Titanium nitride carbon cloth photo-thermal composite material and preparation method thereof

Abstract

The invention discloses a preparation method of a titanium nitride carbon cloth photo-thermal composite material, and belongs to the technical field of photo-thermal composite materials. The preparation method comprises the following steps: S1, activating carbon cloth by adopting an acid oxidation method; s2, immersing the activated carbon cloth in a TiN-sodium alginate suspension for immersion treatment; and S3, immersing the carbon cloth subjected to immersion treatment in a calcium chloride solution for a cross-linking reaction, and then cleaning and drying to obtain the titanium nitride carbon cloth photo-thermal composite material. According to the preparation method of the titanium nitride carbon cloth photo-thermal composite material, a complete synergistic system which is efficient in photo-thermal conversion, stable in structure maintenance, uniform in heat transfer and adaptive to matrix application is formed, meanwhile, multiple pain points of an existing material are solved, the actual requirements of photo-thermal ice prevention and removal are met, and the application prospect is wide. The method has a key supporting effect on promoting industrialization of the technology, guaranteeing safe operation of low-temperature equipment and assisting carbon neutralization.

Description

A titanium nitride carbon cloth photothermal composite material and its preparation method Technical Field

[0001] This invention relates to the field of photothermal composite materials technology, and in particular to a titanium nitride carbon cloth photothermal composite material and its preparation method. Background Technology

[0002] Against the backdrop of global efforts to achieve carbon neutrality and energy structure transformation, photothermal composite materials have become a research hotspot in the materials field due to their ability to efficiently convert light energy (especially solar energy) into heat energy, and their advantages such as being clean, renewable, and producing no pollutants. They hold immense application potential in areas such as solar energy utilization, precision medicine, and low-temperature de-icing. Among these, the demand for solar-thermal de-icing is particularly urgent. In cold environments, power transmission lines, aircraft, and photovoltaic modules are prone to snow and ice accumulation, leading to equipment malfunctions and safety hazards. Traditional methods such as mechanical de-icing, electric heating de-icing, and chemical de-icing agents suffer from high energy consumption, complex operation, equipment or environmental pollution, and low de-icing efficiency, making it difficult to meet the demands for green and efficient solutions.

[0003] Photothermal conversion-based de-icing technology integrates photothermal composite materials onto the substrate surface, utilizing sunlight to achieve photothermal melting without additional energy consumption, making it an ideal alternative. However, current photothermal composite materials (such as single carbon-based materials, metal nanoparticles, and semiconductor materials) face a key bottleneck: under real sunlight intensity (often below 1000 W / m²), they cannot withstand harsh conditions. 2 Inadequate heat generation in low-temperature environments hinders rapid heat production to address rapid icing. Furthermore, some materials suffer from poor stability, weak bonding with the matrix, and high cost, limiting large-scale application. Therefore, developing photothermal composite materials with high photothermal conversion efficiency, excellent stability, strong adaptability, and feasible preparation to meet the practical needs of photothermal anti-icing is of great significance for promoting the industrialization of this technology, ensuring the safe operation of low-temperature equipment, and contributing to carbon neutrality. Summary of the Invention

[0004] This invention discloses a titanium nitride carbon cloth photothermal composite material and its preparation method, in order to solve the above-mentioned technical problems existing in related technologies.

[0005] To solve the above problems, the present invention adopts the following technical solution: In a first aspect, this application provides a method for preparing titanium nitride carbon cloth photothermal composite material, comprising the following steps: S1, activating carbon cloth by acid oxidation, and then immersing the activated carbon cloth in TiN-sodium alginate suspension for impregnation treatment; S2, immersing the impregnated carbon cloth in calcium chloride solution for crosslinking reaction, and then obtaining titanium nitride carbon cloth photothermal composite material after cleaning and drying.

[0006] Secondly, this application provides a titanium nitride carbon cloth photothermal composite material prepared by the above-mentioned preparation method.

[0007] The technical solution adopted in this invention can achieve the following beneficial effects: The preparation method of the titanium nitride carbon cloth photothermal composite material provided in this application, from light absorption to heat utilization, from structural stability to interface bonding, each component and each step supports and enhances each other. It is not an improvement of a single link, but forms a complete synergistic system of efficient photothermal conversion, stable structure maintenance, uniform heat transfer and adaptability to matrix application. At the same time, it solves the multiple pain points of existing photothermal materials, meets the actual needs of photothermal anti-icing, and plays a key supporting role in promoting the industrialization of this technology, ensuring the safe operation of low temperature equipment and helping "carbon neutrality". The specific advantages are reflected in: (1) This application constructs an efficient photothermal absorption system through the synergistic effect of TiN and carbon cloth. On the one hand, TiN nanoparticles can cover a wide spectral range from visible light to near-infrared light by means of local surface plasmon resonance effect and interband absorption characteristics, expanding the solar energy absorption range from the source; on the other hand, the porous structure of carbon cloth can extend the propagation path of light inside the material, increase the number of light scattering and reflection, and with its own high extinction coefficient, greatly reduce light energy escape. The porous structure of carbon cloth provides a uniformly dispersed carrier for TiN nanoparticles, avoiding the decrease in absorption efficiency caused by TiN agglomeration. At the same time, the broad-spectrum absorption characteristics of TiN fill the absorption gap of single carbon cloth in a specific spectral range, forming a synergistic effect of "broad-spectrum absorption-efficient capture", which significantly improves the total amount of light energy absorbed, fundamentally breaking through the bottleneck of photothermal conversion efficiency of existing materials and providing a sufficient thermal energy basis for rapid ice melting.

[0008] (2) This application constructs a stable structure through a three-step synergistic process. First, after the carbon cloth is activated by acid oxidation, a large number of active groups (such as hydroxyl and carboxyl groups) are generated on the surface, which greatly enhances the interaction ability with the TiN-sodium alginate suspension, laying the foundation for subsequent loading. Second, sodium alginate acts as a binder, which can encapsulate TiN nanoparticles and attach them to the surface and pores of the carbon cloth, thus initially fixing TiN. Finally, the cross-linking reaction of calcium chloride causes sodium alginate to form a three-dimensional gel network, realizing the cross-linking of the polymer network. The following reaction is observed: 2-COO-(sodium alginate) + Ca 2+ →-COO-Ca-OOC-(crosslinked gel). This allows TiN nanoparticles to be firmly locked within the carbon cloth structure, while simultaneously enhancing the bonding strength between sodium alginate and the active groups of the carbon cloth. In this process, the activation of the carbon cloth enhances interfacial bonding, the loading of sodium alginate achieves particle dispersion, and the crosslinking of calcium chloride strengthens structural fixation. These three elements synergistically form a stable "anchoring-encapsulation-locking" system, preventing TiN particles from detaching or agglomerating during long-term use. Furthermore, the excellent chemical stability of the carbon cloth resists corrosion from light, low temperatures, and humid environments, significantly extending the material's lifespan and solving the stability challenges in large-scale applications.

[0009] (3) This application solves the problem of performance degradation caused by local overheating by the synergistic heat transfer of TiN and carbon fiber. TiN nanoparticles will generate heat locally after absorbing light energy. If the heat cannot be diffused in time, it will easily lead to excessive local temperature and damage the material structure. Carbon fiber has high thermal conductivity and can quickly conduct the local heat generated by TiN to the entire carbon cloth surface. The synergistic effect of the two is reflected in: TiN is uniformly dispersed in the porous structure of carbon cloth, ensuring uniform distribution of heat generation points and providing a prerequisite for efficient heat transfer; carbon fiber acts as a "heat conduction channel", which quickly integrates and uniformly diffuses the dispersed local heat, forming a synergistic effect of "uniform heat generation - rapid heat conduction", which not only avoids performance degradation caused by local overheating, but also achieves rapid overall heating of the material, improves the de-icing efficiency, solves the contradiction of "local overheating and incomplete overall de-icing", and adapts to the actual needs of photothermal de-icing scenarios.

[0010] (4) This application improves the practicality of the material through interface synergistic optimization. After acid oxidation activation, the surface hydrophilicity of the carbon cloth is enhanced, allowing it to be more fully immersed in the TiN-sodium alginate suspension, enabling TiN and sodium alginate to penetrate deep into the pores of the carbon cloth and form an "embedded" bond. The subsequent calcium chloride crosslinking reaction not only fixes TiN but also further strengthens the chemical bonding between sodium alginate and the active groups of the carbon cloth, reducing the loss of charge and energy transfer at the interface and improving the overall photothermal conversion efficiency. At the same time, the carbon cloth itself has good flexibility and cutability, and can be fitted to the surface of substrates of different shapes such as power transmission lines and photovoltaic modules. The "activation-impregnation-crosslinking" process allows the composite material to maintain the flexible characteristics of the carbon cloth. The interface modification of the carbon cloth improves the bonding strength, the sodium alginate crosslinking optimizes the interface transfer, and the flexibility of the carbon cloth ensures the adaptability. The three work together to achieve the effect of "strong bonding-low loss-high adaptability", solving the problems of easy material detachment and difficulty in adaptation, and laying the foundation for large-scale promotion. Attached Figure Description

[0011] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0012] Figure 1 is a photothermal temperature rise curve of the carbon cloth in Example 1 of this application; Figure 2 is a photothermal temperature rise curve of the activated carbon cloth obtained after step S1 treatment in Example 1 of this application; Figure 3 is a photothermal temperature rise curve of the impregnated carbon cloth obtained after step S2 treatment in Example 1 of this application; Figure 4 is a photothermal temperature rise curve of the titanium nitride carbon cloth photothermal composite material obtained in Example 1 of this application; Figure 5 is an infrared thermogram of the surface of the titanium nitride carbon cloth photothermal composite material obtained in Example 1 of this application under light irradiation; Figure 6 is a photothermal temperature rise curve of the titanium nitride carbon cloth photothermal composite material obtained in Example 2 of this application; Figure 7 is a photothermal temperature rise curve of the titanium nitride carbon cloth photothermal composite material obtained in Example 3 of this application; Figure 8 is a photothermal temperature rise curve of the titanium nitride carbon cloth photothermal composite material obtained in Comparative Example 1 of this application; Figure 9 is a photothermal temperature rise curve of the titanium nitride carbon cloth photothermal composite material obtained in Comparative Example 2 of this application. The obtained photothermal temperature rise curves of the titanium nitride carbon cloth photothermal composite material are shown in Figure 10; Figure 11 is a comparison of the photothermal temperature rise curves of the titanium nitride carbon cloth photothermal composite material in Examples 1-3 and Comparative Examples 1-3 of this application; Figure 12 is a photothermal temperature rise curve of the TiN sheet in Comparative Example 4 of this application; Figure 13 is a photothermal temperature rise curve of the TiN mixed particle coating obtained in Comparative Example 5 of this application; Figure 14 is a photothermal temperature rise curve of the hollow TiN coating obtained in Comparative Example 6 of this application; Figures 15(a) and 15(b) are both scanning electron microscope (SEM) images of the hollow TiN powder prepared in Comparative Example 6; Figures 16(a) and 16(b) are both transmission electron microscope (TEM) images of the hollow TiN powder prepared in Comparative Example 6. Detailed Implementation

[0013] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be described in detail below. Obviously, the described embodiments are merely some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other implementation methods obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0014] The following description, in conjunction with Figures 1-16, details a titanium nitride carbon cloth photothermal composite material and its preparation method provided in this application through specific embodiments and application scenarios.

[0015] This application provides a method for preparing a titanium nitride carbon cloth photothermal composite material, comprising the following steps: S1, activating the carbon cloth using an acid oxidation method; S2, immersing the activated carbon cloth in a TiN-sodium alginate suspension for impregnation treatment; S3, immersing the impregnated carbon cloth in a calcium chloride solution for crosslinking reaction, and then obtaining the titanium nitride carbon cloth photothermal composite material after cleaning and drying.

[0016] Furthermore, in step S2, the TiN-sodium alginate suspension contains: 0.01 g / ml-0.04 g / ml sodium alginate, 0.003 g / ml-0.01 g / ml TiN powder, and 0.5%-5% glycerol by volume. Understandably, a sodium alginate concentration of 0.01 g / ml to 0.04 g / ml ensures sufficient viscosity in the suspension, guaranteeing uniform dispersion of TiN powder and stable adhesion to the substrate (such as activated carbon cloth) during coating. This avoids excessively thick coatings and cracking after drying due to excessive concentration, or TiN particle settling and easy coating detachment due to insufficient concentration. Matching the TiN powder concentration with sodium alginate ensures the core functions (TiN as the functional component) are maintained while preventing uneven dispersion and agglomeration due to excessive TiN, or performance degradation due to insufficient TiN. The glycerol in the TiN-sodium alginate suspension has plasticizing and moisturizing effects. A low volume fraction of glycerol improves the film-forming toughness of sodium alginate, reduces shrinkage and cracking during coating drying, and delays excessive evaporation of moisture after coating and before crosslinking, providing a stable humid environment for subsequent crosslinking reactions and ensuring uniform crosslinking.

[0017] Furthermore, in step S2, a TiN-sodium alginate suspension is prepared using TiN powder, wherein the particle size of the TiN powder is 15nm-120nm.

[0018] Furthermore, in step S2, the TiN powder used to prepare the TiN-sodium alginate suspension has a particle size of 20nm-100nm.

[0019] Furthermore, in step S2, the TiN-sodium alginate suspension contains: 0.02 g / ml-0.03 g / ml sodium alginate, 0.004 g / ml-0.006 g / ml TiN powder, and 0.8%-1.5% glycerol by volume.

[0020] Furthermore, in step S2, the preparation method of the TiN-sodium alginate suspension is as follows: sodium alginate is added to deionized water, stirred continuously and heated to 55℃-65℃, and then maintained at 55℃-65℃ for 25min-35min; stirring is continued for 11-13h until the solution becomes transparent, thus obtaining a sodium alginate solution; glycerol and TiN powder are added to the sodium alginate solution, and ultrasonically dispersed for 25min-35min to obtain a uniform TiN-sodium alginate suspension.

[0021] Furthermore, in step S2, the carbon cloth is immersed in the TiN-sodium alginate suspension for 8-15 minutes.

[0022] Furthermore, step S2 also includes: after the carbon cloth is removed from the TiN-sodium alginate suspension, the TiN-sodium alginate suspension on the surface of the carbon cloth is scraped off.

[0023] Furthermore, in step S1, the activation treatment includes the following sub-steps: S11, immersing the carbon cloth in acetone for ultrasonic cleaning, then washing with water and drying; S12, immersing the carbon cloth in anhydrous ethanol for ultrasonic cleaning, then washing with water and drying; S13, immersing the carbon cloth in an acid pickling solution for ultrasonic acid pickling, then washing with water; S14, immersing the carbon cloth in concentrated nitric acid for ultrasonic oxidation, then quenching with ice water, washing with water, and drying to obtain the activated carbon cloth. It is understood that this application treats the carbon cloth through an acid oxidation activation process of "acetone-anhydrous ethanol ultrasonic cleaning → acid pickling → concentrated nitric acid oxidation → ice water quenching," which can achieve synergistic technical effects in three aspects: "surface cleanliness, microstructure modification, and surface activity enhancement," laying a key foundation for the subsequent coating and functional performance of TiN-sodium alginate suspension. First, ultrasonic cleaning with acetone efficiently removes residual oil and organic impurities (such as release agents from the production process and adsorbed contaminants from storage) from the carbon cloth surface. Then, ultrasonic cleaning with anhydrous ethanol further cleans and accelerates surface drying, preventing impurities from forming a barrier layer on the carbon cloth surface. Subsequent acid washing removes inorganic impurities such as metal oxides and inorganic salts from the carbon cloth surface, ensuring surface cleanliness and allowing the TiN-sodium alginate suspension to directly contact the carbon cloth fiber surface, improving coating adhesion stability and preventing coating peeling and cracking caused by impurities. Oxidation with concentrated nitric acid etches the carbon cloth fiber surface, forming numerous micropores and mesopores, significantly increasing the specific surface area of ​​the carbon cloth and enhancing its load-bearing and thermal conductivity. On one hand, it provides more adhesion sites for TiN powder and sodium alginate, increasing the load and dispersion uniformity of the suspension on the carbon cloth surface; on the other hand, the porous structure optimizes the heat conduction path, allowing the heat energy generated by subsequent photothermal conversion to be rapidly transferred through the porous network of the carbon cloth, reducing localized heat accumulation and improving overall thermal utilization efficiency. In addition, concentrated nitric acid oxidation can introduce a large number of oxygen-containing active functional groups (such as carboxyl-COOH, hydroxyl-OH, and carbonyl-C=O) onto the surface of carbon cloth. These functional groups can form hydrogen bonds or electrostatic interactions with the hydroxyl and carboxyl groups in sodium alginate molecules, significantly enhancing the interfacial bonding force between the coating and the carbon cloth. At the same time, the active functional groups can improve the hydrophilicity of the carbon cloth surface, making it easier for the TiN-sodium alginate suspension to spread on the carbon cloth surface and avoiding uneven coating with "hydrophobic white areas". Subsequent ice-water quenching can fix the surface structure and functional groups formed by oxidation through rapid cooling, reduce the decomposition and loss of functional groups at high temperatures, ensure stable activation effect, and provide a guarantee for the photothermal conversion and structural stability of the final composite material.

[0024] Further, the specific sub-steps of step S1 are as follows: S11, the carbon cloth is immersed in acetone for ultrasonic cleaning, with an ultrasonic frequency of 30-50kHz, a power of 180-220W, and a time of 15-25min; then rinsed with deionized water 2-4 times; finally dried at a temperature of 55-65℃ for 25-35min; S12, the carbon cloth is immersed in anhydrous ethanol for ultrasonic cleaning, with an ultrasonic frequency of 30-50kHz, a power of 180-220W, and a time of 15-25min; then rinsed with deionized water 2-4 times; finally dried at a temperature of 55-65℃ for 25-35min; S13, the carbon cloth is immersed in an acid pickling solution for ultrasonic acid pickling... The ultrasonic frequency is 30-50kHz, the power is 180-220W, and the time is 15-25min. Then, it is rinsed 2-4 times with deionized water until the washing water is neutral. Finally, it is dried at 55-65℃ for 25-35min. The pickling solution is a 0.5-1.5mol / L HCl solution. S14 carbon cloth is immersed in concentrated nitric acid for ultrasonic oxidation at a frequency of 30-50kHz, a power of 70-90W, and a time of 15-25min. After removal, it is quickly immersed in ice water for quenching for 8-15min. Then, it is repeatedly rinsed with deionized water until the washing water is neutral. Finally, it is dried at 55-65℃ for 11-13h to obtain activated carbon cloth.

[0025] Furthermore, in each sub-step of step S1: when the carbon cloth is immersed in acetone for ultrasonic cleaning, the ultrasonic frequency is 40kHz, the power is 200W, and the time is 20min; when the carbon cloth is immersed in anhydrous ethanol for ultrasonic cleaning, the ultrasonic frequency is 40kHz, the power is 200W, and the time is 20min; when the carbon cloth is immersed in pickling solution for ultrasonic pickling, the ultrasonic frequency is 40kHz, the power is 200W, and the time is 20min; when the carbon cloth is immersed in concentrated nitric acid for ultrasonic oxidation, the ultrasonic frequency is 40kHz, the power is 80W, and the time is 20min.

[0026] Furthermore, in step S3, the calcium chloride solution contains 0.005 g / ml to 0.05 g / ml of calcium chloride.

[0027] Furthermore, in step S3, the drying process sequentially includes: drying at room temperature for 3-5 hours; drying at 35℃-45℃ for 1.5-2.5 hours; and drying at 55℃-65℃ for 3.5-4.5 hours. It is understood that this stepped heating avoids the rapid shrinkage of the material surface and the inability to timely remove internal moisture, which can lead to cracking or damage to the pore structure caused by direct high-temperature drying. First, allowing the material to slowly absorb and balance environmental moisture at room temperature allows for slow evaporation, reducing stress. Then, drying at 35℃-45℃ for surface curing fixes the distribution of TiN-sodium alginate on the carbon cloth surface and in the pores, preventing component displacement during subsequent heating. Finally, drying at 55℃-65℃ for thorough dehydration removes residual moisture from the material, preventing moisture from occupying the pores and affecting light capture or causing structural loosening during long-term use. This also ensures the stability of the porous structure of the carbon cloth and the dispersion state of TiN, guaranteeing the stability of the photothermal composite material. Furthermore, the stepped drying process ensures the consistency of performance testing for samples with different variables, avoids performance deviations caused by uneven drying, and improves the reliability of research results.

[0028] Furthermore, in step S3, the time for immersing the impregnated carbon cloth in the calcium chloride solution for the crosslinking reaction is 4-7 minutes. It is understood that limiting the crosslinking reaction time to 4-7 minutes is a key parameter design to ensure the comprehensive performance of the titanium nitride carbon cloth photothermal composite material. Its core function is to avoid excessive crosslinking by precisely controlling the degree of crosslinking. From the perspective of the reaction mechanism, the cross-linking reaction between calcium chloride and sodium alginate is a process in which calcium ions replace sodium ions on the sodium alginate molecular chain to form a three-dimensional gel network. If the reaction time is too short (less than 4 minutes), the sodium alginate will not be cross-linked sufficiently, the gel network structure will be loose, and it will be unable to firmly lock the TiN nanoparticles, making it easy for TiN to fall off during subsequent use. If the reaction time is too long (more than 7 minutes), it will cause excessive cross-linking, making the gel network density too high and the structure rigid. On the one hand, it will block the porous structure of the carbon cloth, destroy its original porosity advantage for enhancing light capture, resulting in increased light reflectivity and decreased photothermal conversion efficiency, which contradicts the core goal of "improving photothermal conversion efficiency". On the other hand, it will cause the composite material to lose the flexibility of the carbon cloth itself, become brittle and hard, and be difficult to adhere to the non-planar substrate surface such as power transmission lines and photovoltaic modules, reducing the material adaptability and failing to meet the needs of large-scale applications. The cross-linking time range of 4-7 minutes ensures that sodium alginate is fully cross-linked to form a stable gel network, thereby firmly fixing TiN nanoparticles and solving the problems of material stability and bonding force. At the same time, it avoids the damage to the porous structure and flexible properties of carbon cloth caused by excessive cross-linking, ensuring the synergistic effect of "light capture-structural stability-matrix adaptation". This allows the composite material to have high photothermal performance, excellent stability and good practicality, and accurately match the actual application requirements of photothermal anti-icing.

[0029] Furthermore, in step S3, the calcium chloride solution contains 0.008 g / ml to 0.03 g / ml of calcium chloride.

[0030] I. Preparation Example: Carbon cloth ①, woven from fine bundles of 3K carbon yarn from Beijing Graphene Research Institute Co., Ltd., with a thickness of 200g / cm². 2 Plain weave carbon cloth; the carbon cloth is cut into squares with a specification of 5cm×5cm and used in Examples 1-5 below. The photothermal temperature rise curve of carbon cloth ① is shown in Figure 1.

[0031] Carbon cloth ②, woven from fine bundles of 12K carbon yarn from Beijing Graphene Research Institute Co., Ltd., weighing 250g / cm². 2 Plain weave carbon cloth; cut the carbon cloth into squares of 5cm × 5cm for use in Example 7 below.

[0032] Carbon cloth ③, woven from fine bundles of 6K carbon yarn from Beijing Graphene Research Institute Co., Ltd., weighing 300g / cm². 2 Plain weave carbon cloth; cut the carbon cloth into squares of 5cm × 5cm for use in Example 8 below.

[0033] Example 1: A method for preparing a titanium nitride carbon cloth photothermal composite material, comprising the following steps: S1, the carbon cloth is pretreated (activated) by acid oxidation, including the following sub-steps: S11, the carbon cloth (using carbon cloth ①) is immersed in acetone for ultrasonic cleaning at a frequency of 40 kHz, a power of 200 W, and a time of 20 min; then rinsed three times with deionized water, and finally dried at 60 °C for 30 min; S12, the carbon cloth treated in step S11 is immersed in anhydrous ethanol for ultrasonic cleaning at a frequency of 40 kHz, a power of 200 W, and a time of 20 min; then rinsed three times with deionized water, and finally dried at 60 °C for 30 min; S13, the carbon cloth treated in step S12 is immersed in a 1 mol / L HCl solution for ultrasonic acid washing at a frequency of 40 kHz, a power of 200 W, and a time of 20 min; then rinsed three times with deionized water until the pH of the washing water is 7; finally dried at 60 °C for 30 min. Dry at 0℃ for 30 min; S14, Immerse the carbon cloth treated in step S13 in 65% concentrated nitric acid for ultrasonic oxidation at a frequency of 40 kHz, a power of 80 W, and a time of 20 min; after removal, quickly immerse in ice water for 10 min; then rinse repeatedly with deionized water until the pH of the washing water is 7; finally, dry at 60℃ for 12 h to obtain activated carbon cloth (pretreated carbon cloth), whose photothermal temperature rise curve is shown in Figure 2; S2, place the activated carbon cloth in T The process involves impregnation in a TiN-sodium alginate suspension, comprising the following sub-steps: S21, preparing a TiN-sodium alginate suspension: S211, adding 2g of sodium alginate to 100ml of deionized water, stirring continuously and heating to 60℃, then maintaining the temperature at 60℃ for 30min; S212, maintaining stirring for 12h until the solution becomes transparent, thus obtaining a sodium alginate solution; S213, adding 1ml of glycerol and 0.5ml of TiN powder with a particle size of 20nm to the sodium alginate solution.5g of the activated carbon cloth was ultrasonically dispersed at a frequency of 40kHz, a power of 200W, and a time of 30min to obtain a uniform TiN-sodium alginate suspension; S22, the activated carbon cloth obtained in step S11 was immersed in the TiN-sodium alginate suspension prepared in step S21 for 10min; then the carbon cloth was slowly removed from the TiN-sodium alginate suspension, and excess TiN-sodium alginate suspension was gently scraped off the surface of the carbon cloth with tweezers to obtain the impregnated carbon cloth (pretreated carbon cloth + sodium alginate), and its photothermal temperature rise curve is shown in Figure 3; S3, the impregnated carbon cloth was immersed in calcium chloride solution for crosslinking reaction, and then washed and dried, specifically including The following sub-steps are performed: S31, Prepare a calcium chloride solution by dissolving 1g of CaCl2 in 100mL of deionized water and stirring until dissolved to obtain a calcium chloride solution; S32, Immerse the carbon cloth treated in step S2 into the calcium chloride solution obtained in step S31 for a crosslinking reaction for 5 minutes; After the crosslinking reaction, rinse with deionized water; S33, Dry the rinsed carbon cloth by the following steps: drying at room temperature for 4 hours; drying in an oven at 40℃ for 2 hours; drying in a drying oven at 60℃ for 4 hours; Obtain the titanium nitride carbon cloth photothermal composite material, whose photothermal temperature rise curve is shown in Figure 4, and whose surface infrared thermogram is shown in Figure 5.

[0034] Example 2: This example differs from Example 1 in that the particle size of the TiN powder in step S2 is 50 nm; otherwise, it is the same as Example 1, and a titanium nitride carbon cloth photothermal composite material is obtained, the photothermal temperature rise curve of which is shown in Figure 6.

[0035] Example 3: This example differs from Example 1 in that the particle size of the TiN powder in step S2 is 100 nm; the rest is the same as in Example 1, and a titanium nitride carbon cloth photothermal composite material is obtained, the photothermal temperature rise curve of which is shown in Figure 7.

[0036] Example 4: A method for preparing a titanium nitride carbon cloth photothermal composite material, comprising the following steps: S1, firstly, the carbon cloth is activated by acid oxidation, including the following sub-steps: S11, the carbon cloth (the carbon cloth used is carbon cloth ①) is immersed in acetone for ultrasonic cleaning at a frequency of 50 kHz, a power of 180 W, and a time of 25 min; then rinsed 4 times with deionized water, and finally dried at a temperature of 65℃ for 25 min; S12, the carbon cloth treated in step S11 is immersed in anhydrous ethanol for ultrasonic cleaning at a frequency of 50 kHz, a power of 180 W, and a time of 25 min; then rinsed 4 times with deionized water, and finally dried at a temperature of 65℃ for 25 min; S13, the carbon cloth treated in step S12 is immersed in 0.The carbon cloth was subjected to ultrasonic acid washing in a 5 mol / L HCl solution at a frequency of 50 kHz, a power of 180 W, and a time of 25 min. It was then rinsed 2-4 times with deionized water until the pH of the washing water reached 7. Finally, it was dried at 65℃ for 25 min. S14: The carbon cloth treated in step S13 was immersed in 65% concentrated nitric acid for ultrasonic oxidation at a frequency of 50 kHz, a power of 70 W, and a time of 25 min. After removal, it was quickly quenched in ice water for 15 min. It was then repeatedly rinsed with deionized water until the pH of the washing water reached 7. Finally, it was dried at 65℃ for 11 h to obtain... S2. The activated carbon cloth is impregnated in a TiN-sodium alginate suspension, including the following sub-steps: S21. Preparation of TiN-sodium alginate suspension: S211. 4g of sodium alginate is added to 100ml of deionized water, stirred continuously and heated to 55℃, and then kept at 55℃ for 35min; S212. Stirring is maintained for 13h, and the solution becomes transparent, obtaining a sodium alginate solution; S213. 4ml of glycerol and 1g of TiN powder with a particle size of 120nm are added to the sodium alginate solution, and ultrasonic dispersion is performed. A uniform TiN-sodium alginate suspension was obtained at a frequency of 40kHz, a power of 200W, and a time of 35min; S22, the activated carbon cloth obtained in step S11 was immersed in the TiN-sodium alginate suspension prepared in step S21 for 8min; then the carbon cloth was removed from the TiN-sodium alginate suspension, and excess TiN-sodium alginate suspension was gently scraped off the surface of the carbon cloth with tweezers to obtain the impregnated carbon cloth; S3, the impregnated carbon cloth was immersed in calcium chloride solution for crosslinking reaction, and then washed and dried, specifically including the following sub-steps: S31 1. Prepare a calcium chloride solution by dissolving 5g of CaCl2 in 100mL of deionized water and stirring until dissolved. 2. Immerse the carbon cloth treated in step S2 into the calcium chloride solution obtained in step S31 for a crosslinking reaction for 4 minutes. After the crosslinking reaction, rinse with deionized water. 3. Dry the rinsed carbon cloth by the following steps: drying at room temperature for 3 hours; drying in an oven at 45℃ for 1.5 hours; and drying in a drying oven at 65℃ for 3.5 hours. This yields a titanium nitride carbon cloth photothermal composite material.

[0037] Example 5: A method for preparing a titanium nitride carbon cloth photothermal composite material, comprising the following steps: S1, firstly, the carbon cloth is activated by acid oxidation, including the following sub-steps: S11, the carbon cloth (the carbon cloth used is carbon cloth ①) is immersed in acetone for ultrasonic cleaning at a frequency of 30kHz, a power of 220W, and a time of 15min; then rinsed twice with deionized water, and finally dried at a temperature of 55℃ for 35min; S12, the carbon cloth treated in step S11 is immersed in anhydrous ethanol for ultrasonic cleaning at a frequency of 30kHz, a power of 220W, and a time of 15min; then rinsed twice with deionized water, and finally dried at a temperature of 55℃ for 35min; S12. Dry at 55℃ for 35 min; S13. Immerse the carbon cloth treated in step S12 in 0.5 mol / L HCl solution for ultrasonic acid washing at a frequency of 30 kHz, a power of 220 W, and a time of 25 min; then rinse with deionized water until the pH of the washing water is 7; finally, dry at 55℃ for 35 min; S14. Immerse the carbon cloth treated in step S13 in 65% concentrated nitric acid for ultrasonic oxidation at a frequency of 30 kHz, a power of 90 W, and a time of 15 min; after removal, quickly immerse in ice water for quenching for 8 min; then rinse repeatedly with deionized water until the pH of the washing water is 7; finally... After drying at 55℃ for 13 hours, activated carbon cloth was obtained; S2, the activated carbon cloth was impregnated in a TiN-sodium alginate suspension, including the following sub-steps; S21, preparation of TiN-sodium alginate suspension: S211, 1g of sodium alginate was added to 100ml of deionized water, stirred continuously and heated to 55℃, and then kept at 55℃ for 35min; S212, the stirring was maintained for 11 hours, and the solution became transparent, obtaining a sodium alginate solution; S213, 0.5ml of glycerol and 0.3g of TiN powder with a particle size of 15nm were added to the sodium alginate solution, and ultrasonic dispersion was performed. The ultrasonic frequency was 50 kHz, the power was 180 W, and the time was 35 min to obtain a uniform TiN-sodium alginate suspension; S22, the activated carbon cloth obtained in step S11 was immersed in the TiN-sodium alginate suspension prepared in step S21 and the immersion treatment was 15 min; then the carbon cloth was taken out of the TiN-sodium alginate suspension and the excess TiN-sodium alginate suspension on the surface of the carbon cloth was gently scraped off with tweezers to obtain the impregnated carbon cloth; S3, the impregnated carbon cloth was immersed in calcium chloride solution for crosslinking reaction, and then washed and dried, specifically including the following sub-steps: S31, prepare calcium chloride solution, and add 0.5g of CaCl2 was dissolved in 100mL of deionized water and stirred to obtain a calcium chloride solution; S32, the carbon cloth treated in step S2 was immersed in the calcium chloride solution obtained in step S31 for a crosslinking reaction for 7 minutes; after the crosslinking reaction, it was rinsed with deionized water; S33, the rinsed carbon cloth was dried, including: drying at room temperature for 5 hours; drying in an oven at 35℃ for 2.5 hours; and drying in a drying oven at 55℃ for 4.5 hours; thus obtaining a titanium nitride carbon cloth photothermal composite material.

[0038] Example 6: This example differs from Example 1 in that the carbon cloth used is carbon cloth ②; otherwise, it is the same as Example 1, and a titanium nitride carbon cloth photothermal composite material is obtained.

[0039] Example 7: This example differs from Example 1 in that the carbon cloth used is carbon cloth ③; otherwise, it is the same as Example 1, and a titanium nitride carbon cloth photothermal composite material is obtained.

[0040] II. Comparative Example 1: This comparative example differs from Example 1 in that: in step S3, steps S31 and S32 are omitted, and the carbon cloth treated in step S2 is rinsed with deionized water and then proceeded to step S33; otherwise, it is the same as Example 1, and a titanium nitride carbon cloth photothermal composite material is obtained, the photothermal temperature rise curve of which is shown in Figure 8.

[0041] Comparative Example 2: This comparative example differs from Example 2 in that: in step S3, steps S31 and S32 are omitted, the carbon cloth treated in step S2 is rinsed with deionized water, and then proceeds to step S33; otherwise, it is the same as Example 2, and a titanium nitride carbon cloth photothermal composite material is obtained, the photothermal temperature rise curve of which is shown in Figure 9.

[0042] Comparative Example 3: This comparative example differs from Example 3 in that: in step S3, steps S31 and S32 are omitted, the carbon cloth treated in step S2 is rinsed with deionized water, and then proceeds to step S33; otherwise, it is the same as Example 3, and a titanium nitride carbon cloth photothermal composite material is obtained, the photothermal temperature rise curve of which is shown in Figure 10.

[0043] Comparative Example 4: The photothermal temperature rise curve of the TiN wafer produced by Fuzhou Kunpeng Optoelectronic Technology Co., Ltd. is shown in Figure 12.

[0044] Comparative Example 5: A TiN mixed particle coating was prepared using TiN nanoparticles with particle sizes of 5μm, 50nm, and 500nm produced by Zhejiang Manli Nanotechnology Co., Ltd.: 20g each of 5μm, 50nm, and 500nm TiN nanoparticles were weighed and added to 300g of an ethanol-water mixed solvent (volume ratio 1:1) containing 0.8% by mass of trisodium citrate dispersant. The mixture was ultrasonically dispersed for 30min to obtain a suspension. Aqueous polyurethane binder was added to adjust the slurry solid content to 25% (by mass), and the mixture was mechanically stirred for 15min.

[0045] The substrate was ultrasonically cleaned with acetone and ethanol and dried at 80°C. The spray gun pressure was 0.3MPa and the gun distance was 18cm. Six thin layers were sprayed, each layer was pre-dried at 80°C for 10min, and finally cured at 110°C for 60min to obtain a TiN coating with a thickness of 30μm. Its photothermal temperature rise curve is shown in Figure 13.

[0046] Comparative Example 6: Preparation of hollow TiN. The preparation method includes the following steps: Step A1: 200 mg PS microspheres and 200 mg carbon spheres are dispersed in 20 mL of aqueous solution containing 2 mL HCl, and ultrasonically treated for 10 min to improve surface hydrophilicity. Then, 200 mg CTAB is added and magnetically stirred for 10 min to obtain a dispersion.

[0047] Step A2: Dissolve another 2 mL of TBOT in 10 mL of anhydrous ethanol to prepare a precursor solution. Add the precursor solution dropwise to the above dispersion while stirring continuously. Continue stirring for 20 min to obtain a suspension.

[0048] Step A3: Transfer the obtained suspension to a 100 mL polytetrafluoroethylene-lined stainless steel high-pressure reactor, add deionized water to dilute to about 80 mL, and carry out a hydrothermal reaction at 180 °C for 12 h; after the reaction, centrifuge the product, wash it with deionized water and ethanol in sequence, and dry it at 60 °C for 12 h; finally, calcine the dried powder in air at 500 °C for 2 h to remove the carbon template and crystallize the oxide shell to obtain hollow shell TiO2.

[0049] Step A4: The prepared hollow TiO2 sample was placed in a tube furnace and nitrided under a flowing ammonia atmosphere: the temperature was increased to 900℃ at a rate of 5℃ / min and held for 2h. During this process, the hollow TiO2 was completely converted into hollow TiN powder through anion exchange mechanism. The scanning electron microscope (SEM) images of the hollow TiN powder are shown in Figure 15(a) and Figure 15(b); the transmission electron microscope (TEM) images of the hollow TiN powder are shown in Figure 16(a) and Figure 16(b).

[0050] Hollow TiN coating was prepared using hollow TiN powder: 60g of hollow TiN powder was weighed and 300g of ethanol solvent containing 0.8% by mass of nonionic surfactant was added. The mixture was ultrasonically dispersed for 40min to form a suspension. Epoxy acrylate binder was added to adjust the slurry viscosity to 200mPa·s and stirred evenly.

[0051] Similar to Comparative Example 5, the substrate was pretreated; the spray gun pressure was 0.25 MPa, the gun distance was 15 cm, 4 layers were sprayed, each layer was pre-dried at 80℃ for 10 min, and UV cured for 30 s to obtain a TiN coating with a thickness of 30 μm. Its photothermal temperature rise curve is shown in Figure 14.

[0052] III. Experimental Example 1, Photothermal Performance Verification Experiment 1.1 The photothermal conversion capability of the materials in Examples 1-3 and Comparative Examples 1-6 was verified by "photothermal temperature rise curve" and "infrared thermogram". The specific operation steps are as follows: ① Place the experimental sample in a dry environment for equilibration for 24 hours to ensure that there is no residual solvent or impurities on the surface.

[0053] ② Place the sample in an environment free from airflow interference with room temperature (approximately 25℃) and humidity of 50%±5%. Use a BBZM-1 laboratory xenon lamp light source to simulate the AM1.5G solar spectrum (wavelength range 300-2500nm). Place the experimental sample on the sample stage and record the surface temperature by having the thermocouple probe in close contact with the material. Fix the shooting distance of the infrared thermal imager at 30cm. Based on the material characteristics of titanium nitride / carbon cloth, set the emissivity (ε) parameter of the infrared thermal imager to 0.97 and use the infrared thermal imager to measure the instantaneous surface temperature.

[0054] ③ Turn on the light source, a xenon lamp simulating sunlight, with a power density set to 100mW / cm². 2 The sample surface was continuously irradiated for 30 minutes. After the temperature of the experimental sample stabilized, the temperature distribution image of the sample surface was captured by an infrared thermal imager, and the infrared thermogram was recorded. Furthermore, after the light source was turned on, the temperature change over time was recorded until the temperature reached a plateau. Then the light source was turned off, and the natural cooling curve, i.e., the photothermal temperature rise curve, was recorded.

[0055] 1.2 Experimental results are shown in Figures 1-14: Figures 1-4 present the evolution of photothermal performance of carbon cloth-based photothermal composite materials from substrate to final product at each process stage, clearly demonstrating the gradual optimization effect of "pretreatment - sodium alginate loading - TiN composite - calcium crosslinking" on photothermal performance. Comparison of Figure 1 and Figure 2: Figure 1 shows the temperature rise curve of the original carbon cloth ①, and Figure 2 shows the temperature rise curve of the pretreated carbon cloth. Within 300 seconds of illumination, the stable temperature of the original carbon cloth is approximately 65℃, while the stable temperature of the pretreated carbon cloth increases to nearly 70℃. This is because after pretreatment, active groups such as hydroxyl and carboxyl groups are generated on the surface of the carbon cloth. On the one hand, this enhances the hydrophilicity of the substrate, creating conditions for subsequent loading; on the other hand, it increases the surface roughness, expanding the light absorption area, thereby achieving an initial improvement in photothermal performance.

[0056] Comparison of Figure 2 and Figure 3: Figure 3 shows the temperature rise curve of the pretreated carbon cloth loaded with TiN-sodium alginate. Its stable temperature is slightly lower than that in Figure 2 (approximately 55℃), but the fluctuation of the temperature rise curve is reduced and the stability is improved. This is because sodium alginate itself has weaker light absorption capacity than carbon cloth, which affects the short-term temperature rise. However, the surface of the carbon cloth is impregnated with TiN-sodium alginate suspension, forming a composite layer of TiN particles and sodium alginate polymer. Sodium alginate can fill the pores of the carbon cloth, improve the surface uniformity, provide a carrier for the uniform dispersion of TiN particles, and lay a stable foundation for the subsequent calcium crosslinking, demonstrating the preparatory value of the process.

[0057] Comparison of Figures 3 and 4: Figure 4 shows the temperature rise curve of carbon cloth composite with 20nm TiN and the addition of calcium chloride, which significantly improves its photothermal performance. In the experiment simulating AM1.5G solar spectrum (wavelength range 300-2500nm), the stable temperature of the titanium nitride carbon cloth photothermal composite material in Example 1 of this application exceeded 90℃ within 300 seconds of illumination, which can generate heat quickly and can be used to deal with scenarios of rapid freezing. This is about 35℃ higher than that in Figure 3, and the thermal stability during the cooling stage is significantly enhanced. This change is due to two factors: First, the local surface plasmon resonance effect of 20nm TiN nanoparticles covers a wide spectral range, which greatly improves the light energy capture efficiency. Second, calcium chloride promotes the formation of a three-dimensional gel network of sodium alginate, which firmly fixes the TiN particles in the carbon cloth structure, resulting in high stability and preventing particle agglomeration. At the same time, it enhances the interfacial bonding strength, reduces heat transfer loss, and ultimately achieves a synergistic effect of efficient photothermal conversion and stable heat retention.

[0058] In summary, the temperature rise curves in Figures 1 to 4 fully demonstrate the performance progression at each stage, verifying the rationality of the step-by-step optimization and synergistic effect design of the technical solution in this application. Ultimately, through the core process of TiN composite and calcium crosslinking, a significant breakthrough in photothermal performance is achieved.

[0059] Figure 5 shows the surface temperature distribution of the titanium nitride carbon cloth photothermal composite material described in Example 1 under illumination. The temperature in the central region of the material surface reaches 85.4℃, a significant increase compared to the ambient temperature (25.8℃), directly demonstrating that the titanium nitride carbon cloth composite material prepared in this application possesses excellent photothermal conversion capabilities, efficiently converting light energy into heat energy. Furthermore, the temperature distribution exhibits a pattern of "high temperature at the center (titanium nitride coating area) and gradient decay at the edges," indicating that the titanium nitride carbon cloth photothermal composite material in this application achieves directional concentration of photothermal energy, avoiding energy dispersion. This characteristic is suitable for the practical needs of precise local heat generation in scenarios such as photothermal catalysis and photothermal heating. In addition, the high temperature of 85.4℃ at the center proves that TiN can generate heat efficiently, while the edge temperature does not drop sharply to the ambient temperature, demonstrating the high thermal conductivity of carbon fiber, which can quickly conduct the local heat generated by TiN to the entire material, avoiding local overheating and structural damage while achieving uniform overall temperature rise. This uniform temperature distribution fully verifies the synergistic effect of "uniform TiN dispersion (uniform hot spot generation) and high thermal conductivity of carbon fiber (rapid heat diffusion), successfully solving the core contradiction of "local overheating and incomplete overall de-icing", and perfectly adapting to the actual application scenario of photothermal de-icing.

[0060] Figure 11 shows a comparison of the photothermal temperature rise curves of the titanium nitride carbon cloth photothermal composite materials in Examples 1-3 and Comparative Examples 1-3 of the present invention. Curves C-TiO2-20, C-TiO2-50, and C-TiO2-100 represent the photothermal temperature rise curves of the titanium nitride carbon cloth photothermal composite materials in Comparative Examples 1, 2, and 3, respectively. Curves C-TiO2-20-Ca, C-TiO2-50-Ca, and C-TiO2-100-Ca represent the photothermal temperature rise curves of the titanium nitride carbon cloth photothermal composite materials in Examples 1, 2, and 3, respectively. In the figure, "light on" indicates the moment the light source is turned on (corresponding to the start of the photothermal heating stage), and "light off" indicates the moment the light source is turned off (corresponding to the start of the photothermal cooling stage). These curves reflect the heating capacity of each material under illumination and its cooling characteristics after illumination is stopped.

[0061] During the light-induced heating stage, the calcium-crosslinked sample examples (curves C-TiO2-20-Ca, C-TiO2-50-Ca, C-TiO2-100-Ca) showed significantly better heating rates and final stable temperatures than their counterparts without calcium crosslinking (curves C-TiO2-20, C-TiO2-50, C-TiO2-100), with a temperature difference of 15-25°C. The core reason for this performance improvement lies in the ionic crosslinking reaction between calcium ions and sodium alginate, forming a stable three-dimensional gel network that firmly locks the TiN nanoparticles within the porous structure of the carbon cloth, effectively preventing particle aggregation. The uniform dispersion of TiN particles not only expands the effective light absorption area but also enhances the synergistic effect between its broad-spectrum absorption characteristics and the light-harvesting performance of the porous carbon cloth structure, thereby improving the conversion efficiency of light energy to heat energy and achieving a more significant temperature rise.

[0062] During the cooling phase after the light source was turned off, the sample containing calcium crosslinking cooled significantly slower than the comparative sample without calcium crosslinking, and was able to maintain a higher temperature for a longer period of time. This is because the dense gel network formed by calcium crosslinking not only optimizes the structural stability of the material, but also reduces heat loss during conduction; at the same time, the crosslinking effect enhances the interfacial bonding strength between TiN particles and carbon cloth substrate, reducing energy transfer loss at the interface, thus giving the material better thermal stability.

[0063] It is noteworthy that the calcium crosslinking process consistently improves the photothermal properties of the corresponding composite materials, and the performance curves of the examples always maintain the performance advantage over the comparative curves with the same parameters. This result indicates that calcium crosslinking, through its core mechanism of fixing active components and enhancing structural stability, has a universal optimization effect on composite materials of TiN with different particle sizes.

[0064] Figure 12 shows the photothermal temperature rise curve of the TiN wafer produced by Fuzhou Kunpeng Optoelectronic Technology Co., Ltd. in Comparative Example 4. Its temperature rise peak is less than 60℃, and the heating rate is relatively slow within 0-300s. The TiN wafer is a dense bulk material that relies solely on its own light absorption characteristics to achieve conversion. However, the spectral coverage of a single TiN is limited, and there is no carrier to expand the light absorption interface, so the heat accumulation efficiency is naturally limited.

[0065] Figure 13 shows the photothermal temperature rise curve of the TiN mixed particle coating prepared in Comparative Example 5. The peak temperature rise of the multi-particle TiN coating in Comparative Example 5 is only about 45°C, which is much lower than the peak temperature rise of the titanium nitride carbon cloth photothermal composite material in Example 1 of this application (exceeding 90°C). Moreover, the heating process is gradual. The multi-particle TiN coating in Comparative Example 5 lacks a high thermal conductivity carrier and relies solely on light scattering between particles to achieve light absorption. Heat is easily retained inside the particles and is difficult to accumulate quickly. The heat dissipation rate is faster, and the continuous photothermal effect in practical applications will be weaker.

[0066] Figure 14 shows the photothermal temperature rise curve of the TiN coating prepared in Comparative Example 6. The temperature rapidly rises to approximately 40℃ within 0-300s, then gradually decreases and stabilizes after 300s. This curve reflects that the hollow TiN coating possesses basic photothermal response capability, but its performance has significant limitations. From the preparation process perspective, the coating is formed by spraying and curing hollow TiN powder. Theoretically, the hollow structure can increase the light scattering interface, but the actual peak temperature rise is only about 40℃. This is because, on the one hand, the coating relies solely on the light absorption characteristics of the hollow TiN itself, without combining it with a carrier such as carbon cloth to expand the light absorption interface. The spectral coverage of a single TiN is limited, and the particles tend to agglomerate during the spraying process, weakening the light capture efficiency. On the other hand, the coating lacks a high thermal conductivity carrier to transfer heat, making it difficult for the localized heat generated by the hollow TiN to diffuse quickly, resulting in insufficient heat accumulation and a limited peak temperature rise. Meanwhile, the coating only fixes the TiN powder with a binder and does not have a stable structural design similar to calcium chloride crosslinking. During long-term use, the particles are prone to falling off, which further affects the stability of photothermal performance.

[0067] Furthermore, it should be noted that the scope of the methods and apparatus in the embodiments of this application is not limited to performing functions in the order shown or discussed, but may also include performing functions substantially simultaneously or in the reverse order, depending on the functions involved. For example, the described methods may be performed in a different order than described, and various steps may be added, omitted, or combined. In addition, features described with reference to certain examples may be combined in other examples.

[0068] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a titanium nitride carbon cloth photothermal composite material, characterized in that, The process includes the following steps: S1, activating the carbon cloth using an acid oxidation method; S2, immersing the activated carbon cloth in a TiN-sodium alginate suspension for impregnation; S3, immersing the impregnated carbon cloth in a calcium chloride solution for crosslinking reaction, and then cleaning and drying to obtain a titanium nitride carbon cloth photothermal composite material.

2. The method for preparing the titanium nitride carbon cloth photothermal composite material according to claim 1, characterized in that, In step S2, the TiN-sodium alginate suspension contains: 0.01 g / ml-0.04 g / ml sodium alginate, 0.003 g / ml-0.01 g / ml TiN powder, and 0.5%-5% glycerol by volume; and / or, in step S2, the TiN-sodium alginate suspension is prepared using TiN powder, wherein the particle size of the TiN powder is 15 nm-120 nm.

3. The method for preparing the titanium nitride carbon cloth photothermal composite material according to claim 2, characterized in that, In step S2, the TiN-sodium alginate suspension contains: 0.02 g / ml-0.03 g / ml sodium alginate, 0.004 g / ml-0.006 g / ml TiN powder, and 0.8%-1.5% glycerol by volume; and / or, in step S2, the TiN powder used to prepare the TiN-sodium alginate suspension has a particle size of 20-100 nm.

4. The method for preparing the titanium nitride carbon cloth photothermal composite material according to claim 1, characterized in that, In step S2, the preparation method of TiN-sodium alginate suspension is as follows: Sodium alginate is added to deionized water, stirred continuously and heated to 55℃-65℃, and then kept at 55℃-65℃ for 25min-35min; stirring is continued for 11-13h until the solution becomes transparent, thus obtaining sodium alginate solution; glycerol and TiN powder are added to sodium alginate solution, and ultrasonically dispersed for 25min-35min to obtain uniform TiN-sodium alginate suspension.

5. The method for preparing the titanium nitride carbon cloth photothermal composite material according to claim 1, characterized in that, In step S2, the carbon cloth is immersed in TiN-sodium alginate suspension for 8-15 minutes. And / or, step S2 further includes: after the carbon cloth is removed from the TiN-sodium alginate suspension, scraping off the TiN-sodium alginate suspension from the surface of the carbon cloth.

6. The method for preparing the titanium nitride carbon cloth photothermal composite material according to claim 1, characterized in that, In step S1, the activation treatment includes the following sub-steps: S11, immersing the carbon cloth in acetone for ultrasonic cleaning, then washing with water and drying; S12, immersing the carbon cloth in anhydrous ethanol for ultrasonic cleaning, then washing with water and drying; S13, immersing the carbon cloth in an acid pickling solution for ultrasonic acid cleaning, then washing with water; S14, immersing the carbon cloth in concentrated nitric acid for ultrasonic oxidation, then quenching with ice water, washing with water, and drying to obtain activated carbon cloth.

7. The method for preparing the titanium nitride carbon cloth photothermal composite material according to claim 6, characterized in that, The specific sub-steps of step S1 are as follows: S11, the carbon cloth is immersed in acetone for ultrasonic cleaning at a frequency of 30-50 kHz, a power of 180-220 W, and a time of 15-25 min; then rinsed with deionized water 2-4 times; finally dried at a temperature of 55-65℃ for 25-35 min; S12, the carbon cloth is immersed in anhydrous ethanol for ultrasonic cleaning at a frequency of 30-50 kHz, a power of 180-220 W, and a time of 15-25 min; then rinsed with deionized water 2-4 times; finally dried at a temperature of 55-65℃ for 25-35 min; S13, the carbon cloth is immersed in an acid pickling solution for acid pickling at a frequency of 30-50 kHz, a power of 180-220 W, and a time of 15-25 min; then rinsed with deionized water 2-4 times; finally dried at a temperature of 55-65℃ for 25-35 min; The ultrasonic frequency is 30-50kHz, the power is 180-220W, and the time is 15-25min. Then, it is rinsed 2-4 times with deionized water until the washing water is neutral. Finally, it is dried at 55-65℃ for 25-35min. The pickling solution is a 0.5-1.5mol / L HCl solution. S14 carbon cloth is immersed in concentrated nitric acid for oxidation. The ultrasonic frequency is 30-50kHz, the power is 70-90W, and the time is 15-25min. After taking it out, it is quickly immersed in ice water for quenching for 8-15min. Then, it is repeatedly rinsed with deionized water until the washing water is neutral. Finally, it is dried at 55-65℃ for 11-13h to obtain activated carbon cloth.

8. The method for preparing the titanium nitride carbon cloth photothermal composite material according to claim 1, characterized in that, In step S1, the carbon cloth is woven from 1-12K carbon yarn with a strength of 200-300g / cm. 2 Plain-weave carbon cloth; and / or, in step S3, the calcium chloride solution contains 0.005 g / ml to 0.05 g / ml of calcium chloride; and / or, in step S3, the drying process sequentially includes: drying at room temperature for 3-5 hours; drying at 35°C-45°C for 1.5-2.5 hours; drying at 55°C-65°C for 3.5-4.5 hours; and / or, in step S3, the time for immersing the impregnated carbon cloth in the calcium chloride solution for crosslinking reaction is 4-7 minutes.

9. The method for preparing the titanium nitride carbon cloth photothermal composite material according to claim 8, characterized in that, In step S1, the carbon cloth is woven from 3-6K carbon yarn with a strength of 200-250g / cm. 2 Plain carbon cloth; and / or, in step S3, the calcium chloride solution contains 0.008 g / ml to 0.03 g / ml of calcium chloride.

10. A titanium nitride carbon cloth photothermal composite material prepared by the preparation method according to any one of claims 1-9.

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