aerogel material according to claim 2, characterized in that, The Ti3C2T mentioned in step (1) X The concentration of the colloidal solution was 10-16 mg / ml, and the stirring time was 30 min.
4. The method for preparing an in-situ TiN-MXene aerogel material according to claim 2, characterized in that, The demolding step described in step (2) includes: letting the frozen container stand at room temperature for 10–20 minutes, and then applying impact force with a plastic tube to separate the ice from the container.
5. The method for preparing an in-situ TiN-MXene aerogel material according to claim 2, characterized in that, In step (4), the ratio of the mixed gas of argon and ammonia introduced is between 9:1 and 7:3, and the gas flow rate is 50-250 ml / min.