A film with self-sensing deicing properties and its preparation method

Abstract

The present invention discloses a film with self-sensing deicing properties and a preparation method thereof, belonging to the field of functional materials and their preparation technology. The present invention constructs a spiral carbon nanotube-graphene three-dimensional structure, utilizes spiral carbon nanotubes to overlap between graphene layers to play a bridging role, constitutes a heat-conducting and electrically conductive network structure, reduces graphene stacking and carbon nanotube agglomeration, and enhances the heat transfer path. Further, the composite dimensional silver grafted with long-chain alkanes is introduced into the coating surface by screen printing technology to reduce the surface energy of the film, realize super-hydrophobicity of the film, and at the same time give the film an excellent conductive path to prepare a film with a super-hydrophobic surface having both photothermal and electrothermal properties. The film has excellent photothermal performance and conductive properties. In an environment with sufficient light, the film converts solar energy into thermal energy without the need for additional energy. In the case of insufficient light or a thick layer of ice, the electrothermal deicing mode is activated, the deicing state is sensed in real time, the deicing efficiency is improved, and energy is saved.

Description

Technical Field

[0001] The invention relates to a film with self-sensing deicing properties and a preparation method thereof, belonging to the technical field of functional materials and preparation thereof. Background Art

[0002] Cable-stayed bridges excel in large-span bridge engineering applications due to their superior spanning capacity, lightweight structure, and excellent aerodynamic stability. Most cable-stayed bridges span rivers and valleys, where humidity is high and icing can occur when ambient temperatures fall below 0°C. Ice melt can disrupt traffic or damage vehicles, endangering public safety and causing economic losses. It can also alter the aerodynamic shape of the cables, exacerbating wind-induced cable vibrations and severely impacting the lifespan of the cable-stayed bridge. Therefore, research on anti-icing / de-icing materials and technologies for cable-stayed bridges, and improving their ability to protect against icing disasters, is of great significance to daily life, industrial production, national defense, and military applications.

[0003] Deicing methods for cable-stayed bridges can be divided into two categories: active anti-icing / deicing technologies such as mechanical deicing and thermal methods (electric heating, plasma heating), and passive anti-icing / deicing technologies such as super-hydrophobic coatings. The patent (CN216640249U) designs a mechanical deicing device for cable-stayed bridge cables. The motor is equipped with a blade to cut the ice layer, and the propulsion device is used to move the cables to achieve comprehensive deicing. However, this method is energy-consuming and inefficient, and will cause certain damage to the surface of the cable. Although the super-hydrophobic coating (CNCN110423523A) has excellent delayed icing performance, its micro-nano structure is fragile and has poor impact resistance. In low temperature and high humidity environments, the micro-nano hierarchical structure fails, resulting in loss of hydrophobicity. Photothermal coatings (CN116656235A) rely on solar energy input to raise the interface temperature above the freezing point to prevent icing, but the photothermal conversion rate is greatly reduced at night or on cloudy days, and the deicing power is limited. Moreover, for materials exposed to cold and harsh environments for a long time, a single-function anti-icing / de-icing method cannot prevent the formation of ice / frost in complex environments. Summary of the Invention

[0004] The present invention addresses the limitations of existing superhydrophobic coatings, such as failure to prevent icing under low temperature and high humidity conditions, and reduced deicing power of photothermal coatings on cloudy days or at night. The invention provides a film with self-sensing deicing properties and a preparation method thereof, thereby achieving real-time anti-icing and all-weather deicing, providing a competitive solution for the anti-icing / deicing of cable-stayed bridges.

[0005] The technical solution of the present invention:

[0006] One of the objects of the present invention is to provide a method for preparing a film having self-sensing deicing properties, the method comprising the following steps:

[0007] (1) A graphene oxide (GO) aqueous solution and a carboxylated helical carbon nanotube (HCNT) aqueous solution are mixed, a reducing agent is added, and the mixture is reacted in a water bath. After the reaction is completed, the mixture is washed with deionized water to obtain HCNTs-rGO;

[0008] (2) HCNTs-rGO was mixed with toluene, ultrasonically dispersed, styrene-ethylene-butadiene-styrene block copolymer (SEBS) was added, and ultrasonic dispersion was continued to obtain an organic suspension;

[0009] (3) Spin coating the organic suspension onto a glass sheet and heat treating it to obtain a HCNTs-rGO / SEBS film;

[0010] (4) The long-chain alkane-grafted composite dimensional silver was mixed with toluene, ultrasonically dispersed, added with SEBS, stirred evenly, and then coated on the HCNTs-rGO / SEBS film by screen printing technology to obtain a film with self-sensing deicing properties.

[0011] It is further defined that the preparation method of the carboxylated helical carbon nanotubes in (1) is as follows: the helical carbon nanotubes and concentrated nitric acid are placed in a high-pressure reactor, kept at a constant temperature of 160° C. in a forced air drying oven for 6 to 8 hours, cooled to room temperature, and then rinsed with ethanol and deionized water until neutral to obtain the carboxylated helical carbon nanotubes.

[0012] It is further defined that the reducing agent in (1) is an aqueous solution of ascorbic acid.

[0013] It is further defined that the water bath reaction temperature in (1) is 80-85°C and the reaction time is 8-12 hours.

[0014] Further defined, the specific operation process of (1) is: take 40 mL of a 2 mg / mL graphene oxide aqueous solution and sonicate for 2 h, mix it with 50 mL of a 1 mg / mL carboxylated helical carbon nanotube aqueous solution and sonicate for 1.5 h, then add 80 mL of a 10 mg / mL ascorbic acid aqueous solution, and mechanically stir it at 400-600 r / min in a constant temperature water bath at 80-85°C for 8-12 h.

[0015] Further defined, the preparation method of graphene oxide aqueous solution is: 13.8mL concentrated sulfuric acid and 0.6g natural flake graphite powder are placed in an ice water bath at -1 to 1°C and stirred for 0.5 to 1h, and then 3.6g potassium permanganate (KMnO4) is added in batches. After the addition of KMnO4 is completed, stirring is continued in an ice water bath for 2.5 to 3h, and the stirring speed is 600 to 800r / min; then placed in a constant temperature water bath at 40 to 45°C, mechanically stirred for 20 to 30min, and a reddish brown viscous liquid is obtained, and the temperature is continued to be raised to 80 to 85°C, 42mL deionized water is added in batches, and after stirring for 20min, 36mL deionized water is added; 10mL 30% hydrogen peroxide was diluted with 30 mL of deionized water and then added to the above mixture. The solution immediately turned golden yellow. The resulting solution was filtered and washed with 40 mL of 3.7 wt% hydrochloric acid for 12 h. After filtering again, the filter cake was dispersed in deionized water and stirred at a speed of 600-800 r / min for 12 h. The solution was then centrifuged at 3500 rpm for 30-40 min to remove unexfoliated graphite. The supernatant was retained and placed in a dialysis bag. Dialysis was performed for one week to remove residual ions to obtain a graphene oxide aqueous solution.

[0016] It is further defined that the molecular weight cut-off of the dialysis bag is 8000 to 14000 Da.

[0017] It is further defined that, in the organic suspension obtained in (2), the mass ratio of HCNTs-rGO to HCNTs-rGO and SEBS is 1:(3-5), and the volume ratio of SEBS mass to toluene is 1 g:(5-20) mL.

[0018] It is further defined that the heat treatment temperature in (3) is 50-60°C and the time is 5-10 minutes.

[0019] It is further defined that (4) the preparation method of the composite dimensional silver grafted with medium and long chain alkanes is as follows: silver microsheets and silver nanowires are mixed with ethanol, stirred evenly, and then decanethiol is added dropwise. After stirring in the dark, the mixture is washed by centrifugation with ethanol. Then, the washed product is dispersed in ethanol, propanethiol is added, stirred in the dark, and washed by centrifugation with ethanol to obtain the composite dimensional silver grafted with long chain alkanes.

[0020] It is further defined that the mass volume ratio of the silver microsheets, silver nanowires, decanethiol and propanethiol is 100 mg: (50-150) mg: (200-330) μL: (0.8-1.32) mL.

[0021] Further defined, (4) the specific preparation process of the composite dimensional silver grafted with medium and long chain alkanes is as follows: silver microsheets, silver nanowires and ethanol are mixed in a mass volume ratio of 100 mg: (50-150) mg: 100 mL, stirred evenly at room temperature, and then 200-330 μL of decanethiol is added dropwise, stirred in the dark for 10-12 h, and then washed with ethanol by centrifugation 4-5 times at a centrifugal speed of 2500-3500 r / min; then the silver microsheets and silver nanowires after centrifugation are dispersed in 100 mL of ethanol, 0.8-1.32 mL of propylthiol is added, stirred in the dark for 2-4 h, and then washed with ethanol by centrifugation 4-5 times at a centrifugal speed of 3500-4500 r / min to obtain the composite dimensional silver grafted with long chain alkanes.

[0022] It is further defined that the preparation process of silver nanowires is as follows: 0.5g of polyvinyl pyrrolidone is added to 50mL of ethylene glycol, dissolved under magnetic stirring at 90°C, and cooled to room temperature after dissolution for use; 0.33g of AgNO3 is weighed and dissolved in 24mL of ethylene glycol and stirred evenly, 30mL of polyvinyl pyrrolidone ethylene glycol solution and 4.5mL of 600μM FeCl3·6H2O ethylene glycol solution are added and stirred for 1-2h, and the reaction is carried out in a forced air oven at 130°C for 6-8h, and finally the product is centrifuged and washed 4-5 times with anhydrous ethanol at a centrifugal speed of 3500-4500r / min to obtain silver nanowires.

[0023] It is further defined that the mass ratio of (4) the composite dimensional silver grafted with a medium-chain alkane, SEBS and toluene is 0.5:(0.03-0.08):(0.18-0.42).

[0024] A second object of the present invention is to provide a film having self-sensing deicing properties obtained by the above preparation method.

[0025] Beneficial effects:

[0026] The present invention combines graphene and spiral carbon nanotubes with excellent electrical, mechanical and thermal properties by constructing a spiral carbon nanotube-graphene three-dimensional structure, and combines the anti-icing properties of the super-hydrophobic surface to prepare a super-hydrophobic surface with both photothermal and electrothermal properties. Spiral carbon nanotubes are used to overlap between graphene layers to act as a bridge, forming a thermally conductive and electrically conductive network structure, reducing the graphene stacking effect and carbon nanotube agglomeration phenomenon, enhancing the heat transfer path, compensating for the defects of electron transmission, and achieving the purpose of improving the thermal and electrical conductivity of the composite structure film. Silver nanowires and silver micron sheets grafted with long-chain alkanes are introduced into the coating surface to reduce the surface energy of the film, achieve super-hydrophobicity of the film, and further reduce the ice adhesion strength. Screen printing technology is used to give the film an excellent conductive path, improve the overall conductivity of the film, and accelerate the electric heating deicing speed. Compared with the prior art, the present invention also has the following advantages:

[0027] (1) The self-sensing deicing film prepared by the present invention has super-hydrophobic properties and anti-corrosion properties, and can be used in harsh environments such as extreme temperature and humidity, while maintaining high sensitivity and rapid self-sensing intelligent response under a large strain range (100-600%).

[0028] (2) The self-sensing deicing film prepared by the present invention has excellent photothermal and conductive properties, and can realize passive (superhydrophobic) deicing and active (photothermal, electrothermal) deicing. In an environment with sufficient light, the film converts solar energy into thermal energy without the need for additional energy. In the case of insufficient light or thick ice, the active electrothermal deicing mode is activated to improve deicing efficiency and save energy.

[0029] (3) The film prepared by the present invention can sense the icing and deicing process, detect changes in ambient temperature, and achieve an integrated solution for the entire process from early warning, control, to deicing by integrating active / passive anti-icing / deicing. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a laser confocal image of the film with self-sensing deicing properties prepared in Example 1;

[0031] Figure 2 for Figure 1 The green box corresponds to the 3D outline of the area;

[0032] Figure 3 This is a SEM photograph of the film with self-sensing deicing properties prepared in Example 1;

[0033] Figure 4 The contact angle of the film with self-sensing deicing properties prepared in Example 1 with water;

[0034] Figure 5 The actual effect diagram of ice layer changes during the photothermal deicing process of the thin film with self-sensing deicing properties prepared in Example 1 and the corresponding infrared thermal imaging diagram (the scale in the figure is 1 cm);

[0035] Figure 6 The following is a diagram showing the actual effect of ice layer changes during the electrothermal deicing process of the self-sensing deicing film prepared in Example 1 under applied voltage conditions, as well as the corresponding infrared thermal imaging image (the scale in the figure is 1 cm);

[0036] Figure 7 This is a curve showing the temperature change over time of the film with self-sensing deicing properties prepared in Example 1;

[0037] Figure 8 This is a curve showing the change of the resistance of the thin film with self-sensing deicing characteristics prepared in Example 1 over time;

[0038] Figure 9 This is a curve showing the change in resistance over time during the freezing and deicing process of the film with self-sensing deicing properties prepared in Example 1. DETAILED DESCRIPTION

[0039] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the embodiments of the specification.

[0040] In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0041] Secondly, the term "one embodiment" or "embodiment" herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in various places throughout this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive of other embodiments.

[0042] The experimental methods used in the following examples are conventional methods unless otherwise specified. All materials, reagents, methods, and instruments used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art. All solid and liquid reagents used were of analytical grade.

[0043] Example 1

[0044] The method for preparing a film with self-sensing deicing properties in this embodiment is carried out according to the following steps:

[0045] Step 1: Preparation of HCNTs-rGO

[0046] (1) Preparation of Carboxylated Helical Carbon Nanotube Aqueous Solution:

[0047] 0.5 g of HCNTs (purchased from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd.) and 5 mL of 68% concentrated nitric acid were placed in an autoclave and maintained at 160°C in a forced air drying oven for 7 h. After cooling to room temperature, the acidified HCNTs were rinsed with ethanol and deionized water eight times until neutralized. The solution was then diluted with deionized water to a concentration of 1 mg / mL and stored.

[0048] (2) Preparation of graphene oxide aqueous solution:

[0049] Place 13.8 mL of 98% concentrated sulfuric acid and 0.6 g of natural flake graphite powder in a 0°C ice-water bath and stir for 1 hour. Then, add a total of 3.6 g of KMnO4 in 8 batches. After all the KMnO4 is added, continue stirring in the ice-water bath for 3 hours at a stirring speed of 600 r / min. Then, place it in a 40°C constant temperature water bath and mechanically stir for 20 minutes to obtain a reddish-brown viscous liquid. Continue to heat to 80°C, add a total of 42 mL of deionized water in 15 batches, stir for 20 minutes, and then add 36 mL of deionized water. 10 mL of 30% hydrogen peroxide was diluted with 30 mL of deionized water and then added to the above mixture. The solution immediately turned golden yellow. The obtained solution was filtered and washed with 40 mL of 3.7 wt% hydrochloric acid for 12 h. After filtering again, the filter cake was dispersed in deionized water and stirred at a speed of 600 r / min for 12 h. The solution was then centrifuged at 3500 rpm for 40 min to remove unexfoliated graphite. The supernatant was retained and poured into a dialysis bag (molecular weight cutoff of 8000-14000 Da). It was dialyzed for one week to remove residual ions to obtain graphene oxide, which was diluted to 2 mg / mL with deionized water to obtain a graphene oxide aqueous solution.

[0050] (3) Preparation of HCNTs-rGO:

[0051] Take 40 mL of 2 mg / mL graphene oxide aqueous solution and sonicate for 2 hours, mix it with 50 mL of 1 mg / mL acidified spiral carbon nanotube aqueous solution and sonicate for 1.5 hours, then add 80 mL of 10 mg / mL ascorbic acid aqueous solution, and mechanically stir it in a constant temperature water bath at 80°C and 600 r / min for 12 hours. After the reaction, wash it with deionized water to obtain HCNTs-rGO.

[0052] Step 2: Prepare the film substrate

[0053] HCNTs-rGO was mixed with toluene and ultrasonically dispersed for 2 hours. SEBS was then added and ultrasonically dispersed for another 5 hours to obtain an organic suspension. The organic suspension was spin-coated onto a glass slide at a speed of 1500 rpm and heat-treated at 60°C for 5 minutes to obtain a 40 μm-thick film substrate.

[0054] The mass ratio of HCNTs-rGO to SEBS in the organic suspension was 1:4.5, and the volume ratio of SEBS to toluene was 1.5 g:10 mL.

[0055] Step 3: Preparation of self-sensing film with electrical / optical-thermal deicing properties

[0056] (1) Preparation of silver nanowires

[0057] 0.5 g of polyvinyl pyrrolidone was added to 50 mL of ethylene glycol and dissolved under magnetic stirring at 90°C. After dissolution, it was cooled to room temperature for use; 0.33 g of silver nitrate (AgNO3) was weighed and dissolved in 24 mL of ethylene glycol and stirred evenly, 30 mL of polyvinyl pyrrolidone ethylene glycol solution and 4.5 mL of 600 μM FeCl3·6H2O ethylene glycol solution were added and stirred for 1.5 h. The mixture was reacted in a 130°C forced air oven for 6 h. Finally, the product was centrifuged and washed four times with anhydrous ethanol at a centrifugal speed of 4000 r / min to obtain silver nanowires.

[0058] (2) Preparation of long-chain alkane-grafted composite dimensional silver

[0059] Silver microsheets, silver nanowires and ethanol were mixed in a mass-to-volume ratio of 100 mg:50 mg:100 mL, stirred evenly at room temperature, and then 200 μL of decanethiol was added dropwise. After stirring in the dark for 10 hours, the mixture was centrifuged and washed 5 times with ethanol at a centrifugal speed of 3000 r / min. The centrifuged silver microsheets and silver nanowires were then dispersed in 100 mL of ethanol, 0.8 mL of propylthiol was added, and after stirring in the dark for 3 hours, the mixture was centrifuged and washed 5 times with ethanol at a centrifugal speed of 4500 r / min to obtain long-chain alkane-grafted composite dimensional silver.

[0060] (3) Preparation of self-sensing films with electrical / optical-thermal deicing properties

[0061] The long-chain alkane-grafted composite silver was mixed with toluene and ultrasonically dispersed for 1 hour. SEBS was then added and stirred at 300 rpm for 10 hours. The mixture was then screen-printed onto a HCNTs-rGO / SEBS film. The mass ratio of the long-chain alkane-grafted composite silver, SEBS, and toluene was 0.5:0.03:0.3. The screen mesh size was 400 mesh, resulting in a film with self-sensing deicing properties.

[0062] The microstructure and performance of the obtained self-sensing deicing film were characterized. The specific test process and results are described as follows:

[0063] (1) The surface morphology of the self-sensing deicing film was characterized using a laser confocal microscope. The results are as follows: Figure 1 and Figure 2 As shown by Figure 1 It can be seen that the surface of the self-sensing deicing film obtained by screen printing forms an ordered micro-cone structure with a roughness of 3.840μm, which is nearly double the roughness of the HCNTs-rGO / SEBS film matrix (roughness value of 1.755μm) whose middle part is not printed. Figure 3 As shown by Figure 3It can be seen that the surface of the film has a micro-nano hierarchical structure, which is consistent with the characterization results of laser confocal microscopy.

[0064] (2) The contact angle between the surface of the film with self-sensing deicing properties prepared in Example 1 and water is as follows: Figure 4 As shown by Figure 4 It can be seen that the film has superhydrophobicity, which is mainly due to the long-chain alkane grafted silver nanowires and silver microsheets, which reduce the surface energy of the film and construct a micro-nano hierarchical structure on the surface of the film, thereby achieving superhydrophobicity on the surface of the film.

[0065] (3) The film prepared in Example 1 was subjected to a deicing experiment. Specifically, a 2 mm ice layer was frozen on the surface of a 4 cm × 5 cm film. The film was placed on a cold plate at -30 ° C and a relative humidity of 60 ± 5%. -2 After irradiation with strong light for 6 minutes, the film can completely melt the surface ice layer and remove it, and the surface temperature will eventually rise to 35-45℃. Figure 5 This is mainly due to the constructed spiral carbon nanotube-graphene three-dimensional structure, which reduces the restacking of graphene layers and the agglomeration of carbon nanotubes, forming a heat conduction network, while enhancing the ability to absorb sunlight, improving the efficiency of photothermal conversion, and rapidly heating the film surface, shortening the de-icing time.

[0066] (4) The film prepared in Example 1 was subjected to a deicing experiment. Specifically, a 3 mm ice layer was frozen on the surface of a 4 cm × 4 cm film. A low voltage of 6 V was applied in an environment of -30°C cold plate and 60±5% relative humidity. The bottom of the ice layer melted and slid off the film surface within 3 minutes. The final temperature of the film surface was 25-35°C. Figure 6 It is further shown that the addition of composite dimensional silver reduces the film resistance, increases the heating power, and exhibits excellent electrothermal deicing performance as a whole.

[0067] (5) The film prepared in Example 1 was placed on a cold plate. The temperature of the cold plate was cooled from 22°C to -30°C. After stabilization for a period of time, the temperature returned to 22°C. Under a relative humidity of 60±5%, the temperature and resistance of the film changed with time as shown in the following curves: Figure 7 and 8 As shown. Figure 7 and 8 As can be seen, the film resistance decreases rapidly as the temperature decreases. When the film returns to 22°C, the film resistance returns to its original value. This indicates that the film resistance is highly sensitive to temperature. This change indicates that the film can detect temperature changes in an icing environment.

[0068] (6) The film prepared in Example 1 was subjected to icing and deicing experiments. Specifically, the film was placed on a -30°C cold plate, 0.5 mL of water was added to the film, and the resistance curve of the film during the icing and deicing process was tested. The results are as follows: Figure 9 As shown. Figure 9 It can be seen that when 0.5mL of water is added to the film, the water temperature (22°C) is higher than the film temperature (-30°C), the heat in the water is transferred to the film, the film temperature rises, and the resistance of this process increases. When the water is completely frozen into ice, the film temperature returns to -30°C, and the resistance gradually decreases to the initial value. When a 10V DC voltage is applied, the film temperature rises rapidly, the bottom of the ice layer melts, and slides off the surface of the film. Turn off the power immediately, and the temperature of the film drops to -30°C under the action of the cold plate, and the resistance returns to its original value. It can be seen that the film provided in this application can sense the icing and deicing process based on this change, and by integrating active (electrothermal, photothermal) and passive (superhydrophobic) anti-icing / deicing, it is conducive to achieving an integrated solution for the entire process from early warning, control, and deicing.

[0069] Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the definition of the claims.

Claims

1. A method for preparing a film with self-sensing deicing properties, characterized in that: include: (1) Mixing graphene oxide aqueous solution and carboxylated helical carbon nanotube aqueous solution, adding reducing agent, reacting in a water bath, and washing with deionized water after the reaction to obtain HCNTs-rGO; (2) Mix HCNTs-rGO with toluene, disperse by ultrasonication, add SEBS, and continue ultrasonic dispersion to obtain an organic suspension; (3) The organic suspension was coated on a glass slide by spin coating and heat treated to obtain a HCNTs-rGO / SEBS film; (4) The long-chain alkane-grafted composite dimensional silver was mixed with toluene, ultrasonically dispersed, added with SEBS, stirred evenly, and then coated on the HCNTs-rGO / SEBS film by screen printing technology to obtain a film with self-sensing deicing properties; The preparation method of the composite dimensional silver grafted with medium- and long-chain alkanes in (4) is as follows: silver microsheets and silver nanowires are mixed with ethanol, stirred evenly, and then decanethiol is added dropwise. After stirring in the dark, the mixture is washed by centrifugation with ethanol. Then, the washed product is dispersed in ethanol, propanethiol is added, stirred in the dark, and washed by centrifugation with ethanol to obtain the composite dimensional silver grafted with long-chain alkanes.

2. The preparation method according to claim 1, characterized in that (1) The preparation method of carboxylated helical carbon nanotubes is as follows: helical carbon nanotubes and concentrated nitric acid are placed in a high-pressure reactor, kept at a constant temperature of 160°C in a forced air drying oven for 6 to 8 hours, cooled to room temperature, and then rinsed with ethanol and deionized water until neutral, thereby obtaining carboxylated helical carbon nanotubes.

3. The preparation method according to claim 1, characterized in that (1) The reducing agent is an aqueous solution of ascorbic acid.

4. The preparation method according to claim 1, characterized in that (1) The reaction temperature in the water bath is 80-85°C and the reaction time is 8-12 hours.

5. The preparation method according to claim 1, characterized in that (2) In the obtained organic suspension, the mass ratio of HCNTs-rGO to HCNTs-rGO and SEBS is 1:(3-5), and the volume ratio of SEBS mass to toluene is 1 g:(5-20) mL.

6. The preparation method according to claim 1, characterized in that (3) The medium heat treatment temperature is 50-60℃ and the time is 5-10 minutes.

7. The preparation method according to claim 1, characterized in that The mass-to-volume ratio of silver microsheets, silver nanowires, decanethiol, and propanethiol is 100 mg: (50-150) mg: (200-330) μL: (0.8-1.32) mL.

8. The preparation method according to claim 1, characterized in that (4) The mass ratio of the composite dimensional silver grafted with medium- and long-chain alkanes to SEBS is 0.5:(0.03-0.15).

9. A film with self-sensing deicing properties obtained by the preparation method according to any one of claims 1 to 8.

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