Silane coupling agent grafted MXene composite material and preparation method thereof
By preparing MXene composite materials grafted with silane coupling agents, the problems of poor compatibility and adhesion between PDMS and MXene were solved, and efficient and low-cost large-scale preparation was achieved, which is suitable for flexible wearable electronic devices.
Patent Information
- Application Number
- CN202510987490.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-17
- Publication Date
- 2025-10-03
AI Technical Summary
In existing flexible wearable electronic devices, PDMS materials have poor compatibility and adhesion with low-dimensional conductive materials such as MXene, which makes it difficult to form good contact and affects the stability and reliability of the devices.
A few-layer MXene dispersion was prepared by wet chemical etching and mechanical stripping methods. The hydroxyl groups were modified by adding a strong base and then reacted with a silane coupling agent to prepare a silane coupling agent-grafted MXene composite material to improve its adhesion to PDMS.
The adhesion ability of MXene to PDMS was significantly improved, the compatibility problem was solved, and efficient and low-cost large-scale preparation was achieved, making it suitable for flexible wearable electronic devices.
Smart Images
Figure CN120737434A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of composite materials, and in particular to a silane coupling agent-grafted MXene composite material and a preparation method thereof. Background Art
[0002] Since the 21st century, with the development of the economy, digitalization, and informatization, society's demand for precision medicine has soared, giving rise to an urgent need to deeply integrate traditional medical technologies with the digital world. Traditional human body sensors, due to their rigidity and rigidity, suffer from limitations such as size limitations, poor biocompatibility, and poor skin adhesion, making it difficult to maintain long-term, stable monitoring in the dynamic human environment. This demand has driven the development of flexible wearable electronic devices.
[0003] Flexible wearable electronic devices are microsystems that heterogeneously integrate flexible polymer substrates, low-dimensional conductive materials, flexible circuits, and wireless transmission modules. Common head-type polymer substrates include polydimethylsiloxane (PDMS), polyimide (PI), polyethylene terephthalate (PET), and other materials. PDMS is widely used due to its Young's modulus, which is similar to that of skin, and its excellent biocompatibility. However, due to the large number of methyl groups in PDMS, it has poor polarity, low surface energy, hydrophobicity, and weak interaction with low-dimensional conductive materials. As the core material in the system, low-dimensional conductive materials are required to have high conductivity, small size, and strong adhesion to the substrate. Commonly used low-dimensional conductive materials include graphene, carbon nanotubes, MXene, and liquid metal. However, liquid metal is prone to oxidation, leakage, and difficult processing, while graphene and carbon nanotubes are incompatible with PDMS and difficult to modify.
[0004] MXene nanosheets, a new class of two-dimensional nanomaterials, boast high conductivity, high surface area, and a rich array of tunable surface functional groups. They have made substantial progress in various fields, including batteries, supercapacitors, and catalysis. However, as a promising low-dimensional conductive material, a surface modification method is urgently needed to ensure good contact between MXene nanosheets and PDMS. Summary of the Invention
[0005] The present invention aims to provide a surface modification method to form good contact with PDMS material, and proposes a preparation method of MXene composite material grafted with a silane coupling agent, which specifically includes the following steps: S1: MAX phase material is subjected to wet chemical etching combined with mechanical exfoliation to obtain a few-layer MXene dispersion; S2: adding a strong base to the few-layer MXene dispersion in step S1, adjusting its pH value, and reacting under an argon environment to obtain a hydroxyl-modified MXene dispersion, i.e., an h-MXene dispersion; S3: Add the h-MXene dispersion described in step S2 to a silane coupling agent and a catalyst, and react under an argon environment to obtain a MXene composite material grafted with a silane coupling agent.
[0006] The present invention is further configured as follows: the MXene material in step S1 is Ti3C2T X 、V2CT X 、Nb2CT X 、Ti3CNT X One of them.
[0007] The present invention is further configured as follows: Step S2 specifically includes the following steps: S2-1: Add deionized water to the few-layer MXene dispersion in step S1 to dilute it to a MXene concentration of 5-10 mg / ml; S2-2: Slowly add a 6 mol / L solid strong base to the diluted solution while stirring continuously during the addition process; S2-3: The solution was ultrasonically treated at 20°C under argon atmosphere for 20 min with an ultrasonic power of 400 W; S2-4: The solution was stirred under argon atmosphere for 24-48 hours.
[0008] The present invention is further configured as follows: the strong base solid in step S2-2 is KOH or NaOH.
[0009] The present invention is further configured as follows: Step S3 specifically includes the following steps: S3-1: adding deionized water to the h-MXene dispersion of step S2, and centrifuging and washing repeatedly until the h-MXene dispersion is neutral; S3-2: Add deionized water to dilute the solution to 20-60 mg / ml; S3-3: Add an equal amount of ethanol to disperse and dilute the solution to 10-30 mg / ml. Ultrasonicate the solution at 20°C under argon atmosphere for 5 min at an ultrasonic power of 400 W. S3-4: adding 3-7 wt% of the h-MXene mass of a silane coupling agent to the solution, and adding anhydrous acetic acid to adjust the pH value of the solution to 4-5; S3-5: The solution was sonicated at 20°C for 5 min under argon atmosphere with an ultrasonic power of 400 W. S3-6: The solution was stirred under an argon atmosphere for 6-10 hours; S3-7: The resulting solution was washed with excess silane coupling agent by adding ethanol and centrifuging twice.
[0010] The present invention is further configured as follows: the silane coupling agent in step S3-4 is one of γ-aminopropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, and tridecafluorooctyltriethoxysilane.
[0011] The present invention also provides a silane coupling agent-grafted MXene composite material, which is prepared using the above-mentioned preparation method.
[0012] The beneficial effects of the present invention are as follows: the MXene composite material grafted with a silane coupling agent disclosed in the present invention greatly improves the adhesion ability of low-dimensional conductive materials and silane-based polymers, solves the problem that conductive materials are difficult to adhere to the surface of silane-based polymers, and can be prepared on a large scale at low cost. BRIEF DESCRIPTION OF THE DRAWINGS
[0013] Figure 1 The X-ray diffraction patterns of the MXene material, the hydroxyl-modified MXene material, and the MXene composite material grafted with a silane coupling agent prepared in the present invention are shown;
[0014] Figure 2 The transmission electron microscope image and selected area diffraction image of the MXene material prepared by the present invention are shown;
[0015] Figure 3 The transmission electron microscopy image and selected area diffraction image of the hydroxyl-modified MXene material prepared by the present invention are shown;
[0016] Figure 4 The transmission electron microscope image and selected area diffraction image of the MXene composite material grafted with a silane coupling agent prepared by the present invention are shown;
[0017] Figure 5 The Si element spectrum of the X-ray photoelectron spectrum of the MXene composite material grafted with a silane coupling agent prepared by the present invention is shown;
[0018] Figure 6 The O element spectrum of the X-ray photoelectron spectrum of the silane coupling agent grafted MXene composite material prepared by the present invention is shown;
[0019] Figure 7 The Ti element spectrum of the X-ray photoelectron spectrum of the MXene composite material grafted with a silane coupling agent prepared by the present invention is shown;
[0020] Figure 8 The HAADF image and Si element spectrum of the MXene composite material grafted with a silane coupling agent prepared in Example 2 are shown;
[0021] Figure 9The HAADF image and Si element spectrum of the MXene composite material grafted with a silane coupling agent prepared in Example 3 are shown;
[0022] Figure 10 An optical microscope image of the MXene composite material grafted with a silane coupling agent prepared in Example 2 attached to a PDMS substrate is shown;
[0023] Figure 11 An optical microscope image showing ungrafted MXene material attached to a PDMS substrate. DETAILED DESCRIPTION
[0024] Those skilled in the art can refer to the content of this article and appropriately improve the process parameters. It is particularly important to point out that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included in the present invention. The methods and applications of the present invention have been described through preferred embodiments. Relevant persons can modify or appropriately change and combine the methods and applications described herein without departing from the content, spirit and scope of the present invention to implement and apply the technology of the present invention.
[0025] Example 1
[0026] The present invention proposes a method for preparing a MXene composite material grafted with a silane coupling agent, which specifically includes the following steps:
[0027] S1: The MAX phase material is subjected to wet chemical etching combined with mechanical exfoliation to obtain a few-layer MXene dispersion.
[0028] S2: Add a strong base to the few-layer MXene dispersion in step S1, adjust its pH value, and react under an argon environment to obtain a hydroxyl-modified MXene dispersion, i.e., an h-MXene dispersion.
[0029] S3: Add the h-MXene dispersion in step S2 to a silane coupling agent and a catalyst, and react under an argon environment to obtain a MXene composite material grafted with a silane coupling agent.
[0030] The MXene material in step S1 is Ti3C2T X 、V2CT X 、Nb2CT X 、Ti3CNT X One of them.
[0031] Wherein step S2 specifically includes the following steps:
[0032] S2-1: Add deionized water to the few-layer MXene dispersion in step S1 to dilute it to a MXene concentration of 5-10 mg / ml.
[0033] S2-2: Slowly add a strong base solid equivalent to 6 mol / L to the diluted solution and continue stirring during the addition process.
[0034] S2-3: The solution was ultrasonically treated at 20°C under argon atmosphere for 20 min with an ultrasonic power of 400W.
[0035] S2-4: The solution was stirred under argon atmosphere for 24-48 hours.
[0036] The strong base solid in step S2-2 is KOH or NaOH.
[0037] Step S3 specifically includes the following steps:
[0038] S3-1: Deionized water is added to the h-MXene dispersion of step S2, and the mixture is centrifuged and repeatedly washed until the h-MXene dispersion is neutral.
[0039] S3-2: Add deionized water to dilute the solution to 20-60 mg / ml.
[0040] S3-3: Add an equal amount of ethanol to disperse and dilute the solution to 10-30 mg / ml. Ultrasonicate the solution at 20°C in an argon atmosphere for 5 minutes at an ultrasonic power of 400 W.
[0041] S3-4: Add 3-7 wt% of the h-MXene mass of silane coupling agent to the solution, and add anhydrous acetic acid to adjust the pH value of the solution to 4-5.
[0042] S3-5: The solution was ultrasonically treated at 20°C under argon atmosphere for 5 min with an ultrasonic power of 400W.
[0043] S3-6: The solution was stirred under argon atmosphere for 6-10 hours.
[0044] S3-7: The resulting solution was washed with excess silane coupling agent by adding ethanol and centrifuging twice.
[0045] The silane coupling agent in step S3-4 is one of γ-aminopropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, and tridecafluorooctyltriethoxysilane.
[0046] Example 2
[0047] This example adopts the preparation method disclosed in Example 1, and selects Ti3C2T X The preparation of the composite material comprises the following steps:
[0048] S1: Ti3C2T X Few-layer Ti3C2T3 was obtained by wet chemical etching combined with mechanical exfoliation. X dispersion.
[0049] S2: To the few-layer Ti3C2T in S1 X Add deionized water to the dispersion and dilute to Ti3C2T X The concentration was 10 mg / ml; 6 mol / L solid KOH was slowly added to the diluted solution, and stirring was continued during the addition process to adjust the pH value; the solution was then ultrasonically treated for 20 min at 20°C argon environment with an ultrasonic power of 400 W; the solution was then stirred and reacted for 36 h under argon environment to obtain h-Ti3C2T X .
[0050] S3: Add h-Ti3C2T in step S2 X Deionized water was added to the dispersion and the mixture was centrifuged and washed repeatedly until h-Ti3C2T X The dispersion is neutral; deionized water is added to dilute the solution to 40 mg / ml; an equal amount of ethanol is added for dispersion, and the solution is diluted to 20 mg / ml. The solution is ultrasonically treated at 20°C in an argon environment for 5 minutes with an ultrasonic power of 400 W; 5 wt% of 3-aminopropyltriethoxysilane is added to the solution, and anhydrous acetic acid is added to adjust the pH value of the solution to 5; the solution is ultrasonically treated at 20°C in an argon environment for 5 minutes with an ultrasonic power of 400 W; the solution is continuously stirred and reacted for 8 hours in an argon environment; the reaction solution is washed with excess 3-aminopropyltriethoxysilane by adding ethanol and centrifuging twice to obtain Ti3C2T3 grafted with a silane coupling agent. X Composite materials.
[0051] Example 3
[0052] The only difference between this embodiment and embodiment 2 is that step S2 is omitted and steps S1 to S3 are directly performed, and Ti3C2T is selected. X The preparation of the composite material comprises the following steps.
[0053] S1: Ti3C2T X Few-layer Ti3C2T3 was obtained by wet chemical etching combined with mechanical exfoliation. X dispersion.
[0054] S2: Add Ti3C2T in step S1 XDeionized water was added to the dispersion to dilute it to 40 mg / ml; an equal amount of ethanol was added to disperse it and the solution was diluted to 20 mg / ml. The solution was ultrasonically treated at 20°C in an argon environment for 5 minutes at an ultrasonic power of 400W; 5 wt% of 3-aminopropyltriethoxysilane was added to the solution, and anhydrous acetic acid was added to adjust the pH value of the solution to 5; the solution was ultrasonically treated at 20°C in an argon environment for 5 minutes at an ultrasonic power of 400W; the solution was continuously stirred and reacted for 8 hours in an argon environment; the reaction solution was washed with excess 3-aminopropyltriethoxysilane by adding ethanol and centrifuging twice to obtain Ti3C2T3 grafted with a silane coupling agent. X Composite materials.
[0055] refer to Figure 8 、 9 The cases of silane coupling agent attached to MXene nanosheets in Examples 2 and 3 were compared. Obviously, the silane coupling agent in Example 2 was well attached to the MXene nanosheets, and the edge traces of the nanosheets were clearly visible under the energy spectrum, while the silane coupling agent in Example 3 was not well attached to the MXene nanosheets, and no edge traces of the nanosheets were observed under the energy spectrum.
[0056] Experimental application examples
[0057] Disclosed is a method for preparing a PDMS conductive film based on a MXene composite material grafted with a silane coupling agent, which specifically comprises the following steps:
[0058] S1: Mix the PDMS liquid and the cross-linking agent in proportion, stir thoroughly, and degas under a vacuum environment of 200 Pa for 30 minutes.
[0059] S2: The liquid obtained in S1 was poured onto a glass plate, flattened with a scraper, and cured at 80°C for 40 minutes to obtain a PDMS film.
[0060] S3: The MXene composite material grafted with the silane coupling agent prepared in Example 1 and Example 2 is drop-coated on the surface of the film and dried under a vacuum degree of 200-1000 Pa and an environment of 60°C.
[0061] The mass ratio of the PDMS liquid to the cross-linking agent in step S1 is 5:1-15:1.
[0062] The MXene nanosheets prepared in Example 2 and the few-layer MXene dispersion without grafting treatment were used to prepare PDMS films using the method disclosed in the experimental application example. The results were shown in Table 1. Figure 10 and 11, showing optical microscope images of the MXene composite material grafted with a silane coupling agent prepared in Example 2 and a pure MXene material without grafting treatment attached to a PDMS substrate. Clearly, the MXene composite material grafted with a silane coupling agent prepared in Example 2 adheres more evenly to the PDMS surface.
[0063] Example 4
[0064] This embodiment discloses a silane coupling agent-grafted MXene composite material, which is prepared using the preparation method disclosed in Example 1.
[0065] In summary, the present invention prepares a MXene composite material grafted with a silane coupling agent by hydroxylating MXene nanosheets with a high concentration of a strong base, followed by a reaction between the nanosheets and a silane coupling agent catalyzed by acetic acid. This preparation method is simple, portable, low-cost, highly efficient, and amenable to large-scale production, with significant production potential. The MXene composite material prepared using this method exhibits high electrical conductivity and excellent adhesion to silane-based polymers such as PDMS, making it suitable for the preparation of flexible wearable electronic devices.
[0066] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be within the scope of protection of the present invention.
Claims
1. A method for preparing a MXene composite material grafted with a silane coupling agent, characterized in that: The specific steps include: S1: MAX phase material is subjected to wet chemical etching combined with mechanical exfoliation to obtain a few-layer MXene dispersion; S2: adding a strong base to the few-layer MXene dispersion in step S1, adjusting its pH value, and reacting under an argon environment to obtain a hydroxyl-modified MXene dispersion, i.e., an h-MXene dispersion; S3: Add the h-MXene dispersion described in step S2 to a silane coupling agent and a catalyst, and react under an argon environment to obtain a MXene composite material grafted with a silane coupling agent.
2. The method for preparing a MXene composite material grafted with a silane coupling agent according to claim 1, wherein: The MXene material in step S1 is Ti3C2T X 、V2CT X 、Nb2CT X 、Ti3CNT X One of them.
3. The method for preparing a MXene composite material grafted with a silane coupling agent according to claim 1, wherein: Step S2 specifically includes the following steps: S2-1: Add deionized water to the few-layer MXene dispersion in step S1 to dilute it to a MXene concentration of 5-10 mg / ml; S2-2: Slowly add a 6 mol / L solid strong base to the diluted solution while stirring continuously during the addition process; S2-3: The solution was ultrasonically treated at 20°C under argon atmosphere for 20 min with an ultrasonic power of 400 W; S2-4: The solution was stirred under argon atmosphere for 24-48 hours.
4. The method for preparing a MXene composite material grafted with a silane coupling agent according to claim 3, wherein: The strong base solid in step S2-2 is KOH or NaOH.
5. The method for preparing a MXene composite material grafted with a silane coupling agent according to claim 1, wherein: Step S3 specifically includes the following steps: S3-1: adding deionized water to the h-MXene dispersion of step S2, and centrifuging and washing repeatedly until the h-MXene dispersion is neutral; S3-2: Add deionized water to dilute the solution to 20-60 mg / ml; S3-3: Add an equal amount of ethanol to disperse and dilute the solution to 10-30 mg / ml. Ultrasonicate the solution at 20°C under argon atmosphere for 5 min at an ultrasonic power of 400 W. S3-4: adding 3-7 wt% of the h-MXene mass of a silane coupling agent to the solution, and adding anhydrous acetic acid to adjust the pH value of the solution to 4-5; S3-5: ultrasonically treat the solution at 20°C under argon atmosphere for 5 min at an ultrasonic power of 400 W; S3-6: continuously stir the solution under argon atmosphere for 6-10 h; S3-7: The resulting solution was washed with excess silane coupling agent by adding ethanol and centrifuging twice.
6. The method for preparing a MXene composite material grafted with a silane coupling agent according to claim 5, characterized in that The silane coupling agent described in step S3-4 is one of γ-aminopropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, and tridecafluorooctyltriethoxysilane.
7. A MXene composite material grafted with a silane coupling agent, characterized in that: The method is as described in any one of claims 1 to 6.
Citation Information
Cited By
Amphiphilic Ti3C2Tx-based flexible nanosheet oil-displacing agent and preparation method thereof
CN120966446A
A method for preparing an amphiphilic Ti3C2T x flexible nanosheet oil displacement agent
CN120966446B
Flexible semitransparent antioxidant corrosion-resistant MXene electromagnetic shielding film and preparation method and application thereof
CN121449959A