CN114854140B - Preparation method of copper calcium titanate nanowire/polystyrene composite material - Google Patents

Abstract

The invention discloses a method for preparing a copper calcium titanate nanowire/polystyrene composite material, which belongs to the technical field of nanocomposite materials; the copper calcium titanate nanowire and polystyrene are dissolved in a solvent and stirred, and then dried and The film is removed to obtain the copper calcium titanate nanowire/polystyrene composite material; the present invention fully mixes the copper calcium titanate nanowire and high impact polystyrene in a solvent through a solution mixing method to obtain CCTO-NWs/ HIPS composite material. Compared with pure HIPS, the dielectric constant value of the CCTO‑NWs/HIPS composite material prepared by the method of the present invention is greatly improved, and at the same time, the dielectric loss is maintained low. It is an environmentally friendly material. , has broad application prospects in fields such as high energy storage capacitors and integrated circuits.

Description

A kind of preparation method of copper calcium titanate nanowire/polystyrene composite material

Technical field

The invention belongs to the technical field of nanocomposite materials, and specifically relates to a preparation method of copper calcium titanate nanowire/polystyrene composite material.

Background technique

Effective large-capacity energy storage technology is a key technology for the current development of smart grids, hybrid vehicles, new energy power generation, pulse power systems, etc. Existing energy storage technologies include dielectric capacitors, supercapacitors and fuel cells, among which dielectric capacitors are Its rapid charge and discharge rate produces high power density and ultra-long cycle life and has unparalleled advantages. It also does not involve electrochemical reactions, making it safer, more reliable and environmentally friendly, thus greatly promoting its application in the field of power electronics. widely used. The core of the dielectric capacitor is the dielectric material, and high dielectric constant is one of the ways to obtain high energy storage performance. Some ferroelectric ceramics have high dielectric constants, but the use of a single ceramic material is restricted by the hardness, complex process, and energy consumption of sintering. Composite ferroelectric ceramics with polymers can combine the high dielectric and polymerization of inorganic materials. It has attracted widespread attention due to its advantages such as high breakdown, low loss, and easy processing into films to achieve large-scale production.

At present, the fillers in ceramic/polymer high-dielectric composite materials generally use barium titanate (BaTiO ₃ ) series and lead titanate (PbTiO ₃ ) with perovskite structure, which have higher dielectric constant and lower dielectric loss. system, or the calcium copper titanate (CaCu ₃ Ti ₄ O ₁₂ , CCTO) ferroelectric ceramic powder reported in recent years, the dielectric constant of the composite material can usually increase from several to more than ten times that of the polymer matrix. However, the amount of ceramic particles added in this type of composite material is often high, and even when the volume fraction of ceramic particles reaches more than 70%, the dielectric constant of the composite material is generally difficult to exceed 100 at room temperature. Excessive ceramic addition in composite materials can easily increase dielectric loss and reduce processing performance, mechanical properties and breakdown resistance. Recent studies have found that ceramic nanofillers with large aspect ratios, such as one-dimensional nanofibers and two-dimensional nanosheets, can form a large number of microcapacitors in the matrix, and overlapping each other can increase the path bending of electrical tree formation during breakdown. Compared with spherical nanoparticles, they are more suitable for increasing the dielectric constant and breakdown field strength, thereby achieving a leap in overall performance. At present, there are few commercialized products of nanowire ceramics, and it is difficult to obtain fillers with various particle sizes and stable properties like ceramic particles in real time.

CaCu ₃ Ti ₄ O ₁₂ (CCTO) is a high dielectric constant ceramic material. In 2000, Subramanian of DuPont Laboratory first discovered the giant dielectric properties of CCTO. The dielectric constant of CCTO ceramics can exceed 10 ⁴ at room temperature. CCTO has attractive application potential in capacitors and electronic equipment due to its stable chemical properties, good temperature stability, and consistently low dielectric loss over a wide frequency range. However, there are currently few commercialized CCTO products, especially CCTO nanowires (CCTO-NWs) with better dielectric properties. There are basically no commercialized products. High-impact polystyrene (HIPS) is a low-cost polymer that is easy to process, has good toughness, and is environmentally friendly. Chinese patent CN101712784B introduces a core-shell structure filler/polymer composite material. The core-shell filler is formed by metal-coated ceramic particles. The ceramic particles include copper calcium titanate (CCTO), barium titanate (BT), titanium Barium strontium oxide (BST), metals include silver, cobalt, copper, aluminum, polymers include polyvinylidene fluoride (PVDF) and its copolymers, polypropylene (PP), polyethylene (PE), polymethacrylate One of the esters (PMMA). In the embodiment, a BT@Ag/PVDF composite material was prepared. Its maximum dielectric constant is 183, which is 80% higher than that of the composite material simply adding BT filler. However, its dielectric loss is about 0.2, which is still higher than that of the composite material simply adding BT filler. big.

At present, there is no plan to prepare composite materials using HIPS as the matrix and CCTO-NWs as the filler.

Contents of the invention

In order to solve the above problems in the prior art, the present invention provides a preparation method of copper calcium titanate nanowire/polystyrene composite material.

In order to achieve the above objects, the present invention provides the following technical solutions:

The invention provides a method for preparing a copper calcium titanate nanowire/polystyrene composite material, which includes the following steps: dissolving the copper calcium titanate nanowire and polystyrene in a solvent and stirring, followed by drying and stripping; That is, the copper calcium titanate nanowire/polystyrene composite material is obtained.

Further, the preparation method of the copper calcium titanate nanowire is a two-step hydrothermal method, specifically:

(1) Heating titanium dioxide and sodium hydroxide solutions to obtain precursor sodium titanate nanowires;

(2) Mix and heat the sodium titanate nanowires with copper salt, calcium salt and ammonia water, then calcine, soak in acid, then wash and dry to obtain the copper calcium titanate nanowires.

Further, in step (1), the heating temperature is 180~240°C and the time is 12~36h; the concentration of the sodium hydroxide solution is 6mol/L; in step (2), the heating temperature is 140°C. ~160°C, and the time is 1~10h. The calcination specifically includes heating up to 700~900°C at a rate of 30~50°C/min and keeping the temperature for 1~6h.

Further, in step (1), the molar ratio of titanium dioxide and sodium hydroxide is 3:2; in step (2), the copper salt is copper nitrate, the calcium salt is calcium nitrate, and the titanate The molar ratio of sodium nanowires to copper salt and calcium salt is 4:12:3; the acid is hydrochloric acid with a concentration of 0.1 to 1.0 M, and the soaking time is 5 to 10 hours.

CCTO-NWs synthesized by a two-step hydrothermal method have a simple process and low cost. By controlling the process parameters, nanowires with specific diameters and lengths can be obtained.

The copper calcium titanate nanowires obtained by the two-step hydrothermal method of the present invention have a diameter of 50-200 nm and a length of 6-35 μm.

Further, the solvent is N,N-dimethylacetamide; the volume of the copper calcium titanate nanowire is 50% or less of the total volume of the copper calcium titanate nanowire and polystyrene.

Further, the stirring is performed at 20 to 30°C; the stirring also includes ultrasonic treatment for 0.5 to 5 hours.

Further, the drying temperature is 50-80°C and the drying time is 0.5-5h.

Further, the defilming was performed in ice water.

The invention also provides a copper calcium titanate nanowire/polystyrene composite material prepared according to the above-mentioned preparation method.

Principle of the present invention: The dielectric properties of polymer-based composite materials are mainly closely related to the matrix, the filler, and the interface compatibility between the two. Among them, functional fillers are key components, and their structure, morphology, surface properties, etc. play a decisive role. The CCTO-NWs prepared by the present invention have a high aspect ratio, which is conducive to mutual overlap in composite materials, can increase the curvature of the path formed by electrical tree branches during breakdown, thereby increasing the breakdown field strength, and using them as fillers can make composite materials seep. The threshold value is lower, and the dielectric constant of the composite material is increased while maintaining low dielectric loss, thereby obtaining a CCTO-NWs/HIPS composite material with excellent comprehensive properties.

The present invention conducts research on the preparation process of ceramic nanowires, composite material preparation process, modified filler morphology and distribution state, interface design and control, etc. First, it uses common, easily available and low-price raw materials, and uses a two-step hydrothermal method. Prepare linear calcium copper titanate, and adjust the reaction temperature and reaction time to control the aspect ratio of the nanowires; use the prepared CCTO-NWs as filler, use HIPS as the matrix, adjust the volume ratio of filler to matrix, and prepare CCTO-NWs/ HIPS composite dielectric material, the resulting composite material has a lower percolation threshold, increased dielectric constant and reduced loss.

Compared with the prior art, the present invention has the following beneficial effects:

The present invention uses CCTO-NWs and HIPS to composite to prepare CCTO-NWs/HIPS composite materials. Compared with CCTO nanoparticles, the linear filler has a larger specific surface area than the granular filler, and the composite of nanowires and polymers increases the contact between the filler and the matrix. Interface, the increase in the interface ratio makes the interface polarization more significant, which is beneficial to improving the dielectric constant. At the same time, it also has excellent performance in increasing the breakdown field strength and reducing the dielectric loss, so that the composite material prepared by the present invention can effectively improve the The dielectric constant is improved while maintaining low dielectric loss. Moreover, CCTO-NWs can enable composite materials to reach the percolation threshold at a lower addition amount, which can significantly improve the mechanical properties of dielectric materials.

The present invention fully mixes copper calcium titanate nanowires and high-impact polystyrene in a solvent through a solution mixing method to obtain a CCTO-NWs/HIPS composite material. Compared with pure HIPS, the composite material prepared by the method of the present invention has a 1Hz At 100 Hz, the dielectric constant increases from 4.21 of pure HIPS to 74.15, maintaining a low dielectric loss (0.127); at 100 Hz, the dielectric constant increases from 3.42 of pure HIPS to 61.63, while maintaining a low dielectric loss (0.072 ). This composite material is conducive to meeting the current demand for high dielectric constant dielectric materials in electronic devices and promotes the development of electronic devices towards higher energy storage density. It is an environmentally friendly material and has broad application in the fields of high energy storage capacitors and integrated circuits. application prospects.

Description of drawings

In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the drawings needed to be used in the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some of the drawings of the present invention. Embodiments, for those of ordinary skill in the art, other drawings can be obtained based on these drawings without exerting creative efforts.

In Figure 1, (a) to (e) are scanning electron microscope images of CCTO-NWs prepared in Examples 1 to 5 respectively;

Figure 2 is the X-ray diffraction pattern of CCTO-NWs prepared in Examples 1 to 5;

In Figure 3, (a) to (f) are the cross-sectional scanning electron microscope images of pure HIPS and CCTO-NWs/HIPS composite materials prepared in Examples 1 to 5 (corresponding to Examples 1-5 in the figure) respectively;

Figure 4 is a diagram showing the relationship between dielectric constant and dielectric loss at room temperature of CCTO-NWs/HIPS composite materials and pure HIPS prepared in Examples 1 to 5 (corresponding to Examples 1-5 in the figure).

Detailed ways

Various exemplary embodiments of the invention will now be described in detail. This detailed description should not be construed as limitations of the invention, but rather as a more detailed description of certain aspects, features and embodiments of the invention. It should be understood that the terms used in the present invention are only used to describe particular embodiments and are not intended to limit the present invention.

In addition, for numerical ranges in the present invention, it should be understood that every intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or value intermediate within a stated range and any other stated value or value intermediate within a stated range is also included within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded from the range.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only the preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and/or materials in connection with which the documents relate. In the event of conflict with any incorporated document, the contents of this specification shall prevail.

It will be apparent to those skilled in the art that various modifications and changes can be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to the skilled person from the description of the invention. The specification and examples of the present invention are exemplary only.

The words "includes", "includes", "has", "contains", etc. used in this article are all open terms, which mean including but not limited to.

Example 1

Preparation of copper calcium titanate nanowire/polystyrene composite material, the steps are as follows:

1. Use a two-step hydrothermal method to prepare CCTO-NWs. The steps are as follows:

(1) Weigh 50.3g TiO ₂ and disperse it evenly in 70mL 6M NaOH solution by stirring. After stirring evenly, transfer the mixture to the lining of a 100mL reactor and conduct a hydrothermal reaction at 180°C for 24 hours. Use deionized water Wash until neutral and dry to obtain sodium titanate nanowires (Na ₂ Ti ₃ O ₇ nanowires).

(2) Mix 1.2g Na ₂ Ti ₃ O ₇ nanowires, 2.9g copper nitrate trihydrate, and 0.7g calcium nitrate tetrahydrate and stir evenly; slowly add 1 mL of ammonia with a concentration of 25 wt%, stir for another 0.5 hours, and place in the reaction kettle React at 150°C for 10 hours.

(3) Wash the product obtained in step (2) with deionized water until neutral, dry it, put it into a crucible and heat it to 700°C in a muffle furnace at a rate of 30°C/min for 6 hours, and then soak it in 0.1 M in hydrochloric acid for 10 hours, washed with deionized water until neutral, and dried to obtain CCTO-NWs.

2. Use solution mixing method to prepare CCTO-NWs/HIPS composite film. The specific steps are as follows:

(1) Weigh 1.89 grams of HIPS (polystyrene) and add it to N,N-dimethylacetamide, stir to dissolve.

(2) Weigh 0.59 grams of CCTO-NWs powder (CCTO-NWs powder accounts for 10% of the total volume of HIPS and CCTO-NWs powder) and add it to the solution obtained in step (1), and stir thoroughly.

(3) Ultrasonicate the solution obtained in step (2) for 0.5 hours, add ice cubes while ultrasonic, and keep the water temperature at 25°C to mix the solution more uniformly to obtain a composite material solution.

(4) Pour the composite material solution obtained in step (3) into a petri dish and place it in a vacuum drying oven to dry at 50°C for 5 hours.

(5) Place the petri dish into ice water, remove the film from the material, rinse it with distilled water and dry it to obtain the CCTO-NWs/HIPS composite material.

The CCTO-NWs/HIPS composite material prepared in this example was copper plated, and the dielectric properties were tested after polarization at 50°C.

Example 2

Preparation of copper calcium titanate nanowire/polystyrene composite material, the steps are as follows:

1. Use a two-step hydrothermal method to prepare CCTO-NWs. The steps are as follows:

(1) Weigh 50.3g TiO ₂ and disperse it evenly in 70mL 6M NaOH solution. After stirring evenly, transfer the mixture to the lining of a 100mL reactor, react hydrothermally at 200°C for 12 hours, and wash with deionized water. to neutrality, and then dried to obtain Na ₂ Ti ₃ O ₇ nanowires.

(2) Mix 1.2g Na ₂ Ti ₃ O ₇ nanowires, 2.9g copper nitrate trihydrate, and 0.7g calcium nitrate tetrahydrate and stir evenly; slowly add 1 mL of ammonia with a concentration of 28 wt%, stir for another 1 hour, and place in the reaction kettle React at 140°C for 7 hours.

(3) Wash the product obtained in step (2) with deionized water until neutral, dry it, put it into a crucible, heat it to 750°C in a muffle furnace at a rate of 35°C/min for 6 hours, and then soak it in 0.3 M in hydrochloric acid for 8 hours, washed with deionized water until neutral, and dried to obtain CCTO-NWs.

2. Use solution mixing method to prepare CCTO-NWs/HIPS composite film. The steps are as follows:

(1) Weigh 1.68 grams of HIPS and add it to N,N-dimethylacetamide, stir to dissolve.

(2) Weigh 1.19 grams of CCTO-NWs powder (CCTO-NWs powder accounts for 20% of the total volume of HIPS and CCTO-NWs powder) and add it to the solution obtained in step (1), and stir thoroughly.

(3) Ultrasonicate the solution obtained in step (2) for 1 hour, add ice cubes while ultrasonic, and keep the water temperature at 20°C to mix the solution more uniformly to obtain a composite material solution.

(4) Pour the composite material solution obtained in step (3) into a petri dish and place it in a vacuum drying oven to dry at 60°C for 3 hours.

(5) Put the Petri dish into ice water, remove the film from the material, rinse it with distilled water and dry it to obtain the CCTO-NWs/HIPS composite material.

The CCTO-NWs/HIPS composite material prepared in this example was copper plated, and the dielectric properties were tested after polarization at 60°C.

Example 3

Preparation of copper calcium titanate nanowire/polystyrene composite material, the steps are as follows:

1. Use a two-step hydrothermal method to prepare CCTO-NWs. This method specifically includes the following steps:

(1) Weigh 50.3g TiO ₂ and disperse it evenly in 70mL 6M NaOH solution. After stirring evenly, transfer the mixture to the lining of a 100mL reactor, conduct a hydrothermal reaction at 240°C for 36 hours, and wash with deionized water. to neutrality, and then dried to obtain Na ₂ Ti ₃ O ₇ nanowires.

(2) Mix 1.2g Na ₂ Ti ₃ O ₇ nanowires, 2.9g copper nitrate trihydrate, and 0.7g calcium nitrate tetrahydrate and stir evenly; slowly add 1 mL of ammonia with a concentration of 25 wt%, stir for another 0.5 hours, and place in the reaction kettle React at 160°C for 1 hour.

(3) Wash the product obtained in step (2) with deionized water until neutral, dry it, put it into a crucible, heat it in a muffle furnace to a constant temperature of 800°C at a rate of 40°C/min for 2 hours, and then soak it in 0.2 M in hydrochloric acid for 5 hours, washed with deionized water until neutral, and dried to obtain CCTO-NWs.

2. Use solution mixing method to prepare CCTO-NWs/HIPS composite film. The steps are as follows:

(1) Weigh 1.47 grams of HIPS and add it to N,N-dimethylacetamide, stir to dissolve.

(2) Weigh 1.78 grams of CCTO-NWs powder (CCTO-NWs powder accounts for 30% of the total volume of HIPS and CCTO-NWs powder) and add it to the solution obtained in step (1), and stir thoroughly.

(3) Ultrasonicate the solution obtained in step (2) for 2 hours, add ice cubes while ultrasonic, and keep the water temperature at 24°C to mix the solution more uniformly to obtain a composite material solution.

(4) Pour the composite material solution obtained in step (3) into a petri dish and place it in a vacuum drying oven to dry at 70°C for 3 hours.

(5) Place the petri dish into ice water, remove the film from the material, rinse it with distilled water and dry it to obtain the CCTO-NWs/HIPS composite material.

The CCTO-NWs/HIPS composite material prepared in this example was copper plated, and the dielectric properties were tested after polarization at 70°C.

Example 4

Preparation of copper calcium titanate nanowire/polystyrene composite material, the steps are as follows:

1. Use a two-step hydrothermal method to prepare CCTO-NWs. The steps are as follows:

(1) Weigh 50.3g TiO ₂ and disperse it evenly in 70mL 6M NaOH solution. After stirring evenly, transfer the mixture to the lining of a 100mL reactor, react hydrothermally at 240°C for 12 hours, and wash with deionized water. to neutrality, and then dried to obtain Na ₂ Ti ₃ O ₇ nanowires.

(2) Mix 1.2g Na ₂ Ti ₃ O ₇ nanowires, 2.9g copper nitrate trihydrate, and 0.7g calcium nitrate tetrahydrate and stir evenly; slowly add 2 mL ammonia with a concentration of 25 wt% and stir for another 2 hours, then place it in the reaction kettle React at 140°C for 3 hours.

(3) Wash the product obtained in step (2) with deionized water until neutral, dry it, put it into a crucible, heat it in a muffle furnace to a constant temperature of 900°C at a rate of 50°C/min for 1 hour, and then soak it in 1M immersed in hydrochloric acid for 5 hours, washed with deionized water until neutral, and dried to obtain CCTO-NWs.

2. Use solution mixing method to prepare CCTO-NWs/HIPS composite film. The steps are as follows:

(1) Weigh 1.26 grams of HIPS and add it to N,N-dimethylacetamide, stir to dissolve.

(2) Weigh 2.37 grams of CCTO-NWs powder (CCTO-NWs powder accounts for 40% of the total volume of HIPS and CCTO-NWs powder) and add it to the solution obtained in step (1), and stir thoroughly.

(3) Ultrasonicate the solution obtained in step (2) for 3 hours, add ice cubes while ultrasonic, and keep the water temperature at 30°C to mix the solution more uniformly to obtain a composite material solution.

(4) Pour the composite material solution obtained in step (3) into a petri dish and place it in a vacuum drying oven to dry at 80°C for 1 hour.

(5) Put the Petri dish into ice water, remove the film from the material, rinse it with distilled water and dry it to obtain the CCTO-NWs/HIPS composite material.

The CCTO-NWs/HIPS composite material prepared in this example was copper plated, and the dielectric properties were tested after polarization at 80°C.

Example 5

Preparation of copper calcium titanate nanowire/polystyrene composite material, the steps are as follows:

1. Use a two-step hydrothermal method to prepare CCTO-NWs. The steps are as follows:

(1) Weigh 50.3g TiO ₂ and disperse it evenly in 70mL 6M NaOH solution. After stirring evenly, transfer the mixture to the lining of a 100mL reactor, react hydrothermally at 220°C for 24 hours, and wash with deionized water. to neutrality, and then dried to obtain Na ₂ Ti ₃ O ₇ nanowires.

(2) Mix 1.2g Na ₂ Ti ₃ O ₇ nanowires, 2.9g copper nitrate trihydrate, and 0.7g calcium nitrate tetrahydrate and stir evenly; slowly add 1mL of ammonia with a concentration of 28wt% and stir for another 2 hours, then place it in the reaction kettle React at 155°C for 8 hours.

(3) Wash the product obtained in step (2) with deionized water until neutral, dry it, put it into a crucible, heat it in a muffle furnace to a constant temperature of 800°C at a rate of 45°C/min for 3 hours, and then soak it in 0.7 M in hydrochloric acid for 8 hours, washed with deionized water until neutral, and dried to obtain CCTO-NWs.

2. Use solution mixing method to prepare CCTO-NWs/HIPS composite film. The steps are as follows:

(1) Weigh 1.05 grams of HIPS and add it to N,N-dimethylacetamide, stir to dissolve.

(2) Weigh 2.96 grams of CCTO-NWs powder (CCTO-NWs powder accounts for 50% of the total volume of HIPS and CCTO-NWs powder) and add it to the solution obtained in step (1), and stir thoroughly.

(3) Ultrasonicate the solution obtained in step (2) for 5 hours, add ice cubes while ultrasonic, and keep the water temperature at 28°C to mix the solution more uniformly to obtain a composite material solution.

(4) Pour the composite material solution obtained in step (3) into a petri dish and place it in a vacuum drying oven to dry at 80°C for 2 hours.

(5) Place the petri dish into ice water, remove the film from the material, rinse it with distilled water and dry it to obtain the CCTO-NWs/HIPS composite material.

The CCTO-NWs/HIPS composite material prepared in this example was copper plated, and the dielectric properties were tested after polarization at 80°C.

The scanning electron microscope images of the CCTO-NWs prepared in Examples 1 to 5 are shown in Figure 1(a) to (e) respectively. It can be seen from the figures that the diameters of the CCTO-NWs prepared in each Example are distributed in Between 50 and 200nm, the length is between 6 and 35μm, and the dispersion is relatively uniform.

The X-ray diffraction pattern of the CCTO-NWs prepared in Examples 1 to 5 is shown in Figure 2. It can be seen from the figure that no other impurity peaks appear except for CCTO-NWs, indicating that the prepared CCTO-NWs are pure phases. .

The cross-sectional scanning electron microscope images of the HIPS used in the present invention and the CCTO-NWs/HIPS composite materials prepared in Examples 1 to 5 (corresponding to Examples 1 to 5 in the figure) are shown in Figure 3(a) to (f) respectively. It can be seen from the figure that in the composite material, CCTO-NWs and HIPS are fully mixed, and the fillers are evenly distributed in the matrix.

The HIPS was copper plated and its dielectric properties were tested. Figure 4 shows the relationship between the dielectric constant and the relationship between dielectric loss and frequency obtained by testing the dielectric properties of CCTO-NWs/HIPS composite materials prepared by HIPS and Examples 1 to 5 (corresponding to Examples 1-5 in the figure) at room temperature. The dielectric constant and dielectric loss of each material at 1Hz and 100Hz are shown in Table 1:

Table 1

Comparative example 1

Same as Example 1, except that the HIPS in step 1(1) of Example 1 is replaced with polyvinylidene fluoride.

Comparative example 2

Same as Example 1, except that the CCTO-NWs in step 2(2) of Example 1 are replaced with CCTO nanoparticles.

Comparative example 3

The same as Example 1, except that step (5) is: hot-press the film obtained in step (4) through a tablet press at 180°C and 10 MPa for 5 minutes to obtain a CCTO-NWs/HIPS composite material.

The composite materials finally prepared in Comparative Examples 1 to 3 were copper plated, and the dielectric properties were tested at room temperature after polarization at 50°C. The dielectric constants of the materials prepared in Comparative Examples 1 to 3 at 1 Hz were respectively 12.32, 9.42 and 8.89, the dielectric losses are 0.031, 0.047 and 0.028 respectively; the dielectric constants at 100Hz are 10.42, 8.53 and 6.87 respectively, and the dielectric losses are 0.026, 0.039 and 0.021 respectively.

The above are only preferred specific embodiments of the present invention, and the protection scope of the present invention is not limited thereto. Any person familiar with the technical field shall, within the technical scope disclosed in the present invention, according to the technical solutions of the present invention and Any equivalent substitution or change of the inventive concept shall be covered by the protection scope of the present invention.

Claims (6)

1. A method for preparing a calcium copper titanate nanowire/polystyrene composite material, which is characterized by comprising the following steps: dissolving the copper calcium titanate nanowire and polystyrene in a solvent and stirring, followed by drying, Remove the film in ice water to obtain the copper calcium titanate nanowire/polystyrene composite material; The polystyrene is high impact polystyrene; The volume of the copper calcium titanate nanowire is 50% or less of the total volume of the copper calcium titanate nanowire and polystyrene; The preparation method of the copper calcium titanate nanowire is: (1) Heating titanium dioxide and sodium hydroxide solutions to obtain precursor sodium titanate nanowires; (2) Mix and heat the sodium titanate nanowires with copper salt, calcium salt and ammonia, then calcine, soak in acid, then wash and dry to obtain the copper calcium titanate nanowires; The diameter of the copper calcium titanate nanowire is 50-200nm and the length is 6-35μm; In step (1), the molar ratio of titanium dioxide and sodium hydroxide is 3:2; In step (2), the copper salt is copper nitrate, the calcium salt is calcium nitrate, the molar ratio of the sodium titanate nanowires to the copper salt and calcium salt is 4:12:3; the acid is a concentration of It is 0.1~1.0M hydrochloric acid, and the soaking time is 5~10h. 2. The preparation method of copper calcium titanate nanowire/polystyrene composite material according to claim 1, characterized in that, in step (1), the heating temperature is 180~240°C and the time is 12~36h ; In step (2), the heating temperature is 140-160°C and the time is 1-10h, and the calcination temperature is 700-900°C and the time is 1-6h. 3. The preparation method of copper calcium titanate nanowire/polystyrene composite material according to claim 1, characterized in that the solvent is N, N-dimethylacetamide. 4. The preparation method of calcium copper titanate nanowire/polystyrene composite material according to claim 1, characterized in that the stirring is carried out at 20-30°C; after the stirring, it also includes ultrasonic treatment of 0.5-30°C. 5h operation. 5. The preparation method of copper calcium titanate nanowire/polystyrene composite material according to claim 1, characterized in that the drying temperature is 50-80°C and the time is 0.5-5h. 6. A copper calcium titanate nanowire/polystyrene composite material prepared according to the preparation method according to any one of claims 1 to 5.