Fluorine-free modified mxene-based superhydrophobic photothermal coating and preparation method thereof

Abstract

The application discloses a preparation method of a fluorine-free modified MXene-based super-hydrophobic photothermal coating. The method first prepares multilayer MXene powder through an in-situ etching method, then disperses the multilayer MXene powder and modifies the surface of the multilayer MXene powder by using fluorine-free cage-shaped polysilsesquioxane to obtain fluorine-free cage-shaped polysilsesquioxane MXene super-hydrophobic photothermal material, and finally prepares the fluorine-free modified MXene-based super-hydrophobic photothermal coating through spraying. The fluorine-free modified MXene-based super-hydrophobic photothermal coating prepared by the method has excellent super-hydrophobic performance and exhibits photothermal conversion performance that is higher than that of an original MXene-based coating and a fluorine-modified MXene-based super-hydrophobic photothermal coating, and the preparation method is simple and avoids pollution caused by fluorine-containing modifiers. Furthermore, the fluorine-free modified MXene-based super-hydrophobic photothermal coating can not only prevent ice by using a super-hydrophobic surface but also actively remove ice by using photothermal conversion characteristics, and has excellent ice prevention and ice removal performance.

Description

Technical Field

[0001] This invention belongs to the field of superhydrophobic coating technology, specifically relating to a fluorine-free modified MXene-based superhydrophobic photothermal coating and its preparation method. Background Technology

[0002] In nature, icing has numerous adverse effects on daily life and industrial production. For example, icing on aircraft wings and wind turbine blades severely weakens their operational stability and efficiency; icy road surfaces significantly increase the risk of traffic accidents; and icing on power transmission lines not only endangers the safety of power systems but can also cause widespread power outages and traffic disruptions. Traditional de-icing methods, such as mechanical scraping, thermal melting, and spraying chemical de-icing agents, suffer from low efficiency, high energy consumption, complex operation, and environmental pollution.

[0003] In recent years, biomimetic anti-icing materials have attracted widespread attention, especially superhydrophobic surfaces, which significantly reduce the contact area and heat conduction between water droplets and solid surfaces, delay freezing time, and reduce ice adhesion, exhibiting excellent passive anti-icing performance. However, in extreme low-temperature and high-humidity environments, water vapor condensation easily interlocks with the surface, and structural damage caused by de-icing cycles limits the sustainability of their anti-icing effect. To improve the stability of surface anti-icing performance, photothermal effects are combined with superhydrophobic surfaces to construct photothermal superhydrophobic surfaces, thus enabling both passive anti-icing and active photothermal de-icing. MXenes, as a new class of two-dimensional transition metal carbides / nitrides, possess excellent electrical conductivity, thermal conductivity, and photothermal conversion performance, but their strong hydrophilicity limits their application in the superhydrophobic field. Currently, researchers mostly modify MXene surfaces with low surface energy perfluorides to construct superhydrophobic surfaces, which not only significantly improves the environmental stability of MXenes but also expands their application space in de-icing and anti-icing fields. However, fluorine modification not only affects the photothermal conversion efficiency of MXene-based coatings, but the perfluorinated modifiers used are also difficult to degrade, posing a serious threat to the ecological environment and human health. In addition, fluorinated modifiers are expensive, including raw material costs and waste treatment costs. These drawbacks of fluorinated modifiers limit their industrial application.

[0004] Therefore, a method for preparing a fluorine-free modified MXene-based superhydrophobic photothermal coating is needed. Summary of the Invention

[0005] The technical problem to be solved by this invention is to address the shortcomings of the prior art by providing a method for preparing a fluorine-free modified MXene-based superhydrophobic photothermal coating. This method involves superhydrophobically modifying the surface of MXene with a fluorine-free cage-like polysilsesquioxane to obtain a fluorine-free cage-like polysilsesquioxane MXene superhydrophobic photothermal material. This cage-like polysilsesquioxane MXene superhydrophobic photothermal material is then composited with an epoxy resin system and coated using a spraying process to obtain a fluorine-free modified MXene-based superhydrophobic photothermal coating. This coating not only provides anti-icing protection using its superhydrophobic surface but also actively de-ices using its photothermal conversion properties, exhibiting excellent anti-icing and de-icing performance.

[0006] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is: a method for preparing a fluorine-free modified MXene-based superhydrophobic photothermal coating, characterized in that the method includes the following steps:

[0007] Step 1: LiF is added to concentrated hydrochloric acid solution and stirred to dissolve, thus obtaining HF etching solution. Then Ti3AlC2 is slowly added to HF etching solution and stirred. After centrifugation, washing and freeze-drying, multilayer MXene powder is obtained.

[0008] Step 2: Disperse the multilayer MXene powder obtained in Step 1 in an organic solvent to obtain an MXene organic dispersion. Then, add the MXene organic dispersion to an organic solution containing fluorine-free cage-type polysilsesquioxane, and stir, heat and reflux to obtain fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material.

[0009] Step 3: The fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material obtained in Step 2 is processed to obtain a fluorine-free modified MXene-based superhydrophobic photothermal coating with anti-icing and de-icing properties.

[0010] This invention disperses multilayer MXene powder in an organic solvent and mixes it with an organic solution of fluorine-free cage-like polysilsesquioxane. The mixture is then stirred and heated under reflux to obtain a fluorine-free cage-like polysilsesquioxane MXene superhydrophobic photothermal material. In this material, the functional groups of the cage-like polysilsesquioxane form covalent or hydrogen bonds with the active groups on the MXene surface, allowing the cage-like polysilsesquioxane molecules to uniformly adhere to the MXene surface. This not only improves the photothermal conversion performance of MXene but also allows the cage-like polysilsesquioxane molecules to overcome steric hindrance through their significant steric effect. The original highly oriented structure of MXene was disrupted, making the surface micro-nano structure rougher. This, combined with the abundant silicon content and long-chain non-functional side groups, endowed the MXene surface with superhydrophobicity. Subsequently, by treating the fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material, a fluorine-free modified MXene-based superhydrophobic photothermal coating was finally obtained. Based on the different cage-type polysilsesquioxane molecular structures on the modified MXene surface, the performance improvement directions of the obtained MXene-based superhydrophobic photothermal coatings are diverse, with significant improvements in hydrophobicity and photothermal conversion efficiency.

[0011] The above-described method for preparing a fluorine-free modified MXene-based superhydrophobic photothermal coating is characterized in that the concentration of the concentrated hydrochloric acid solution in step one is 9 mol / L, the mass ratio of LiF to Ti3AlC2 is 1~1.6:1, and the stirring temperature is 35℃~55℃ for 20h~40h. This invention ensures the successful preparation of multilayer MXene powder by controlling the preparation parameters.

[0012] The above-mentioned method for preparing a fluorine-free modified MXene-based superhydrophobic photothermal coating is characterized in that the fluorine-free cage-like polysilsesquioxane in step two is aminopropylheptyl cage-like polysilsesquioxane, silanetriol isobutyl cage-like polysilsesquioxane, silanetriol phenyl cage-like polysilsesquioxane, or mercaptopropyl isooctyl cage-like polysilsesquioxane. This invention, by controlling the type of fluorine-free cage-like polysilsesquioxane, firstly allows it to interact with MXene, imparting superhydrophobicity to the MXene surface. Secondly, the fluorine-free cage-like polysilsesquioxane molecules, through their significant steric hindrance effect, disrupt the original highly oriented structure of MXene, making the surface micro / nano structure rougher. Furthermore, all of these have a high silicon content, ensuring the performance of the fluorine-free cage-like polysilsesquioxane MXene superhydrophobic photothermal material.

[0013] The above-mentioned method for preparing a fluorine-free modified MXene-based superhydrophobic photothermal coating is characterized in that, in step two, the mass ratio of the fluorine-free cage-type polysilsesquioxane to MXene is 1~8:1; the mass ratio of the sum of the organic solvents in the MXene organic dispersion and the organic solvents used in the organic solution containing the fluorine-free cage-type polysilsesquioxane to the mass of MXene is 110~270:1; and the stirring, heating, and reflux temperature is 60℃~90℃, and the time is 6h~36h. This invention, by controlling the amount of each raw material and the preparation parameters, ensures that the fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material has optimal performance.

[0014] The above-mentioned method for preparing a fluorine-free modified MXene-based superhydrophobic photothermal coating is characterized in that the treatment in step three involves sequentially adding the fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material, epoxy resin, and epoxy curing agent to an organic solvent, stirring until uniformly mixed and dispersed, then spraying it onto a substrate, followed by defoaming and isothermal curing. This invention provides a matrix for the fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material by adding epoxy resin and epoxy curing agent, enabling it to be better prepared on the surface of other materials to form a coating. The addition of an organic solvent to dilute the fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material facilitates subsequent spraying. Defoaming prevents coating defects, and isothermal curing cures the epoxy resin, ultimately yielding the coating.

[0015] The method for preparing a fluorine-free modified MXene-based superhydrophobic photothermal coating is characterized by the following: the mass ratio of epoxy resin to fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material is 0-2:1; the mass ratio of epoxy resin to epoxy curing agent is 1-9:1; and the mass ratio of organic solvent to fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material is 70-110:1. This invention achieves adjustment of the amount of epoxy resin used by controlling the mass ratio of epoxy resin to fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material, and can also eliminate the need for epoxy resin. By controlling the mass ratio of epoxy resin to epoxy curing agent, the epoxy resin is fully cured and its post-curing strength is controlled. By controlling the mass ratio of organic solvent to fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material, the degree of dilution is controlled, ensuring the uniformity of the subsequently formed coating.

[0016] The above-mentioned method for preparing a fluorine-free modified MXene-based superhydrophobic photothermal coating is characterized in that the epoxy resin is one or more of epoxy resin E44, epoxy resin E51, epoxy resin E54 and epoxy resin E55, and the curing agent is ethylenediamine, polyamide curing agent or polyetheramine curing agent.

[0017] The method for preparing a fluorine-free modified MXene-based superhydrophobic photothermal coating is characterized in that the organic solvent is n-hexane, tetrahydrofuran, xylene, acetone, N-methylpyrrolidone, or N,N-dimethylformamide.

[0018] It should be noted that the organic solutions used in step two and the organic solutions containing fluorine-free cage-type polysilsesquioxane are also hexane, tetrahydrofuran, xylene, acetone, N-methylpyrrolidone, or N,N-dimethylformamide.

[0019] The above-mentioned method for preparing a fluorine-free modified MXene-based superhydrophobic photothermal coating is characterized by the following steps: the coating is placed in a vacuum oven, then evacuated and allowed to stand for 0.25 h to 1 h for defoaming, followed by heating to 70 °C to 110 °C for constant temperature curing for 6 h to 18 h. This invention ensures the coating's performance by controlling the defoaming parameters to fully remove air bubbles, and by controlling the constant temperature curing parameters to ensure complete curing of the coating, thus also guaranteeing its performance.

[0020] In addition, the present invention also provides a fluorine-free modified MXene-based superhydrophobic photothermal coating, characterized in that the fluorine-free modified MXene-based superhydrophobic photothermal coating is prepared by the above method.

[0021] Compared with the prior art, the present invention has the following advantages:

[0022] 1. This invention utilizes cage-type polysilsesquioxane to modify MXene, obtaining a fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material. It not only possesses photothermal conversion performance exceeding that of the original MXene, but also exhibits comparable photothermal conversion performance to fluorine-modified MXene. Furthermore, the significant steric hindrance effect, high silicon content, and multiple long-chain side groups of the cage-type polysilsesquioxane molecule endow it with excellent superhydrophobicity, integrating superhydrophobic and photothermal properties into one, enabling both anti-icing and efficient de-icing.

[0023] 2. This invention modifies the surface of MXene with a fluorine-free cage-type polysilsesquioxane to obtain a fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material. Then, the cage-type polysilsesquioxane MXene superhydrophobic photothermal material is compounded with an epoxy resin system and a fluorine-free modified MXene-based superhydrophobic photothermal coating is prepared by spraying. This coating can not only prevent icing by utilizing the superhydrophobic surface, but also actively de-ic it by utilizing the photothermal conversion characteristics, thus exhibiting excellent anti-icing and de-icing performance.

[0024] 3. The cage-type polysilsesquioxane modified MXene proposed in this invention has a simple preparation method that is free of fluorides, and is also highly efficient and environmentally friendly. It avoids pollution from fluorine-containing modifiers and avoids the problems of cumbersome processes and significant environmental pollution in existing modification methods. It also solves the problems of insufficient photothermal conversion efficiency and significant pollution during the preparation process of perfluorinated modified MXene superhydrophobic photothermal coating.

[0025] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0026] Figure 1 This is a flowchart illustrating the preparation process of the fluorine-free modified MXene-based superhydrophobic photothermal coating of this invention.

[0027] Figure 2 The contact angles are those of the fluorine-free modified MXene-based superhydrophobic photothermal coating prepared in Example 1 of the present invention, the original MXene-based coating prepared in Comparative Example 1, and the fluorine-modified MXene-based superhydrophobic photothermal coating prepared in Comparative Example 2.

[0028] Figure 3 The temperature rise curves of the fluorine-free modified MXene-based superhydrophobic photothermal coating prepared in Example 1 of the present invention, the original MXene-based coating prepared in Comparative Example 1, and the fluorine-modified MXene-based superhydrophobic photothermal coating prepared in Comparative Example 2 under one solar irradiance are shown.

[0029] Figure 4 The anti-icing process of the fluorine-free modified MXene-based superhydrophobic photothermal coating prepared in Example 1 of the present invention and the original MXene-based coating prepared in Comparative Example 1.

[0030] Figure 5 The de-icing process of the fluorine-free modified MXene-based superhydrophobic photothermal coating prepared in Example 1 of the present invention and the original MXene-based coating prepared in Comparative Example 1. Detailed Implementation

[0031] Figure 1 This is a flowchart illustrating the preparation process of the fluorine-free modified MXene-based superhydrophobic photothermal coating of this invention. Figure 1As can be seen from the above, the present invention first adds LiF to concentrated hydrochloric acid solution and stirs to dissolve it to obtain HF etching solution. Then, Ti3AlC2 is slowly added to HF etching solution and stirred. After centrifugation, washing and freeze drying, multilayer MXene powder is obtained. Then, the multilayer MXene powder is dispersed in an organic solvent to obtain MXene organic dispersion. Subsequently, the MXene organic dispersion is added to an organic solution containing fluorine-free cage-type polysilsesquioxane, and after stirring and heating under reflux, fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material is obtained. Finally, the fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material is processed to obtain a fluorine-free modified MXene-based superhydrophobic photothermal coating with anti-icing and de-icing properties.

[0032] Example 1

[0033] This embodiment includes the following steps:

[0034] Step 1: Add 3.2g LiF to 40mL of concentrated hydrochloric acid solution with a concentration of 9mol / L and stir to dissolve to obtain HF etching solution. Then slowly add 2g Ti3AlC2 to HF etching solution and stir to react at 50℃ for 24h. Then centrifuge, wash and freeze dry to obtain multilayer MXene powder.

[0035] Step 2: Disperse 1g of the multilayer MXene powder obtained in Step 1 in 90g of tetrahydrofuran to obtain an MXene organic dispersion. Dissolve 4g of aminopropylheptyl cage-like polysilsesquioxane in 90g of tetrahydrofuran to obtain an organic solution containing fluorine-free cage-like polysilsesquioxane. Then add the MXene organic dispersion to the organic solution containing fluorine-free cage-like polysilsesquioxane and stir and heat under reflux at 70°C for 12h to obtain fluorine-free cage-like polysilsesquioxane MXene superhydrophobic photothermal material.

[0036] Step 3: Add 0.5g of the fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material obtained in Step 2, 0.5g of epoxy resin E51, and 0.25g of polyamide curing agent to 45g of tetrahydrofuran in sequence, and then stir until uniformly mixed and dispersed. Spray the mixture onto a glass slide treated with anhydrous ethanol, then place it in a vacuum oven, evacuate the vacuum, and let it stand for 1 hour to remove bubbles. Then heat it to 80℃ and cure it at a constant temperature for 12 hours to obtain a fluorine-free modified MXene-based superhydrophobic photothermal coating with anti-icing and de-icing properties.

[0037] Example 2

[0038] The preparation steps in this embodiment are the same as those in Example 1, except that the amount of LiF added in step one is 2g, and the reaction is stirred at 40°C for 36h.

[0039] Example 3

[0040] The preparation steps in this embodiment are the same as those in Example 1, except that in step two, 6g of aminopropylheptyl cage-like polysilsesquioxane is dissolved in 135g of N-methylpyrrolidone.

[0041] Example 4

[0042] The preparation steps in this embodiment are the same as those in Example 1. The difference is that in step two, the fluorine-free cage-type polysilsesquioxane is silanetriol isobutyl cage-type polysilsesquioxane, the amount added is 1g, and it is dissolved in 20g of N,N-dimethylformamide and stirred and heated under reflux at 60°C for 36h.

[0043] Example 5

[0044] The preparation steps in this embodiment are the same as those in Example 1. The difference is that in step two, the fluorine-free cage-type polysilsesquioxane is mercaptopropyl isooctyl cage-type polysilsesquioxane, the amount added is 8g, and it is dissolved in 180g of xylene and stirred and heated under reflux at 90°C for 6h.

[0045] Example 6

[0046] The preparation steps of this embodiment are the same as those of Example 1. The difference is that in step three, the epoxy resin is E55 and the amount added is 0.25g, the curing agent is a polyetheramine curing agent and the amount added is 0.1g, the amount added is tetrahydrofuran is 40g, the standing time is 0.5h to remove bubbles, and the temperature is heated to 70℃ for constant temperature curing for 18h.

[0047] Example 7

[0048] The preparation steps of this embodiment are the same as those of Example 1. The difference is that in step three, the epoxy resin is E44, the amount added is 0.5g, it is left to stand for 0.25h to remove bubbles, and then heated to 90℃ for constant temperature curing for 10h.

[0049] Example 8

[0050] The preparation steps in this embodiment are the same as those in Example 1. The difference is that in step three, the epoxy resin is E54, the amount added is 1g, the curing agent is ethylenediamine, the amount added is 0.11g, the amount added is tetrahydrofuran, and the temperature is heated to 110℃ and cured for 6h.

[0051] Example 9

[0052] The preparation steps in this embodiment are the same as those in Example 1, except that in step three, the amount of epoxy resin added is 0 and the amount of tetrahydrofuran added is 35g.

[0053] Example 10

[0054] The preparation steps in this embodiment are the same as those in Example 1, except that in step one, the amount of LiF added is 2.4g, and the reaction is stirred at 35°C for 40h. In step two, the fluorine-free cage-type polysilsesquioxane is silanetriol phenyl cage-type polysilsesquioxane.

[0055] Example 11

[0056] The preparation steps in this embodiment are the same as those in Example 1, except that in step one, the amount of LiF added is 2.8g and the reaction is carried out at 55°C for 20h, and in step three, the amount of polyamide curing agent added is 0.5g.

[0057] Comparative Example 1

[0058] The preparation steps in this embodiment are the same as those in Example 1, except that in step two, no fluorine-free cage-type polysilsesquioxane is added to obtain the original MXene-based coating.

[0059] Comparative Example 2

[0060] The preparation steps in this embodiment are the same as those in Example 1. The difference is that in step two, the fluorine-free cage-type polysilsesquioxane is replaced with perfluorodecyltrimethoxysilane, and the mixture is stirred and heated under reflux at room temperature for 24 hours to obtain a fluorine-modified MXene-based superhydrophobic photothermal coating.

[0061] Hydrophobic performance test: The water contact angle of the fluorine-free modified MXene-based superhydrophobic photothermal coatings prepared in Examples 1-11 of this invention, the original MXene-based coating prepared in Comparative Example 1, and the fluorine-modified MXene-based superhydrophobic photothermal coating prepared in Comparative Example 2 was tested using a water contact angle measuring instrument. The test results are shown in Table 1 below.

[0062] Table 1

[0063]

[0064] As can be seen from Table 1, compared to the original MXene-based coating (Comparative Example 1, the contact angle is only 48°), o The contact angles of the fluorine-free modified MXene-based superhydrophobic photothermal coatings prepared in Examples 1-7 and Examples 9-11 of this invention all exceeded 150°. o The first example achieved a superhydrophobic state, while in Example 8, due to excessive epoxy resin addition, the fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material was coated, resulting in a decreased contact angle, but it could still reach 122°. o In addition, the fluorine-free modified MXene-based superhydrophobic photothermal coating prepared in Example 1 and the fluorine-modified MXene-based superhydrophobic photothermal coating prepared in Comparative Example 2 exhibit the same superhydrophobic state. Figure 2The static contact angle diagrams of the coatings prepared in Example 1, Comparative Example 1, and Comparative Example 2 show that the fluorine-free modified MXene-based superhydrophobic photothermal coating provided by the present invention has excellent superhydrophobic properties, comparable to fluorine-modified MXene-based superhydrophobic photothermal coatings.

[0065] Photothermal performance testing: The temperature change of the coating surface under one day of sunlight was tested using a xenon lamp source and an infrared thermal imager for the fluorine-free modified MXene-based superhydrophobic photothermal coatings prepared in Examples 1-11 of this invention, the original MXene-based coating prepared in Comparative Example 1, and the fluorine-modified MXene-based superhydrophobic photothermal coating prepared in Comparative Example 2. Specifically, the xenon lamp source was adjusted to one solar irradiance (1000 W / m²). 2 The coating was vertically irradiated for 600 seconds, and the temperature change of the coating surface was recorded using an infrared thermal imager. The test results are shown in Table 2 below.

[0066] Table 2

[0067]

[0068] As shown in Table 2, the surface temperature of the fluorine-free modified MXene-based superhydrophobic photothermal coatings prepared in Examples 1-11 of this invention increased from room temperature to over 76°C under one solar irradiance. In particular, the surface temperature of the fluorine-free modified MXene-based superhydrophobic photothermal coating prepared in Example 9 increased to 124°C, which is related to the absence of epoxy resin. In contrast, the surface temperature of the conventional MXene-based coating prepared in Comparative Example 1 only increased to 43°C, which is related to the large number of polar groups on the MXene surface. The number of polar functional groups on the modified MXene surface decreased. The fluorine-free modified MXene-based superhydrophobic photothermal coating prepared in Example 8 had a reduced photothermal conversion efficiency due to the excessive amount of epoxy resin coating the fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material. In addition, the surface temperature of the fluorine-modified MXene-based superhydrophobic photothermal coating prepared in Comparative Example 2 increased from room temperature to 67°C under one solar irradiance, which is lower than that of Example 1. Figure 3 The temperature rise curves of the coatings prepared in Example 1, Comparative Example 1 and Comparative Example 2 under a solar irradiance are shown. The results show that the fluorine-free modified MXene-based superhydrophobic photothermal coating provided by the present invention has excellent photothermal performance, and its photothermal conversion efficiency is higher than that of the currently reported fluorine-modified MXene-based superhydrophobic photothermal coatings.

[0069] Anti-icing and de-icing performance tests: The anti-icing and de-icing performance of the fluorine-free modified MXene-based superhydrophobic photothermal coatings prepared in Examples 1-11 of this invention, the original MXene-based coating prepared in Comparative Example 1, and the fluorine-modified MXene-based superhydrophobic photothermal coating prepared in Comparative Example 2 were tested using a cooling platform and a xenon lamp light source, respectively. The anti-icing process was as follows: the coating was placed on a cooling platform at -20°C (no light), a drop of water was dropped on the coating surface, and the freezing process and time were recorded. The de-icing process was as follows: after complete freezing, the xenon lamp light source was turned on and adjusted to the intensity of sunlight, and the melting process and time were recorded. The test results are shown in Table 3 below.

[0070] Table 3

[0071]

[0072] As can be seen from Table 3, the anti-icing time of the fluorine-free modified MXene-based superhydrophobic photothermal coatings prepared in Examples 1-7 and Examples 9-11 of this invention all exceeded 270s, and the de-icing time was all less than 140s. The icing time was longer than the de-icing time, showing excellent anti-icing and de-icing performance. In contrast, the conventional MXene-based coating prepared in Comparative Example 1 had a larger contact area and a shorter de-icing time of only 96s, while the anti-icing time was only 24s. The icing time was shorter than the de-icing time, indicating insufficient anti-icing and de-icing performance. Although the anti-icing time of the fluorine-free modified MXene-based superhydrophobic photothermal coating prepared in Example 8 was shortened, it was still longer than the de-icing time, and it still had excellent anti-icing and de-icing performance. In addition, the fluorine-free modified MXene-based superhydrophobic photothermal coating prepared in Example 1 and the fluorine-modified MXene-based superhydrophobic photothermal coating prepared in Comparative Example 2 showed equally excellent anti-icing and de-icing performance. Figure 4 and Figure 5 The anti-icing and de-icing processes of the coatings prepared in Example 1 and Comparative Example 1 are shown respectively. The results show that the fluorine-free modified MXene-based superhydrophobic photothermal coating provided by the present invention has excellent anti-icing and de-icing performance.

[0073] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any way. Any simple modifications, alterations, and equivalent changes made to the above embodiments based on the technical essence of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A method for preparing a fluorine-free modified MXene-based superhydrophobic photothermal coating, characterized in that, The method includes the following steps: Step 1: LiF is added to concentrated hydrochloric acid solution and stirred to dissolve, thus obtaining HF etching solution. Then Ti3AlC2 is slowly added to HF etching solution and stirred. After centrifugation, washing and freeze-drying, multilayer MXene powder is obtained. Step 2: Disperse the multilayer MXene powder obtained in Step 1 in an organic solvent to obtain an MXene organic dispersion. Then, add the MXene organic dispersion to an organic solution containing a fluorine-free cage-like polysilsesquioxane, and stir and heat under reflux to obtain a fluorine-free cage-like polysilsesquioxane MXene superhydrophobic photothermal material. The fluorine-free cage-like polysilsesquioxane is aminopropylheptyl cage-like polysilsesquioxane, silanetriol isobutyl cage-like polysilsesquioxane, silanetriol phenyl cage-like polysilsesquioxane, or mercaptopropyl isooctyl cage-like polysilsesquioxane. The mass ratio of the fluorine-free cage-like polysilsesquioxane to MXene is 1~8:

1. Step 3: The fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material obtained in Step 2 is processed to obtain a fluorine-free modified MXene-based superhydrophobic photothermal coating with anti-icing and de-icing properties. The processing involves sequentially adding the fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material, epoxy resin, and epoxy curing agent to an organic solvent, stirring until uniformly mixed and dispersed, then spraying it onto a substrate, followed by defoaming and constant-temperature curing. The mass ratio of epoxy resin to fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material is 0~1:1, the mass ratio of epoxy resin to epoxy curing agent is 1~9:1, and the mass ratio of organic solvent to fluorine-free cage-type polysilsesquioxane MXene superhydrophobic photothermal material is 70~110:

1.

2. The method for preparing a fluorine-free modified MXene-based superhydrophobic photothermal coating according to claim 1, characterized in that, The concentration of the concentrated hydrochloric acid solution in step one is 9 mol / L, and the mass ratio of LiF to Ti3AlC2 is 1~1.6:1; the stirring temperature is 35℃~55℃, and the stirring time is 20h~40h.

3. The method for preparing a fluorine-free modified MXene-based superhydrophobic photothermal coating according to claim 1, characterized in that, In step two, the mass ratio of the organic solvent in the MXene organic dispersion and the organic solvent in the organic solution containing fluorine-free cage-type polysilsesquioxane to the mass of MXene is 110~270:1; the stirring, heating, and reflux temperature is 60℃~90℃, and the time is 6h~36h.

4. The method for preparing a fluorine-free modified MXene-based superhydrophobic photothermal coating according to claim 1, characterized in that, The epoxy resin is one or more of epoxy resin E44, epoxy resin E51, epoxy resin E54 and epoxy resin E55, and the curing agent is ethylenediamine, polyamide curing agent or polyetheramine curing agent.

5. The method for preparing a fluorine-free modified MXene-based superhydrophobic photothermal coating according to claim 1, characterized in that, The organic solvent is n-hexane, tetrahydrofuran, xylene, acetone, N-methylpyrrolidone, or N,N-dimethylformamide.

6. The method for preparing a fluorine-free modified MXene-based superhydrophobic photothermal coating according to claim 1, characterized in that, The defoaming and constant temperature curing process is as follows: place it in a vacuum oven, then evacuate the vacuum and let it stand for 0.25h~1h to defoam, and then heat it to 70℃~110℃ for constant temperature curing for 6h~18h.

7. A fluorine-free modified MXene-based superhydrophobic photothermal coating, characterized in that, The fluorine-free modified MXene-based superhydrophobic photothermal coating is prepared by the method described in any one of claims 1 to 6.

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