Preparation method of core-shell nano zirconium oxide@titanium oxide particle-polypropylene-polytetramethyl one pentene composite

Abstract

The application discloses a preparation method of a core-shell nano zirconium oxide@titanium oxide particle-polypropylene-polytetramethylpentene composite material, and the method comprises the following steps: mixing solution A and solution B to obtain a mixed solution with ZrO2@Ti(OH)4 nanoparticles; pouring slurry A into slurry B, and performing a modification reaction through constant-temperature heating, stirring and dehydration condensation; after the modification reaction is completed, centrifugal treatment and centrifugal cleaning are performed on the mixed solution to obtain modified hydroxyl-rich ZrO2@TiO2 core-shell nanoparticles; and poly-4-methyl-1-pentene, polypropylene and the modified hydroxyl-rich ZrO2@TiO2 core-shell nanoparticles with a mass ratio of 49.75wt%:49.75wt%:0.5wt% are poured into a torque rheometer to be blended to obtain the core-shell nano zirconium oxide@titanium oxide particle-polypropylene-poly-4-methyl-1-pentene composite material.

Description

Technical Field

[0001] This invention belongs to the field of power capacitor technology, specifically a method for preparing core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material. Background Technology

[0002] With the continuous development of AC / DC power transmission technology and the integration of new energy sources in my country, power capacitors need to meet more stringent usage requirements. The performance of a capacitor is mainly determined by its dielectric material. Currently, the most widely used capacitor dielectric material is biaxially oriented polypropylene (BOPP) film, which has advantages such as excellent electrical properties and simple processing. However, as a non-polar polymer, the low dielectric constant of BOPP film results in excessively low energy storage density, leading to excessively large volume in various power equipment. Furthermore, as the temperature rises, the breakdown field strength of BOPP film decreases rapidly, and the conductivity loss increases sharply, failing to meet the requirements of high-temperature energy storage. Therefore, it is necessary to modify polypropylene to obtain composite materials with high energy storage density and high-temperature resistance.

[0003] Currently, common methods for modifying polypropylene include nanocompositing and blending. Nanocomposite dielectrics refer to composites with nanostructures formed by filling inorganic particles with sizes between 1 and 100 nm into a polymer matrix, resulting in at least one altered property. Nanocomposite modification can achieve complementary advantages between inorganic and organic materials. Adding high-dielectric-constant inorganic nanoparticles to polypropylene can significantly improve the dielectric constant of the composite material. Simultaneously, due to the unique properties of nanoparticles, nanofilling also has a certain gain effect on the breakdown field strength of the composite material. However, because of the significant differences in physicochemical properties between nanoparticles and polypropylene, nanoparticles are prone to agglomeration and uneven dispersion in the matrix, leading to electric field distortion. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a method for preparing a core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, which improves the dispersion of nanoparticles in the matrix and enhances the energy storage density and high-temperature electrical properties of the material.

[0005] The preparation methods of core-shell zirconia@titanium oxide nanoparticles-polypropylene-polytetramethylpentene composite materials include:

[0006] ZrO2@TiO2 core-shell nanofiller was ground to obtain nanoparticles, which were then dried.

[0007] Weigh out nanoparticles and place them in a container. Add water and isopropanol, heat at a constant temperature and stir to mix evenly to obtain solution A. The ratio of nanoparticles: water: isopropanol is 1g:200ml:50ml.

[0008] Weigh out anhydrous ethanol, isopropanol, tetrabutyl titanate and deionized water in a ratio of 1ml:1ml:0.1ml:0.5ml. First, place the weighed anhydrous ethanol, isopropanol and tetrabutyl titanate (TBOT) in another container and stir to mix evenly. Then, add the weighed deionized water to the container and stir evenly to obtain solution B.

[0009] Mix solution A and solution B, maintain the heating temperature of solution A and magnetic stirring, add solution B and continue the reaction for a predetermined time to generate Ti(OH)4 on the surface of nanoparticles, and obtain a mixed solution with ZrO2@Ti(OH)4 nanoparticles;

[0010] The mixed solution was poured into a centrifuge tube and centrifuged with deionized water as the cleaning solvent to obtain moist ZrO2@Ti(OH)4 nanoparticles.

[0011] ZrO2@Ti(OH)4 nanoparticles are transferred into a sintering furnace for sintering, causing Ti(OH)4 to undergo a dehydration condensation reaction to generate ZrO2@TiO2 core-shell nanoparticles, which are then uniformly ground.

[0012] The nanoparticles were enriched with hydroxyl groups. ZrO2@TiO2 core-shell nanoparticles with a ratio of 1g:100mL and 0.1mol / L hydrochloric acid solution were weighed and mixed into a slurry. The mixture was then magnetically stirred until homogeneous. After centrifugation, washing, drying, grinding and sieving, hydroxylated ZrO2@TiO2 core-shell nanoparticles were obtained.

[0013] Hydroxylated ZrO2@TiO2 core-shell nanoparticles in a ratio of 1g:100ml were weighed and added to a container with anhydrous ethanol. After stirring, the mixture was ultrasonically dispersed to obtain slurry A. Silane coupling agent KH570, anhydrous ethanol, and 0.1mol / L hydrochloric acid solution in a ratio of 1ml:4ml:4ml were weighed and mixed evenly by heating at a constant temperature to obtain slurry B. Slurry A was poured into slurry B and heated at a constant temperature with stirring to dehydrate and condense for modification. After the modification reaction was completed, the mixed solution was centrifuged and washed to obtain modified hydroxylated ZrO2@TiO2 core-shell nanoparticles.

[0014] A composite material of core-shell zirconia nanoparticles-polypropylene-polytetramethyl-1-pentene was obtained by blending poly(4-methyl-1-pentene), polypropylene, and modified hydroxylated ZrO2@TiO2 core-shell nanoparticles with a mass ratio of 49.75wt%:49.75wt%:0.5wt% in a torque rheometer.

[0015] In the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, ZrO2@TiO2 core-shell nanofiller is ground in an agate mortar, and then the temperature of the forced-air drying oven is set to 60℃ and the drying time is more than 12 hours.

[0016] In the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, the heating temperature of the constant temperature magnetic heating stage for uniformly mixing and heating to obtain solution A is 40℃, and the magnetic stirring time is 30 minutes.

[0017] In the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, the predetermined reaction time is 20 hours.

[0018] In the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, the mixed solution containing ZrO2@Ti(OH)4 nanoparticles is treated with a centrifuge with a centrifugal force of 3000g for 10 minutes. After centrifugation, the mixed solution is poured out and centrifuged repeatedly four times with deionized water as the cleaning solvent.

[0019] In the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, the sintering temperature of the sintering furnace is 650℃ and the holding time is 10 hours.

[0020] In the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, after the mixed slurry is magnetically stirred evenly, it is ultrasonically dispersed for 15 minutes.

[0021] In the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, hydroxylated ZrO2@TiO2 core-shell nanoparticles are added to a container with anhydrous ethanol and stirred, and then ultrasonically dispersed for 30 minutes.

[0022] In the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, the silane coupling agent KH570, anhydrous ethanol, and 0.1 mol / L hydrochloric acid solution are mixed in a ratio of 1 ml:4 ml:4 ml and heated and stirred at a constant temperature of 80°C with magnetic stirring for 30 min.

[0023] In the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, slurry A is poured into slurry B and heated and stirred at a constant temperature of 110°C for 4 hours.

[0024] Compared with the prior art, the present invention has the following advantages:

[0025] A method for preparing core-shell zirconia@titanium oxide nanoparticles-polypropylene-polytetramethyl-pentene composite materials reveals a high energy storage density and maintains a high DC breakdown field strength even at high temperatures. Poly(4-methyl-1-pentene) is a nonpolar semi-crystalline polymer with a higher melting temperature (~233℃) and lower density (0.84 g / cm³) compared to BOPP, showing potential for use as a capacitor film at high temperatures. By preparing core-shell structured zirconia@titanium oxide nanoparticles and blending them with poly(4-methyl-1-pentene) and polypropylene, the energy storage density and high-temperature electrical properties of the material can be improved. Attached Figure Description

[0026] The accompanying drawings illustrate exemplary embodiments of the invention and, together with the description thereof, serve to explain the principles of the invention. These drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification.

[0027] Figure 1 This is a Weibull distribution diagram of the DC breakdown field strength of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethyl-pentene composite material prepared by the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethyl-pentene composite material in one embodiment of the present invention at different temperatures.

[0028] Figure 2 This is a schematic diagram showing the energy storage density of the core-shell zirconia@titanium oxide particle-polypropylene-polytetramethylpentene composite material prepared by the preparation method of the core-shell zirconia@titanium oxide particle-polypropylene-polytetramethylpentene composite material in one embodiment of the present invention at different temperatures. Detailed Implementation

[0029] The following is in conjunction with the appendix Figures 1 to 2 The present invention will be further described in detail below with reference to the embodiments. It is to be understood that the specific embodiments described herein are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be noted that, for ease of description, only the parts relevant to the present invention are shown in the accompanying drawings.

[0030] It should be noted that, unless otherwise specified, the embodiments and features described in this invention can be combined with each other. The technical solution of this invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0031] Unless otherwise stated, the exemplary embodiments / exemplifications shown are to be understood as providing exemplary features of various details that provide ways in which the technical concept of the invention can be implemented in practice. Therefore, unless otherwise stated, the features of the various embodiments / exemplifications may be additionally combined, separated, interchanged and / or rearranged without departing from the technical concept of the invention.

[0032] Crosshairs and / or shading may be used in the accompanying drawings to clarify the boundaries between adjacent components. Thus, unless otherwise stated, the presence or absence of crosshairs or shading does not convey or indicate any preference or requirement for the specific material, material properties, dimensions, proportions, commonalities between the illustrated components, or any other characteristics, properties, etc., of the components. Furthermore, the dimensions and relative dimensions of components may be exaggerated in the accompanying drawings for clarity and / or descriptive purposes. When exemplary embodiments can be implemented differently, a specific process sequence may be performed in a manner different from the described order of steps. For example, two consecutively described processes may be performed substantially simultaneously or in the reverse order of the described process. Moreover, the same reference numerals denote the same components.

[0033] When a component is referred to as being "on" or "above" another component, "connected to," or "joined to" another component, the component may be directly on, directly connected to, or directly joined to the other component, or there may be intermediate components. However, when a component is referred to as being "directly on" another component, "directly connected to," or "directly joined to" another component, there are no intermediate components. Therefore, the term "connection" can refer to a physical connection, an electrical connection, etc., and may or may not have intermediate components.

[0034] For descriptive purposes, the present invention may use spatial relative terms such as “below,” “under,” “below,” “down,” “above,” “above,” “higher,” and “side (e.g., in a “sidewall”)” to describe the relationship between one component and another component as shown in the accompanying drawings. In addition to the orientations depicted in the drawings, the spatial relative terms are also intended to encompass different orientations of the device during use, operation, and / or manufacture. For example, if the device in the drawings is flipped, a component described as “below” or “under” another component or feature would subsequently be positioned “above” said other component or feature. Thus, the exemplary term “below” can encompass both “above” and “below” orientations. Furthermore, the device may be otherwise positioned (e.g., rotated 90 degrees or in other orientations), thus interpreting the spatial relative descriptive terms used herein accordingly.

[0035] The terminology used herein is for the purpose of describing particular embodiments and is not intended to be limiting. As used herein, unless the context clearly indicates otherwise, the singular forms “a” and “the” are intended to include the plural forms as well. Furthermore, when the terms “comprising” and / or “including” and variations thereof are used in this specification, it indicates the presence of the stated features, integrals, steps, operations, parts, components, and / or groups thereof, but does not exclude the presence or addition of one or more other features, integrals, steps, operations, parts, components, and / or groups thereof. It should also be noted that, as used herein, the terms “substantially,” “about,” and other similar terms are used as approximate terms rather than as terms of degree, thus explaining the inherent biases in measurements, calculated values, and / or provided values ​​that would be recognized by one of ordinary skill in the art.

[0036] See Figures 1 to 2 In one embodiment, the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material of the present invention includes:

[0037] ZrO2@TiO2 core-shell nanofiller was ground to obtain nanoparticles, which were then dried.

[0038] Weigh out nanoparticles and place them in a container. Add water and isopropanol, heat at a constant temperature and stir to mix evenly to obtain solution A. The ratio of nanoparticles: water: isopropanol is 1g:200ml:50ml.

[0039] Weigh out anhydrous ethanol, isopropanol, tetrabutyl titanate and deionized water in a ratio of 1ml:1ml:0.1ml:0.5ml. First, place the weighed anhydrous ethanol, isopropanol and tetrabutyl titanate (TBOT) in another container and stir to mix evenly. Then, add the weighed deionized water to the container and stir evenly to obtain solution B.

[0040] Mix solution A and solution B, maintain the heating temperature of solution A and magnetic stirring, add solution B and continue the reaction for a predetermined time to generate Ti(OH)4 on the surface of nanoparticles, and obtain a mixed solution with ZrO2@Ti(OH)4 nanoparticles;

[0041] The mixed solution was poured into a centrifuge tube and centrifuged with deionized water as the cleaning solvent to obtain moist ZrO2@Ti(OH)4 nanoparticles.

[0042] ZrO2@Ti(OH)4 nanoparticles are transferred into a sintering furnace for sintering, causing Ti(OH)4 to undergo a dehydration condensation reaction to generate ZrO2@TiO2 core-shell nanoparticles, which are then uniformly ground.

[0043] The nanoparticles were enriched with hydroxyl groups. ZrO2@TiO2 core-shell nanoparticles with a ratio of 1g:100mL and 0.1mol / L hydrochloric acid solution were weighed and mixed into a slurry. The mixture was then magnetically stirred until homogeneous. After centrifugation, washing, drying, grinding and sieving, hydroxylated ZrO2@TiO2 core-shell nanoparticles were obtained.

[0044] Hydroxylated ZrO2@TiO2 core-shell nanoparticles in a ratio of 1g:100ml were weighed and added to a container with anhydrous ethanol. After stirring, the mixture was ultrasonically dispersed to obtain slurry A. Silane coupling agent KH570, anhydrous ethanol, and 0.1mol / L hydrochloric acid solution in a ratio of 1ml:4ml:4ml were weighed and mixed evenly by heating at a constant temperature to obtain slurry B. Slurry A was poured into slurry B and heated at a constant temperature with stirring to dehydrate and condense for modification. After the modification reaction was completed, the mixed solution was centrifuged and washed to obtain modified hydroxylated ZrO2@TiO2 core-shell nanoparticles.

[0045] Polypropylene is the most commonly used solid dielectric material, possessing advantages such as low loss, high breakdown field strength, and ease of preparation. Poly(4-methyl-1-pentene) has a high melting temperature and excellent electrical properties at high temperatures. Mixing polypropylene and poly(4-methyl-1-pentene) in a 1:1 ratio combines the advantages of both materials. The effect of varying core-shell nanoparticle concentrations on the DC breakdown field strength of the material was compared. When the core-shell nanoparticle concentrations were 0%, 0.5 wt%, 1 wt%, and 3 wt%, the corresponding breakdown field strengths were 398.1 kV / mm, 447.9 kV / mm, 429.8 kV / mm, and 404.6 kV / mm, respectively. Higher nanoparticle concentrations led to agglomeration, resulting in a decrease in the breakdown field strength; the optimal concentration was 0.5 wt%. Therefore, a composite material of core-shell zirconia nanoparticles-polypropylene-polytetramethyl-1-pentene was obtained by blending poly(4-methyl-1-pentene), polypropylene, and modified hydroxylated ZrO2@TiO2 core-shell nanoparticles with a mass ratio of 49.75wt%:49.75wt%:0.5wt% in a torque rheometer.

[0046] In a preferred embodiment of the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, ZrO2@TiO2 core-shell nanofiller is ground in an agate mortar, and then the temperature of the forced-air drying oven is set to 60°C and the drying time is more than 12 hours.

[0047] In a preferred embodiment of the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, the heating temperature of the constant temperature magnetic heating stage for uniformly mixing and heating to obtain solution A is 40°C, and the magnetic stirring time is 30 minutes.

[0048] In a preferred embodiment of the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, the predetermined reaction time is 20 hours.

[0049] In a preferred embodiment of the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, the mixed solution containing ZrO2@Ti(OH)4 nanoparticles is treated with a centrifuge with a centrifugal force of 3000g for 10 minutes. After centrifugation, the mixed solution is poured out and centrifuged repeatedly four times with deionized water as the cleaning solvent.

[0050] In a preferred embodiment of the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, the sintering temperature of the sintering furnace is 650°C and the holding time is 10 hours.

[0051] In a preferred embodiment of the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, after the mixed slurry is magnetically stirred evenly, it is ultrasonically dispersed for 15 minutes.

[0052] In a preferred embodiment of the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, hydroxylated ZrO2@TiO2 core-shell nanoparticles are added to a container with anhydrous ethanol and stirred before being ultrasonically dispersed for 30 minutes.

[0053] In a preferred embodiment of the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, the silane coupling agent KH570, anhydrous ethanol, and 0.1 mol / L hydrochloric acid solution are mixed in a ratio of 1 ml:4 ml:4 ml and heated and stirred at a constant temperature of 80°C with magnetic stirring for 30 min.

[0054] In a preferred embodiment of the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, slurry A is poured into slurry B and heated and stirred at a constant temperature of 110°C for 4 hours.

[0055] In one embodiment, the preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material includes,

[0056] Before preparing the shell, the raw materials are pretreated, mainly including screening the particle size of the nanofiller and surface drying, to ensure that the nanoparticles used are relatively uniform in size and that there is no moisture on the surface that could affect the reaction process. The nanoparticles are ground in an agate mortar and pestle, and the drying oven is set at 60°C for more than 12 hours. The pretreated nanoparticles are then removed and set aside for use.

[0057] Weigh 0.5g of ZrO2 nanoparticles and place them in a clean 250mL three-necked flask. Add 100mL of water, 25mL of isopropanol and a small magnetic stir bar. Set the heating temperature of the constant temperature magnetic heating stage to 40℃ and the magnetic stirring time to 30 minutes to prepare a well-mixed solution A.

[0058] Take another clean beaker and measure 20 mL of anhydrous ethanol, 20 mL of isopropanol, and 2 mL of tetrabutyl titanate (TBOT) into it using a graduated cylinder. Add the beaker to a small magnetic stirrer and mix thoroughly with a magnetic stirrer. Then weigh 10 mL of deionized water and slowly add it to the beaker while stirring rapidly with a glass rod to prepare solution B.

[0059] Mixing of solutions A and B: While maintaining the heating temperature and magnetic stirring of solution A, pour solution B into a three-necked flask and set the reaction time to 20 hours. During this process, TBOT will slowly hydrolyze, generating Ti(OH)4 on the surface of the nanoparticles.

[0060] Nanoparticle cleaning: After the reaction was completed, a mixed solution containing ZrO2@Ti(OH)4 nanoparticles was obtained. The mixed solution was poured into centrifuge tubes, and the centrifuge force was adjusted to 3000g for 10 minutes to centrifuge the mixed solution. After the centrifugation, the solution was poured out and washed repeatedly by centrifugation 4 times with deionized water as the washing solvent.

[0061] High-temperature dehydration of Ti(OH)4: After washing, initially moistened ZrO2@Ti(OH)4 nanoparticles are obtained. The temperature of the forced-air drying oven is set to 60℃, and the drying time is about 12 hours or more. Using a clean spatula, the granular material, which is in block form, is transferred into a ceramic crucible of appropriate size. After covering, it is transferred into a high-temperature precision sintering furnace. The sintering temperature is set to 650℃, and the holding time is 10 hours. During this process, Ti(OH)4 will undergo a dehydration condensation reaction to generate ZrO2@TiO2 "core-shell" nanoparticles.

[0062] Grinding of "core-shell" nanoparticles: After calcination, the granules are formed into blocks. The blocks of granules are scooped out and ground into uniform particles using an agate mortar and pestle for further use.

[0063] Hydroxylation of nanoparticle surface: First, nanoparticles and 0.1mol / L hydrochloric acid solution are weighed at a ratio of 1g:100mL and mixed into a slurry. Then, the mixture is magnetically stirred to initially disperse it evenly. Next, the ultrasonic dispersion time is set for 15min. The mixed solution is then poured out and subjected to centrifugation, washing, drying, grinding and sieving.

[0064] Preparation of slurry A and slurry B: Weigh 2g of hydroxylated "core-shell" nanoparticles and add them together with 200mL of anhydrous ethanol into a beaker of appropriate size. Set the magnetic stirring time to 5 minutes, then set the ultrasonic dispersion time to 30 minutes to prepare a homogeneous mixed solution A. Take another clean three-necked flask and pour in 10mL of silane coupling agent KH570, 40mL of anhydrous ethanol, 40mL of 0.1mol / L hydrochloric acid solution, and a magnetic stir bar of appropriate size. Set the constant temperature heater to maintain the temperature at 80℃ and stir magnetically for 30 minutes.

[0065] Mixing of slurry A and slurry B: After the two solutions have been mixed, pour slurry A into a flask containing slurry B, change the heating temperature to 110°C, and set the magnetic stirring time to 4 hours. During this process, the solution system undergoes a modification reaction through dehydration condensation.

[0066] Separation and cleaning of nanoparticles: After the reaction, the mixed solution was poured into centrifuge tubes. The centrifuge was set to 3000g and centrifuged for 10 minutes. After centrifugation, the solution was poured out, and then clean anhydrous ethanol was added as a cleaning solution. The mixture was then centrifuged again under the same conditions. This process was repeated four times to ensure the nanoparticle surface remained clean.

[0067] Preparation of composite material: 49.75 wt% poly(4-methyl-1-pentene) and 49.75 wt% polypropylene were mixed with modified hydroxylated ZrO2@TiO2 core-shell nanoparticles and poured into a torque rheometer. The heating temperature was set to 180 ℃ and the rotation speed to 40 r / min. The mixture was blended for 10 minutes to obtain a core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethyl-pentene composite material.

[0068] Figure 1 This is a Weibull distribution diagram of the DC breakdown field strength of a core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethyl-pentene composite material of the present invention at different temperatures. It can be seen that the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethyl-pentene composite material still maintains a high DC breakdown field strength at a high temperature of 120 degrees Celsius.

[0069] Figure 2This invention relates to the energy storage density of a core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethyl-pentene composite material at different temperatures. It can be seen that the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethyl-pentene composite material still maintains a high energy storage density at a high temperature of 120 degrees Celsius.

[0070] In the description of this specification, the references to terms such as "one embodiment / mode," "some embodiments / modes," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment / mode or example is included in at least one embodiment / mode or example of this application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment / mode or example. Moreover, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments / modes or examples. Furthermore, without contradiction, those skilled in the art can combine and integrate the different embodiments / modes or examples described in this specification, as well as the features of different embodiments / modes or examples.

[0071] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this application, "multiple" means at least two, such as two, three, etc., unless otherwise explicitly specified.

[0072] Those skilled in the art should understand that the above embodiments are merely for illustrating the present invention and are not intended to limit the scope of the invention. Those skilled in the art can make other changes or modifications based on the above disclosure, and these changes or modifications still fall within the scope of the present invention.

Claims

1. A method for preparing a core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material, characterized in that, It includes the following steps: ZrO2@TiO2 core-shell nanofiller was ground to obtain nanoparticles, which were then dried. Weigh out nanoparticles and place them in a container. Add water and isopropanol, heat at a constant temperature and stir to mix evenly to obtain solution A. The ratio of nanoparticles: water: isopropanol is 1g:200ml:50ml. Weigh out anhydrous ethanol, isopropanol, tetrabutyl titanate and deionized water in a ratio of 1ml:1ml:0.1ml:0.5ml. First, place the weighed anhydrous ethanol, isopropanol and tetrabutyl titanate (TBOT) in another container and stir to mix evenly. Then, add the weighed deionized water to the container and stir evenly to obtain solution B. Mix solution A and solution B, maintain the heating temperature of solution A and magnetic stirring, add solution B and continue the reaction for a predetermined time to generate Ti(OH)4 on the surface of nanoparticles, and obtain a mixed solution with ZrO2@Ti(OH)4 nanoparticles; The mixed solution was poured into a centrifuge tube and centrifuged with deionized water as the cleaning solvent to obtain moist ZrO2@Ti(OH)4 nanoparticles. ZrO2@Ti(OH)4 nanoparticles are transferred into a sintering furnace for sintering, causing Ti(OH)4 to undergo a dehydration condensation reaction to generate ZrO2@TiO2 core-shell nanoparticles, which are then uniformly ground. The nanoparticles were enriched with hydroxyl groups. ZrO2@TiO2 core-shell nanoparticles with a ratio of 1g:100mL were weighed and mixed with 0.1mol / L hydrochloric acid solution to prepare a mixed slurry. The mixture was then magnetically stirred until homogeneous. After centrifugation, washing, drying, grinding and sieving, hydroxylated ZrO2@TiO2 core-shell nanoparticles were obtained. Hydroxylated ZrO2@TiO2 core-shell nanoparticles in a ratio of 1g:100ml were weighed and added to a container with anhydrous ethanol. After stirring, the mixture was ultrasonically dispersed to obtain slurry A. Silane coupling agent KH570, anhydrous ethanol, and 0.1mol / L hydrochloric acid solution in a ratio of 1ml:4ml:4ml were weighed and mixed evenly by heating at a constant temperature to obtain slurry B. Slurry A was poured into slurry B and heated at a constant temperature with stirring to dehydrate and condense for modification. After the modification reaction was completed, the mixed solution was centrifuged and washed to obtain modified hydroxylated ZrO2@TiO2 core-shell nanoparticles. A composite material of core-shell zirconia@titanium oxide nanoparticles-polypropylene-polytetramethyl-1-pentene was obtained by blending poly(4-methyl-1-pentene), polypropylene, and modified hydroxylated ZrO2@TiO2 core-shell nanoparticles in a torque rheometer at a mass ratio of 49.75wt%:49.75wt%:0.5wt%. The composite material exhibits a strength of 0.98 J / cm² at 120°C. 3 The energy storage density is determined. Slurry A is poured into slurry B and heated and stirred at a constant temperature of 110°C. The magnetic stirring time is set to 4 hours.

2. The method for preparing the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material according to claim 1, characterized in that, The ZrO2@TiO2 core-shell nanofiller was ground in an agate mortar and pestle, and then the temperature of the forced-air drying oven was set to 60℃ and the drying time was more than 12 hours.

3. The preparation method of the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material according to claim 1, characterized in that, The temperature of the constant-temperature magnetic heating table for obtaining solution A by constant-temperature heating and stirring is 40℃, and the magnetic stirring time is 30 minutes.

4. The method for preparing the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material according to claim 1, characterized in that, The planned response time is 20 hours.

5. The method for preparing the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material according to claim 1, characterized in that, The mixed solution containing ZrO2@Ti(OH)4 nanoparticles was centrifuged at a centrifuge with a centrifugal force of 3000 g for 10 minutes. After centrifugation, the mixed solution was poured out and washed with deionized water as the washing solvent, and then centrifuged and washed 4 times.

6. The method for preparing the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material according to claim 1, characterized in that, The sintering temperature of the sintering furnace is 650℃, and the holding time is 10 hours.

7. The method for preparing the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material according to claim 1, characterized in that, After mixing the slurry, stir it magnetically until it is uniform, and then disperse it ultrasonically for 15 minutes.

8. The method for preparing the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material according to claim 1, characterized in that, Hydroxylated ZrO2@TiO2 core-shell nanoparticles were added to a container with anhydrous ethanol and stirred before being ultrasonically dispersed for 30 minutes.

9. The method for preparing the core-shell nano-zirconia@titanium oxide particles-polypropylene-polytetramethylpentene composite material according to claim 1, characterized in that, The mixture of silane coupling agent KH570, anhydrous ethanol, and 0.1 mol / L hydrochloric acid solution in a ratio of 1 ml:4 ml:4 ml was heated and stirred at a constant temperature of 80°C with magnetic stirring for 30 min.

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