Petal-shaped copper calcium titanate nano material and preparation method thereof

Abstract

According to the petal-shaped copper calcium titanate nano material and the preparation method thereof, TiO2 nano flowers are prepared through a hydrothermal method, the TiO2 nano flowers are used as a template and subjected to a hydrothermal reaction with a calcium source and a copper source, and the petal-shaped copper calcium titanate nano material is obtained. The surface of the prepared copper calcium titanate is subjected to secondary modification, on one hand, dielectric mismatch is relieved through a dielectric constant gradient established through modification, and electric field distortion is homogenized; on the other hand, the compatibility between the CCTONF and a polymer matrix is improved, and the interface defects of the CCTONF and the polymer matrix are reduced; finally, the prepared composite dielectric film is subjected to thermal stretching, secondary dispersion of the filler is achieved, distribution of the filler in a polymer matrix is homogenized, and the performance of the composite material is further improved. According to the method, the petal-shaped copper calcium titanate nanocluster is synthesized for the first time, the preparation process is simple, the cost is low, pollution is avoided, and the dielectric constant and the energy storage density of polyarylene ether nitrile can be effectively improved.

Description

Technical Field

[0001] This invention belongs to the field of composite material technology, specifically relating to a petal-shaped calcium copper titanate nanomaterial (CCTONF) and its preparation method. Background Technology

[0002] Polymer-based dielectric materials, as an important component of dielectric capacitors, have made significant contributions to improving capacitor performance, miniaturizing devices, and reducing weight due to their excellent electrical properties and processability.

[0003] Introducing high ε into polymers r Inorganic nanomaterials are a common method for improving the dielectric properties of materials. However, numerous literature reports indicate that simple two-phase or multi-phase doping cannot effectively improve the dielectric properties of materials. This is mainly due to the significant differences in properties between nanomaterials and polymers. On the one hand, nanomaterials have high surface energy and exhibit severe agglomeration, affecting their dispersion in the polymer matrix. On the other hand, the large difference in dielectric constant between the filler and the matrix leads to electric field distortion at the filler-matrix interface. Furthermore, the poor compatibility of nanofillers in the polymer matrix results in significant interfacial defects.

[0004] Therefore, designing nanofillers to improve the dielectric and energy storage properties of composite materials has become one of the important research directions in this field. Summary of the Invention

[0005] (a) Technical problems to be solved

[0006] This invention proposes a petal-shaped copper-calcium titanate nanomaterial and its preparation method to solve the technical problem of how to improve the dielectric and energy storage performance of polymers.

[0007] (II) Technical Solution

[0008] To address the aforementioned technical problems, this invention proposes a method for preparing petal-shaped calcium copper titanate nanomaterials, which includes the following steps:

[0009] S1. Preparation of petal-shaped TiO2

[0010] Tetrabutyl titanate (TBOT) and hydrochloric acid solution were added to a high-pressure reactor, stirred evenly, and subjected to hydrothermal reaction. After the reaction was completed, the mixture was centrifuged, washed with deionized water until pH=7, and then dried to obtain petal-shaped TiO2.

[0011] S2. Preparation of petal-shaped calcium copper titanate

[0012] S2-1. Cu(NO3)2·3H2O, Ca(NO3)2·4H2O and petal-shaped TiO2 prepared in step S1 were placed in a beaker, and stirring and ultrasonic treatment were carried out at room temperature after adding anhydrous ethanol until a uniform suspension was formed;

[0013] S2-2. The suspension was transferred to a high-pressure reaction kettle for solvothermal treatment, and after solvothermal reaction, the system was suction filtered to obtain a yellowish-brown filter cake;

[0014] S2-3. The filter cake was washed and dried, and then calcined in an air atmosphere, and the calcined product was stirred in dilute hydrochloric acid at room temperature, and after washing and drying, petal-shaped copper calcium titanate nanomaterials, i.e. CCTONF, were obtained;

[0015] S3. Modification of petal-shaped copper calcium titanate nanomaterials

[0016] S3-1. The surface of CCTONF prepared in step S2 was treated with silane coupling agent KH550 to obtain KH550-modified CCTONF, i.e. CCTONF-KH550;

[0017] S3-2. Functionalized CCTONF with covalently bonded SPEN on the surface was prepared by esterification reaction of CCTONF and sulfonated polyarylether nitrile SPEN to obtain SPEN-modified CCTONF, i.e. SPEN@CCTONF;

[0018] S4. Preparation of petal-shaped copper calcium titanate-doped polyarylether nitrile composite material

[0019] S4-1. SPEN@CCTONF prepared in step S3 was dispersed in NMP and ultrasonically treated to obtain a dispersed SPEN@CCTONF system;

[0020] S4-2. The polymer matrix was added to the dispersed SPEN@CCTONF system and stirred until completely dissolved, and after the mixture was naturally cooled to room temperature, it was poured onto a glass plate;

[0021] S4-3. The glass plate in step S4-2 was placed in an oven, and the mixture was dried in the oven to obtain a petal-shaped copper calcium titanate nanomaterial composite dielectric film.

[0022] Further, in step S1, V TBOT :V HCl = 1: (30-70); the hydrothermal reaction temperature was 180°C, and the reaction time was 2h; and drying was carried out in an oven at 60°C for 12h.

[0023] Further, in step S2-1, stirring is performed at room temperature for 24 hours, and ultrasonic treatment is performed for 2 hours; in step S2-2, the solvothermal reaction temperature is 155 DEG C, and the reaction time is 24 hours; in step S2-3, the calcination temperature is 800 DEG C, and the calcination time is 2 hours; after calcination, the product is stirred in dilute hydrochloric acid at room temperature for 1 day.

[0024] Further, in step S3-1, CCTONF is mixed with anhydrous ethanol and deionized water, the ratio of anhydrous ethanol to deionized water is V EtOH :V H2O = 9:1, stirring is performed at room temperature for 6 hours, and ultrasonic treatment is performed for 0.5 hours, then silane coupling agent KH550 is added to the dispersion system, and heating reflux is performed, the reflux temperature is 80 DEG C, and the reflux time is 24 hours; after suction filtration and drying, CCTONF modified by KH550 is obtained.

[0025] Further, in step S3-2, CCTONF-KH550 prepared in step S3-1 is dispersed in NMP, stirring is performed at room temperature for 6 hours, and ultrasonic treatment is performed for 0.5 hours, then SPEN is added, and stirring and ultrasonic treatment are continued; the dispersed system is poured into a solvothermal reactor to perform solvothermal reaction, the solvothermal reaction temperature is 200 DEG C, and the reaction time is 2 hours; after the reaction is completed, the obtained product is filtered, washed and dried to obtain SPEN modified CCTONF, namely SPEN@CCTONF.

[0026] Further, in step S4-2, the polymer matrix material includes at least one of polyethylene, polyester amide, biaxially oriented polypropylene, polyarylene ether nitrile, polyvinylidene fluoride, epoxy resin and polymethyl methacrylate.

[0027] Further, the method further includes step S5, heat stretching the petal-shaped calcium copper titanate nanomaterial composite dielectric film.

[0028] Further, in step S5, the uniaxial heat stretching method is used to heat stretch the composite dielectric film.

[0029] Further, in step S5, the original size of the composite dielectric film is 20 mm*60 mm, both ends of the composite dielectric film are fixed, and the original stretching distance is controlled to be 50 mm; one end of the composite dielectric film is hung at the top of an oven, and the other end is hung with a counterweight of 100 g, the distance between the bottom of the oven and the counterweight is adjusted, the heat stretching temperature is 200 DEG C, the composite dielectric film reaches a stretching ratio of 100%, and the composite dielectric film is naturally cooled to room temperature before the counterweight is released.

[0030] In addition, the application also provides a petal-shaped calcium copper titanate nanomaterial, which is prepared by the above method.

[0031] (Three) beneficial effects

[0032] The application provides a petal-shaped copper calcium titanate nanomaterial and a preparation method thereof. TiO2 nanoflowers are prepared by a hydrothermal method, and the TiO2 nanoflowers are used as a template to perform a hydrothermal reaction with a calcium source and a copper source to obtain the petal-shaped copper calcium titanate nanomaterial. The step is suitable for a series of compounds taking TiO2 as a precursor template, such as copper calcium titanate, barium titanate, strontium titanate, barium strontium titanate and calcium titanate. The surface of the prepared copper calcium titanate is secondarily modified. On one hand, a dielectric constant gradient is established by the modification to relieve dielectric mismatch and homogenize electric field distortion. On the other hand, the compatibility between the CCTONF and the polymer matrix is improved, and the interface defects of the two are reduced. Finally, the prepared composite dielectric film is hot stretched to realize secondary dispersion of the filler, homogenize the distribution of the filler in the polymer matrix and further improve the performance of the composite material. The petal-shaped copper calcium titanate nanoclusters are synthesized for the first time by the method, the preparation process is simple, the cost is low, no pollution is caused, and the dielectric constant and the energy storage density of the polyarylene ether nitrile can be effectively improved. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 A flow chart for preparation and modification of the petal-shaped copper calcium titanate is shown.

[0034] Figure 2 A microstructure of the titanium dioxide nanoflowers prepared in Example 1 is shown.

[0035] Figure 3 A microstructure of the petal-shaped copper calcium titanate prepared in Example 1 is shown.

[0036] Figure 4 A comparison of the dielectric constants of the composite dielectric film before and after modification in Example 1 is shown.

[0037] Figure 5 A comparison of the dielectric loss performance of the composite dielectric film before and after modification in Example 1 is shown.

[0038] Figure 6 A comparison of the energy storage densities of the composite dielectric film before and after modification in Example 1 is shown.

[0039] Figure 7 A comparison of the energy storage densities of the composite dielectric film before and after hot stretching in Example 1 is shown. DETAILED DESCRIPTION

[0040] In order to make the purpose, content and advantages of the application clearer, the specific embodiments of the application are further described in detail below with reference to the drawings and examples.

[0041] Example 1

[0042] The embodiment provides a preparation method of the petal-shaped copper calcium titanate nanomaterial, and a flow chart thereof is shown as Figure 1 The main steps include the following steps.

[0043] S1. Preparation of petal-shaped TiO2

[0044] Tetrabutyl titanate TBOT and 5M hydrochloric acid solution were put into a high-pressure reaction kettle at V TBOT :V HCl = 1:70, stirred uniformly, and subjected to hydrothermal reaction, the hydrothermal reaction temperature was 180°C, and the reaction time was 2h; after the reaction was completed, the product was attached to the lining wall of the reaction kettle, which was taken down, centrifuged, washed with deionized water until pH = 7, and then dried in a 60°C oven for 12h to obtain petal-shaped TiO2(TiO2NF).

[0045] S2. Preparation of petal-shaped copper calcium titanate

[0046] S2-1. Cu(NO3)2·3H2O (1.087g, 4.5mmol), Ca(NO3)2·4H2O (0.354g, 1.5mmol) and TiO2NF (0.479g, 6mmol) prepared in step S1 were placed in a beaker, 100mL of anhydrous ethanol was added, and stirring was carried out at room temperature for 24h, and ultrasonic treatment was continued for 2h until a uniform suspension was formed;

[0047] S2-2. The suspension was transferred to a high-pressure reaction kettle for solvothermal treatment, the solvothermal reaction temperature was 155°C, and the reaction time was 24h; after the solvothermal reaction, the system was subjected to suction filtration to obtain a tan filter cake;

[0048] S2-3. The filter cake was washed and dried, and then calcination was carried out in an air atmosphere, the calcination temperature was 800°C, and the calcination time was 2h; the product after calcination was stirred in 0.1M dilute hydrochloric acid at room temperature for 1 day, and after washing and drying, petal-shaped copper calcium titanate nanomaterials (CCTONF) were obtained.

[0049] S3. Modification of petal-shaped copper calcium titanate nanomaterials

[0050] S3-1. Amino treatment was carried out on the surface of CCTONF prepared in step S2 using silane coupling agent KH550: CCTONF (1.0g) was mixed with anhydrous ethanol (90mL) and deionized water (10mL), stirred at room temperature for 6h, and then subjected to ultrasonic treatment for 0.5h, silane coupling agent KH550 (0.1g) was added to the dispersion system, heated to reflux, the reflux temperature was 80°C, and the reflux time was 24h; after suction filtration and drying, KH550-modified CCTONF (CCTONF-KH550) was obtained;

[0051] S3-2. Preparation of functionalized CCTONF (SPEN@CCTONF) with SPEN covalently bonded on the surface by esterification reaction: CCTONF-KH550 (0.5 g) prepared in step S3-1 was dispersed in NMP, stirred at room temperature for 6 h and ultrasonically treated for 0.5 h, then SPEN (0.2 g) was added thereto, and stirring and ultrasonic treatment were continued for 0.5 h; the dispersed system was poured into a hydrothermal reactor for solvothermal reaction, the solvothermal reaction temperature was 200℃, and the reaction time was 2 h; after the reaction was completed, the obtained product was filtered, washed and dried to obtain SPEN@CCTONF.

[0052] S4. Preparation of petal-shaped calcium copper titanate doped polyarylether nitrile composite material

[0053] S4-1. SPEN@CCTONF prepared in step S3 was dispersed in NMP and ultrasonically treated for 1.5 h to obtain a dispersed SPEN@CCTONF system;

[0054] S4-2. The polymer matrix PEN was added to the dispersed SPEN@CCTONF system, and stirred at 60℃ until completely dissolved; after the mixture was naturally cooled to room temperature, it was poured onto a clean glass plate;

[0055] S4-3. The glass plate in step S4-2 was placed in an oven, and the mixture was dried in the oven with a heating program of 60℃ (1 h), 80℃ (1 h), 100℃ (1 h), 120℃ (2 h) and 160℃ (2 h) to obtain a petal-shaped calcium copper titanate nanomaterial composite dielectric film SPEN@CCTONF / PEN.

[0056] S5. Thermal stretching of petal-shaped calcium copper titanate nanomaterial dielectric film

[0057] The composite dielectric film SPEN@CCTONF / PEN was thermally stretched by uniaxial thermal stretching: the two ends of the composite dielectric film (20 mm x 60 mm) were fixed by clamps, and the original stretching distance was controlled to be 50 mm; one end of the composite dielectric film was hung at the top of the oven, and the other end was hung with a counterweight of 100 g; the distance between the bottom of the oven and the counterweight was adjusted so that the composite dielectric film reached a stretching ratio of 100%; before releasing the counterweight, the composite dielectric film was naturally cooled to room temperature to obtain PEN@CCTONF / PEN-HS, thereby improving the dielectric and energy storage performance of the composite dielectric film.

[0058] The petal-shaped TiO2 micro-morphology prepared in this example is shown in Figure 2 The petal-shaped calcium copper titanate micro-morphology is shown in Figure 3 Figure 4 Comparison of dielectric constant before and after modification of the composite dielectric film;​Figure 5 Comparison of dielectric loss performance of the composite dielectric film before and after modification; Figure 6 Comparison of energy storage density of the composite dielectric film before and after modification; Figure 7 Comparison of energy storage density of the composite dielectric film before and after thermal stretching. As can be seen from the figure, the dielectric and energy storage performance of the modified composite dielectric film is better, and thermal stretching can further improve the energy storage density of the composite dielectric film.

[0059] Example 2

[0060] S1. Preparation of petal-shaped TiO2

[0061] Tetrabutyl titanate TBOT and 5M hydrochloric acid solution were put into a high-pressure reaction kettle at V TBOT :V HCl = 1:50, stirred uniformly, and subjected to hydrothermal reaction, the hydrothermal reaction temperature was 180℃, and the reaction time was 2h; after the reaction was completed, the product was attached to the lining wall of the reaction kettle, which was taken out, centrifuged, washed with deionized water until pH = 7, and then dried in a 60℃ oven for 12h to obtain petal-shaped TiO2(TiO2NF).

[0062] S2. Preparation of petal-shaped copper calcium titanate

[0063] S2-1. Cu(NO3)2·3H2O (1.087g, 4.5mmol), Ca(NO3)2·4H2O (0.354g, 1.5mmol) and TiO2NF (0.479g, 6mmol) prepared in step S1 were placed in a beaker, 100mL of anhydrous ethanol was added, and stirred at room temperature for 24h, and then ultrasonicated for 2h until a uniform suspension was formed;

[0064] S2-2. The suspension was transferred to a high-pressure reaction kettle for solvothermal treatment, the solvothermal reaction temperature was 155℃, and the reaction time was 24h; after the solvothermal reaction, the system was subjected to suction filtration to obtain a tan filter cake;

[0065] S2-3. The filter cake was washed and dried, and then calcined in air atmosphere, the calcination temperature was 800℃, and the calcination time was 2h; the calcined product was stirred in 0.1M dilute hydrochloric acid at room temperature for 1 day, and after washing and drying, petal-shaped copper calcium titanate nanomaterial (CCTONF) was obtained.

[0066] S3. Modification of petal-shaped copper calcium titanate nanomaterial

[0067] S3-1. Ammonia treatment of the surface of CCTONF prepared in step S2 using silane coupling agent KH550: CCTONF (1.0 g) was mixed with anhydrous ethanol (90 mL) and deionized water (10 mL), stirred at room temperature for 6 h and then ultrasonically treated for 0.5 h, and then silane coupling agent KH550 (0.1 g) was added to the dispersion system, heated to reflux, the reflux temperature was 80°C, and the reflux time was 24 h; after suction filtration and drying, KH550-modified CCTONF (CCTONF-KH550) was obtained;

[0068] S3-2. Preparation of functionalized CCTONF with covalently bonded SPEN on the surface (SPEN@CCTONF) by esterification reaction of CCTONF and sulfonated polyarylene ether nitrile SPEN: CCTONF-KH550 (0.5 g) prepared in step S3-1 was dispersed in NMP, stirred at room temperature for 6 h and then ultrasonically treated for 0.5 h, and then SPEN (0.2 g) was added, and stirring and ultrasonic treatment were continued for 0.5 h; the dispersed system was poured into a hydrothermal reactor for solvothermal reaction, the solvothermal reaction temperature was 200°C, and the reaction time was 2 h; after the reaction was completed, the product was filtered, washed and dried to obtain SPEN@CCTONF.

[0069] S4. Preparation of petal-shaped copper-calcium titanate doped polyarylene ether nitrile composite material

[0070] S4-1. SPEN@CCTONF prepared in step S3 was dispersed in NMP and ultrasonically treated for 1.5 h to obtain a dispersed SPEN@CCTONF system;

[0071] S4-2. The polymer matrix PEN was added to the dispersed SPEN@CCTONF system, and stirred at 60°C until completely dissolved, and then the mixture was naturally cooled to room temperature and poured onto a clean glass plate;

[0072] S4-3. The glass plate in step S4-2 was placed in an oven, and the mixture was dried in the oven with a heating program of 60°C (1 h), 80°C (1 h), 100°C (1 h), 120°C (2 h) and 160°C (2 h) to obtain a petal-shaped copper-calcium titanate nanomaterial composite dielectric film SPEN@CCTONF / PEN.

[0073] S5. Thermal stretching of the petal-shaped copper-calcium titanate nanomaterial dielectric film

[0074] The composite dielectric film SPEN@CCTONF / PEN is subjected to uniaxial thermal stretching: the two ends of the composite dielectric film (20 mm x 60 mm) are fixed by clamps, and the original stretching distance is controlled to be 50 mm; one end of the composite dielectric film is hung at the top of the oven, and the other end is hung with a counterweight of 100 g; the distance between the bottom of the oven and the counterweight is adjusted so that the composite dielectric film reaches a stretching ratio of 100%; before the counterweight is released, the composite dielectric film is naturally cooled to room temperature to obtain PEN@CCTONF / PEN-HS, thereby improving the dielectric and energy storage properties of the composite dielectric film.

[0075] Example 3

[0076] S1. Preparation of petal-shaped TiO2

[0077] Tetrabutyl titanate TBOT and 5M hydrochloric acid solution are put into a high-pressure reaction kettle at V TBOT :V HCl = 1:30, stirred uniformly, and subjected to hydrothermal reaction, the hydrothermal reaction temperature is 180℃, and the reaction time is 2h; after the reaction is completed, the product is attached to the lining wall of the reaction kettle, which is taken down, centrifuged, washed with deionized water until pH = 7, and then dried in a 60℃ oven for 12h to obtain petal-shaped TiO2(TiO2NF).

[0078] S2. Preparation of petal-shaped calcium copper titanate

[0079] S2-1. Cu(NO3)2·3H2O (1.087g, 4.5mmol), Ca(NO3)2·4H2O (0.354g, 1.5mmol) and TiO2NF (0.479g, 6mmol) prepared in step S1 are placed in a beaker, 100mL of anhydrous ethanol is added, and stirring is carried out at room temperature for 24h, and ultrasonic treatment is continued for 2h until a uniform suspension is formed;

[0080] S2-2. The suspension is transferred to a high-pressure reaction kettle for solvothermal treatment, the solvothermal reaction temperature is 155℃, and the reaction time is 24h; after the solvothermal reaction, the system is subjected to suction filtration to obtain a tan filter cake;

[0081] S2-3. The filter cake is washed and dried, and then calcined in an air atmosphere, the calcination temperature is 800℃, and the calcination time is 2h; the calcined product is stirred in 0.1M dilute hydrochloric acid at room temperature for 1 day, and after washing and drying, petal-shaped calcium copper titanate nanomaterial (CCTONF) is obtained.

[0082] S3. Modification of petal-shaped calcium copper titanate nanomaterial

[0083] S3-1. Ammonia treatment of the surface of CCTONF prepared in step S2 with silane coupling agent KH550: CCTONF (1.0 g) was mixed with anhydrous ethanol (90 mL) and deionized water (10 mL), stirred at room temperature for 6 h and then ultrasonically treated for 0.5 h, and then silane coupling agent KH550 (0.1 g) was added to the dispersion system, heated to reflux, the reflux temperature was 80°C, and the reflux time was 24 h; after suction filtration and drying, KH550-modified CCTONF (CCTONF-KH550) was obtained;

[0084] S3-2. Preparation of functionalized CCTONF with covalently bonded SPEN on the surface (SPEN@CCTONF) by esterification reaction of CCTONF and sulfonated polyarylene ether nitrile SPEN: CCTONF-KH550 (0.5 g) prepared in step S3-1 was dispersed in NMP, stirred at room temperature for 6 h and then ultrasonically treated for 0.5 h, and then SPEN (0.2 g) was added, and stirring and ultrasonic treatment were continued for 0.5 h; the dispersed system was poured into a hydrothermal reactor for solvothermal reaction, the solvothermal reaction temperature was 200°C, and the reaction time was 2 h; after the reaction was completed, the product was filtered, washed and dried to obtain SPEN@CCTONF.

[0085] S4. Preparation of petal-shaped calcium copper titanate doped polyarylene ether nitrile composite material

[0086] S4-1. SPEN@CCTONF prepared in step S3 was dispersed in NMP and ultrasonically treated for 1.5 h to obtain a dispersed SPEN@CCTONF system;

[0087] S4-2. The polymer matrix PEN was added to the dispersed SPEN@CCTONF system, and stirred at 60°C until completely dissolved, and then the mixture was naturally cooled to room temperature and poured onto a clean glass plate;

[0088] S4-3. The glass plate in step S4-2 was placed in an oven, and the mixture was dried in the oven with a heating program of 60°C (1 h), 80°C (1 h), 100°C (1 h), 120°C (2 h) and 160°C (2 h) to obtain a petal-shaped calcium copper titanate nanomaterial composite dielectric film SPEN@CCTONF / PEN.

[0089] S5. Thermal stretching of the petal-shaped calcium copper titanate nanomaterial dielectric film

[0090] The composite dielectric film SPEN@CCTONF / PEN is uniaxially heat stretched: the two ends of the composite dielectric film (20 mm×60 mm) are fixed by clamps, and the original stretching distance is controlled to be 50 mm; one end of the composite dielectric film is hung at the top of the oven, and the other end is hung with a counterweight of 100 g; the distance between the bottom of the oven and the counterweight is adjusted so that the composite dielectric film reaches a stretching ratio of 100%; before the counterweight is released, the composite dielectric film is naturally cooled to room temperature to obtain PEN@CCTONF / PEN-HS, thereby improving the dielectric and energy storage performance of the composite dielectric film.

[0091] The above only describes the preferred embodiments of the present application, and it should be noted that those skilled in the art can make several improvements and modifications without departing from the technical principles of the present application, and these improvements and modifications should also be considered as the protection scope of the present application.

Claims

1. A method for preparing petal-shaped calcium copper titanate nanomaterials, characterized in that, The preparation method comprises the following steps: S1. Preparation of petal-shaped TiO2 TBOT and hydrochloric acid solution are put into a high-pressure reactor, stirred uniformly, and subjected to hydrothermal reaction. After the reaction is completed, centrifugation is performed, deionized water is used for washing until pH is 7, and then drying is performed, to obtain petal-shaped TiO2; S2. Preparation of petal-shaped calcium copper titanate S2-1. Cu(NO3)2·3H2O, Ca(NO3)2·4H2O and the petal-shaped TiO2 prepared in step S1 are placed in a beaker, anhydrous ethanol is added, and stirring and ultrasonic treatment are performed under normal temperature conditions until a uniform suspension is formed; S2-2. The suspension is transferred to a high-pressure reactor for solvothermal treatment. After solvothermal reaction, the system is subjected to suction filtration, to obtain a brownish yellow filter cake; S2-3. The filter cake is washed and dried, and then calcination is performed in an air atmosphere. The product after calcination is stirred in dilute hydrochloric acid at normal temperature. After washing and drying, petal-shaped calcium copper titanate nanomaterial, namely CCTONF, is obtained; S3. Modification of petal-shaped calcium copper titanate nanomaterial S3-1. The surface of CCTONF prepared in step S2 is subjected to aminization treatment by using silane coupling agent KH550, to obtain KH550-modified CCTONF, namely CCTONF-KH550; S3-2. Functionalized CCTONF with covalently bonded SPEN on the surface is prepared by esterification reaction of CCTONF and sulfonated polyarylether nitrile SPEN, to obtain SPEN-modified CCTONF, namely SPEN@CCTONF; S4. Preparation of petal-shaped calcium copper titanate-doped polyarylether nitrile composite material S4-1. SPEN@CCTONF prepared in step S3 is dispersed in NMP, and ultrasonic treatment is performed, to obtain a dispersed SPEN@CCTONF system; S4-2. The polymer matrix is added to the dispersed SPEN@CCTONF system, and stirring is performed until complete dissolution. After the mixture is naturally cooled to room temperature, it is poured onto a glass plate; S4-3. The glass plate in step S4-2 is placed in an oven, and the mixture is dried in the oven, to obtain a petal-shaped calcium copper titanate nanomaterial composite dielectric film.

2. The petal-shaped copper calcium titanate nanomaterial preparation method of claim 1, wherein, In step S1, V TBOT :V HCl = 1 : (30-70); hydrothermal reaction temperature is 180°C, reaction time is 2h; drying in 60°C oven for 12h.

3. The petal-shaped copper calcium titanate nanomaterial preparation method of claim 1, wherein, In step S2-1, stirring is performed for 24 h under normal temperature conditions, and ultrasonic treatment is continued for 2 h. In step S2-2, the solvothermal reaction temperature is 155℃, and the reaction time is 24 h. In step S2-3, the calcination temperature is 800℃, and the calcination time is 2 h. The product after calcination is stirred in dilute hydrochloric acid at normal temperature for 1 day.

4. The petal-shaped copper calcium titanate nanomaterial preparation method of claim 1, wherein, In step S3-1, the CCTONF is mixed with anhydrous ethanol and deionized water, the ratio of anhydrous ethanol and deionized water is V EtOH :V H2O = 9:1, stirred at room temperature for 6h, then ultrasonic treated for 0.5h, then silane coupling agent KH550 is added in the dispersion system, heated to reflux, the reflux temperature is 80℃, the reflux time is 24h; after suction filtration and drying, the KH550 modified CCTONF is obtained.

5. The petal-shaped copper calcium titanate nanomaterial preparation method of claim 1, wherein, In step S3-2, CCTONF-KH550 prepared in step S3-1 is dispersed in NMP, and stirring is performed at room temperature for 6 h and ultrasonic treatment is performed for 0.5 h. Then, SPEN is added, and stirring and ultrasonic treatment are continued. The dispersed system is poured into a hydrothermal reactor for solvothermal reaction. The solvothermal reaction temperature is 200℃, and the reaction time is 2 h. After the reaction is completed, the obtained product is subjected to filtration, washing and drying, to obtain SPEN-modified CCTONF, namely SPEN@CCTONF.

6. The petal-shaped copper calcium titanate nanomaterial preparation method of claim 1, wherein, In step S4-2, the polymer matrix material comprises at least one of polyethylene, polyester amide, biaxially oriented polypropylene, polyarylether nitrile, polyvinylidene fluoride, epoxy resin and polymethyl methacrylate.

7. The method for preparing petal-shaped calcium copper titanate nanomaterials as described in claim 1, characterized in that, Further comprising, step S5. The petal-shaped calcium copper titanate nanomaterial composite dielectric film is heat stretched.

8. The petal-shaped copper calcium titanate nanomaterial preparation method of claim 7, wherein, In step S5, the uniaxial heat stretching method is used to heat stretch the composite dielectric film.

9. The petal-shaped copper calcium titanate nanomaterial preparation method of claim 8, wherein, In step S5, the original size of the composite dielectric film is 20mm*60mm, both ends of the composite dielectric film are fixed, the original stretching distance is controlled to be 50mm; one end of the composite dielectric film is hung at the top of the oven, the other end is hung with a counterweight of 100g, the distance between the bottom of the oven and the counterweight is adjusted, the heat stretching temperature is 200℃, the composite dielectric film reaches a stretching ratio of 100%, and the composite dielectric film is naturally cooled to room temperature before the counterweight is released.

10. A petal-shaped copper calcium titanate nanomaterial, characterized in that, The petal-shaped calcium copper titanate nanomaterial is prepared by the method in any one of claims 1-9.

Images