CN108003520B - Preparation method of polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property - Google Patents

Preparation method of polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property Download PDF

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CN108003520B
CN108003520B CN201711290938.1A CN201711290938A CN108003520B CN 108003520 B CN108003520 B CN 108003520B CN 201711290938 A CN201711290938 A CN 201711290938A CN 108003520 B CN108003520 B CN 108003520B
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polyvinylidene fluoride
titanium carbide
composite material
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刘晓旭
李彦鹏
李娜
闫凯
岳东
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Datong Copolymerization Xi'an Technology Co ltd
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Shaanxi University of Science and Technology
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Abstract

A preparation method of a polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property relates to a preparation method of a polyvinylidene fluoride composite material. The invention aims to solve the problem of low dielectric constant of the conventional polyvinylidene fluoride. The method comprises the following steps: firstly, preparing a two-dimensional layered TiC nanosheet; and compounding to obtain the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property, wherein the mass fraction of the titanium carbide nanosheets is 5-20%. The polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property prepared by the invention can be applied to the fields of microelectronic processing, integrated circuits and high-efficiency energy storage elements; the dielectric constant of the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property prepared by the invention is 9.8-19.1. The polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property can be obtained.

Description

Preparation method of polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property
Technical Field
The invention relates to a preparation method of a polyvinylidene fluoride composite material.
Background
Nowadays, the efficiency of electronic products is increasing exponentially. With this rapid increase in efficiency, new materials with high dielectric constants are produced. High dielectric constant materials can store more electrical energy than low dielectric constant materials. Therefore, applying it to an electronic device can improve efficiency. Electronic systems are typically composed of active components, such as integrated circuits, and passive components. Interest in passive components is increasing because their usage is steadily increasing as the electronics industry moves towards higher functionality. To reduce the volume of high performance electronic devices, it is desirable to integrate passive components, such as resistors, capacitors, and inductors, which are used in quantities exceeding the active integrated circuit elements and occupy a large portion of the area of the substrate. In fact, ceramics and metals have a high hardness and good thermal stability as well as high dielectric properties. However, their high density, brittleness, and challenging processing conditions have hindered their use as high dielectric materials. On the other hand, polymers have the advantage of being easy to process, mechanically flexible and low-cost. The mechanical flexibility and tunable properties of polymer-based composites make them attractive. However, organic polymer materials generally have a low dielectric constant in the range of 2 to 5 compared to inorganic materials. In special cases, pure polymers can have dielectric constants in excess of 10 despite their excellent physical properties, but still be low, which has prevented their use as high dielectric materials. Therefore, a key problem is to greatly increase the dielectric constant of the polymer while maintaining its excellent mechanical properties.
Disclosure of Invention
The invention aims to solve the problem of low dielectric constant of the existing polyvinylidene fluoride, and provides a preparation method of a polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property.
A preparation method of a polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property comprises the following steps:
firstly, preparing a two-dimensional layered TiC nanosheet:
①, mixing Ti3AlC2Adding the mixture into a mixed acid solution, stirring and reacting for 0.5 to 2 hours at a stirring speed of 100 to 300r/min, adding sodium fluoride powder, and reacting for 10 to 14 hours at a temperature of between 35 and 50 ℃ to obtain a reaction solution;
the mixed acid solution in the first step ① is a mixed solution of 98% by mass of concentrated sulfuric acid and 85% by mass of concentrated phosphoric acid, and the volume ratio of the 98% by mass of concentrated sulfuric acid to the 85% by mass of concentrated phosphoric acid in the mixed acid solution is 9: 1;
ti as described in step one ①3AlC2The volume ratio of the mass of the mixed acid solution (2 g-4 g) to the mixed acid solution is 30 mL;
the volume ratio of the mass of the sodium fluoride powder and the mixed acid solution in the step one ① is (0.5 g-2 g) 30 mL;
②, cooling the reaction solution to room temperature, centrifuging at the speed of 6000-8000 r/min for 10-20 min, and removing the supernatant to obtain a solid substance, wherein the solid substance is washed by distilled water for 2-4 times, and then washed by absolute ethyl alcohol until the pH value of the washing solution is neutral to obtain a washed solid substance;
③, adding N, N-dimethylformamide into the cleaned solid matter, then performing ultrasonic treatment for 3 to 5 hours under the protection of argon and the ultrasonic power of 100 to 500W, then performing centrifugation for 10 to 20 minutes at the centrifugation speed of 3000 to 4000r/min, then taking the supernatant, then performing centrifugation for 10 minutes at the centrifugation speed of 10000r/min, and then taking the precipitate;
ti as described in step one ①3AlC2The volume ratio of the mass of the N, N-dimethylformamide in the step one ③ is (2 g-4 g) to 100 mL;
④, adding N, N-dimethylformamide into the precipitate obtained in the step one ③ to obtain a two-dimensional layered TiC nanosheet solution with the concentration of 5-10 mg/mL;
II,
①, placing polyvinylidene fluoride in an oven with the temperature of 70-90 ℃ for drying treatment for 6-9 h to obtain dried polyvinylidene fluoride;
②, adding dried polyvinylidene fluoride into a two-dimensional layered TiC nanosheet solution with the concentration of 5-10 mg/mL, and stirring and reacting for 7-9 h at the temperature of 45-55 ℃ and the stirring speed of 100r/min to obtain a viscous mixed solution B;
the volume ratio of the mass of the dried polyvinylidene fluoride in the step two ② to the two-dimensional layered TiC nanosheet solution with the concentration of 5 mg/mL-10 mg/mL (0.4 g-0.95 g) is 10 mL;
③, performing ultrasonic treatment on the viscous mixed solution B for 3 to 5 hours under the ultrasonic power of 100 to 500W to obtain uniformly dispersed polyvinylidene fluoride-two-dimensional layered TiC nanosheet composite colloid;
④, dripping the uniformly dispersed polyvinylidene fluoride-two-dimensional layered TiC nanosheet composite colloid onto a clean glass substrate, naturally casting the composite colloid into a film, performing heat treatment at the temperature of 70-80 ℃ for 8-12 h, placing the film in distilled water to naturally fall off, and then hanging and drying the film;
⑤, carrying out vacuum heat treatment on the dried film at the temperature of 90-100 ℃ for 8-12 h to obtain the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property and 5-20% of titanium carbide nanosheets by mass fraction;
the thickness of the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property, wherein the mass fraction of the titanium carbide nanosheets in the step two ⑤ is 5% -20%, is 100-150 μm.
The principle and the advantages of the invention are as follows:
the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property is prepared by a solution casting method, and has excellent performances of high dielectric constant, low dielectric loss, flexible mechanical property and stable physicochemical property;
the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property prepared by the invention can be applied to the fields of microelectronic processing, integrated circuits and high-efficiency energy storage elements;
and thirdly, the dielectric constant of the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property is 9.8-19.1.
The polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property can be obtained.
Drawings
FIG. 1 is an SEM image of a high-dielectric-property polyvinylidene fluoride titanium carbide nanosheet composite material with 5% by mass of titanium carbide nanosheets prepared in the first example;
FIG. 2 is an SEM image of a high-dielectric-property polyvinylidene fluoride titanium carbide nanosheet composite material with 15% by mass of titanium carbide nanosheets prepared in example III;
fig. 3 is a dielectric constant curve, in fig. 3, a is a dielectric constant of pure polyvinylidene fluoride prepared in a comparative example, B is a dielectric constant of a high dielectric property polyvinylidene fluoride titanium carbide nanosheet composite material with a titanium carbide nanosheet mass fraction of 5% prepared in the first example, C is a dielectric constant of a high dielectric property polyvinylidene fluoride titanium carbide nanosheet composite material with a titanium carbide nanosheet mass fraction of 10% prepared in the second example, D is a dielectric constant of a high dielectric property polyvinylidene fluoride titanium carbide nanosheet composite material with a titanium carbide nanosheet mass fraction of 15% prepared in the third example, and E is a dielectric constant of a high dielectric property polyvinylidene fluoride titanium carbide nanosheet composite material with a titanium carbide nanosheet mass fraction of 20% prepared in the fourth example.
Detailed Description
The first embodiment is as follows: the embodiment is a preparation method of a polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property, which is specifically completed according to the following steps:
firstly, preparing a two-dimensional layered TiC nanosheet:
①, mixing Ti3AlC2Adding the mixture into a mixed acid solution, stirring and reacting for 0.5 to 2 hours at a stirring speed of 100 to 300r/min, adding sodium fluoride powder, and reacting for 10 to 14 hours at a temperature of between 35 and 50 ℃ to obtain a reaction solution;
the mixed acid solution in the first step ① is a mixed solution of 98% by mass of concentrated sulfuric acid and 85% by mass of concentrated phosphoric acid, and the volume ratio of the 98% by mass of concentrated sulfuric acid to the 85% by mass of concentrated phosphoric acid in the mixed acid solution is 9: 1;
ti as described in step one ①3AlC2The volume ratio of the mass of the mixed acid solution (2 g-4 g) to the mixed acid solution is 30 mL;
the volume ratio of the mass of the sodium fluoride powder and the mixed acid solution in the step one ① is (0.5 g-2 g) 30 mL;
②, cooling the reaction solution to room temperature, centrifuging at the speed of 6000-8000 r/min for 10-20 min, and removing the supernatant to obtain a solid substance, wherein the solid substance is washed by distilled water for 2-4 times, and then washed by absolute ethyl alcohol until the pH value of the washing solution is neutral to obtain a washed solid substance;
③, adding N, N-dimethylformamide into the cleaned solid matter, then performing ultrasonic treatment for 3 to 5 hours under the protection of argon and the ultrasonic power of 100 to 500W, then performing centrifugation for 10 to 20 minutes at the centrifugation speed of 3000 to 4000r/min, then taking the supernatant, then performing centrifugation for 10 minutes at the centrifugation speed of 10000r/min, and then taking the precipitate;
ti as described in step one ①3AlC2The volume ratio of the mass of the N, N-dimethylformamide in the step one ③ is (2 g-4 g) to 100 mL;
④, adding N, N-dimethylformamide into the precipitate obtained in the step one ③ to obtain a two-dimensional layered TiC nanosheet solution with the concentration of 5-10 mg/mL;
II,
①, placing polyvinylidene fluoride in an oven with the temperature of 70-90 ℃ for drying treatment for 6-9 h to obtain dried polyvinylidene fluoride;
②, adding dried polyvinylidene fluoride into a two-dimensional layered TiC nanosheet solution with the concentration of 5-10 mg/mL, and stirring and reacting for 7-9 h at the temperature of 45-55 ℃ and the stirring speed of 100r/min to obtain a viscous mixed solution B;
the volume ratio of the mass of the dried polyvinylidene fluoride in the step two ② to the two-dimensional layered TiC nanosheet solution with the concentration of 5 mg/mL-10 mg/mL (0.4 g-0.95 g) is 10 mL;
③, performing ultrasonic treatment on the viscous mixed solution B for 3 to 5 hours under the ultrasonic power of 100 to 500W to obtain uniformly dispersed polyvinylidene fluoride-two-dimensional layered TiC nanosheet composite colloid;
④, dripping the uniformly dispersed polyvinylidene fluoride-two-dimensional layered TiC nanosheet composite colloid onto a clean glass substrate, naturally casting the composite colloid into a film, performing heat treatment at the temperature of 70-80 ℃ for 8-12 h, placing the film in distilled water to naturally fall off, and then hanging and drying the film;
⑤, carrying out vacuum heat treatment on the dried film at the temperature of 90-100 ℃ for 8-12 h to obtain the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property and 5-20% of titanium carbide nanosheets by mass fraction;
the thickness of the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property, wherein the mass fraction of the titanium carbide nanosheets in the step two ⑤ is 5% -20%, is 100-150 μm.
Centrifuging for 10-20 min at a centrifugation speed of 3000-4000 r/min in the first step ③ to remove large stripped titanium carbide particles, wherein a supernatant obtained after centrifuging is a thin-layer titanium carbide nanosheet solution, centrifuging for 10min at a centrifugation speed of 10000r/min, precipitating the thin-layer titanium carbide nanosheet, namely a two-dimensional layered TiC nanosheet, and obtaining N, N-dimethylformamide;
in the first embodiment, the precipitated substance obtained in step one ③ is a two-dimensional layered TiC nanosheet, and a two-dimensional layered TiC nanosheet solution with a concentration of 5mg/mL to 10mg/mL can be prepared by adding N, N-dimethylformamide to the two-dimensional layered TiC nanosheet.
The principle and advantages of the embodiment are as follows:
the method is characterized in that a solution casting method is adopted to prepare the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property, and the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property has excellent performances of high dielectric constant, low dielectric loss, flexible mechanical property and stable physicochemical property;
the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property prepared by the embodiment can be applied to the fields of microelectronic processing, integrated circuits and high-efficiency energy storage elements;
thirdly, the dielectric constant of the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property prepared by the embodiment is 9.8-19.1.
According to the embodiment, the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property can be obtained.
Second embodiment the present embodiment is different from the first embodiment in that Ti is used in ①3AlC2Adding the mixture into mixed acid solution, stirring and reacting for 0.5-1 h at the stirring speed of 100-200 r/min, adding sodium fluoride powder, and reacting for 10-12 h at the temperature of 45-50 ℃ to obtain reaction liquid. Other steps are the same as in the first embodiment.
The third concrete implementation mode: this embodiment and the first embodimentOr either difference is Ti as described in step one ①3AlC2The volume ratio of the mass of (2 g-3 g) to the mixed acid solution is 30 mL. The other steps are the same as in the first or second embodiment.
Fourth embodiment the present embodiment is different from the first to third embodiments in that the ratio of the mass of the sodium fluoride powder to the volume of the mixed acid solution in the first step ① is (0.5g to 1g):30ml, and other steps are the same as in the first to third embodiments.
Fifth embodiment A difference between the fifth embodiment and the first to fourth embodiments is that the Ti is obtained in the first step ①3AlC2The mass of N, N-dimethylformamide described in the first step ③ was (2g to 3g):100 mL.
Sixth embodiment a difference between this embodiment and any one of the first to fifth embodiments is that N, N-dimethylformamide is added to the precipitated substance obtained in the first step ③ in the first step ④ to obtain a two-dimensional layered TiC nanosheet solution having a concentration of 5mg/mL to 7.5mg/mL, and the other steps are the same as in the first to fifth embodiments.
Seventh embodiment mode, the difference between this embodiment mode and one of the first to sixth embodiment modes is that, in the second step ①, polyvinylidene fluoride is dried in an oven at 80-90 ℃ for 6-8 h to obtain dried polyvinylidene fluoride, and other steps are the same as those in the first to sixth embodiment modes.
Eighth embodiment mode the present embodiment is different from the first to seventh embodiment modes in that the volume ratio of the mass of the dried polyvinylidene fluoride to the two-dimensional layered TiC nanosheet solution having a concentration of 5mg/mL to 10mg/mL in step two ② is (0.4g to 0.75g):10 mL.
Ninth embodiment mode the present embodiment is different from the first to eighth embodiment modes in that, in the second step ④, a uniformly dispersed polyvinylidene fluoride-two-dimensional layered TiC nanosheet composite colloid is dropped onto a clean glass substrate to be naturally cast into a film, then the film is subjected to a heat treatment at a temperature of 70 to 75 ℃ for 8 to 10 hours, then the film is placed in distilled water to naturally fall off, and then the film is hung and dried.
The tenth embodiment is different from the first to ninth embodiments in that the dried film is subjected to vacuum heat treatment at 95-100 ℃ for 8-10 h in step two ⑤ to obtain the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property, wherein the mass fraction of the titanium carbide nanosheets is 10-20%.
The first embodiment is as follows: the preparation method of the polyvinylidene fluoride titanium carbide nanosheet composite material with the high dielectric property and the titanium carbide nanosheet mass fraction of 5% comprises the following steps:
firstly, preparing a two-dimensional layered TiC nanosheet:
①, mixing Ti3AlC2Adding the mixture into a mixed acid solution, stirring and reacting for 1h at the stirring speed of 200r/min, adding sodium fluoride powder, and reacting for 12h at the temperature of 45 ℃ to obtain a reaction solution;
the mixed acid solution in the first step ① is a mixed solution of 98% by mass of concentrated sulfuric acid and 85% by mass of concentrated phosphoric acid, and the volume ratio of the 98% by mass of concentrated sulfuric acid to the 85% by mass of concentrated phosphoric acid in the mixed acid solution is 9: 1;
ti as described in step one ①3AlC2The mass ratio of the mixed acid solution to the mixed acid solution is 3g to 30 mL;
the volume ratio of the mass of the sodium fluoride powder in the first step ① to the volume of the mixed acid solution is 1g:30 mL;
②, cooling the reaction solution to room temperature, centrifuging at 7000r/min for 15min, and removing the supernatant to obtain solid substance, firstly washing the solid substance with distilled water for 3 times, and then washing with absolute ethanol until the pH value of the washing solution is neutral to obtain washed solid substance;
③, adding N, N-dimethylformamide into the cleaned solid matter, performing ultrasound for 4h under the protection of argon and at the ultrasonic power of 300W, centrifuging at the centrifugal speed of 4000r/min for 15min, taking the supernatant, centrifuging at the centrifugal speed of 10000r/min for 10min, and taking the precipitate;
ti as described in step one ①3AlC2The mass to volume ratio of N, N-dimethylformamide described in step one ③ is 3g:100 mL;
④, adding N, N-dimethylformamide into the precipitate obtained in the step one ③ to obtain a two-dimensional layered TiC nanosheet solution with the concentration of 5 mg/mL;
II,
①, placing polyvinylidene fluoride in an oven with the temperature of 80 ℃ for drying treatment for 8h to obtain dried polyvinylidene fluoride;
②, adding dried polyvinylidene fluoride into a two-dimensional layered TiC nanosheet solution with the concentration of 5mg/mL, and stirring and reacting for 8 hours at the temperature of 50 ℃ and the stirring speed of 100r/min to obtain a viscous mixed solution B;
the volume ratio of the mass of the dried polyvinylidene fluoride in the step two ② to the two-dimensional layered TiC nanosheet solution with the concentration of 5mg/mL is 0.95g:10 mL;
③, performing ultrasonic treatment on the viscous mixed solution B for 4 hours under the ultrasonic power of 300W to obtain uniformly dispersed polyvinylidene fluoride-two-dimensional layered TiC nanosheet composite colloid;
④, dripping the uniformly dispersed polyvinylidene fluoride-two-dimensional layered TiC nanosheet composite colloid onto a clean glass substrate, naturally casting the composite colloid into a film, performing heat treatment at the temperature of 75 ℃ for 10 hours, placing the film in distilled water to naturally fall off, and then hanging and airing the film;
⑤, carrying out vacuum heat treatment on the dried film at the temperature of 100 ℃ for 10h to obtain the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property and 5% of titanium carbide nanosheet mass fraction.
And step two ⑤, the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property and 5% of titanium carbide nanosheets by mass is 100 microns thick.
Example two: the preparation method of the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property and 10% of titanium carbide nanosheet mass fraction comprises the following steps:
firstly, preparing a two-dimensional layered TiC nanosheet:
①, mixing Ti3AlC2Adding the mixture into a mixed acid solution, stirring and reacting for 1h at the stirring speed of 200r/min, adding sodium fluoride powder, and reacting for 12h at the temperature of 45 ℃ to obtain a reaction solution;
the mixed acid solution in the first step ① is a mixed solution of 98% by mass of concentrated sulfuric acid and 85% by mass of concentrated phosphoric acid, and the volume ratio of the 98% by mass of concentrated sulfuric acid to the 85% by mass of concentrated phosphoric acid in the mixed acid solution is 9: 1;
ti as described in step one ①3AlC2The mass ratio of the mixed acid solution to the mixed acid solution is 3g to 30 mL;
the volume ratio of the mass of the sodium fluoride powder in the first step ① to the volume of the mixed acid solution is 1g:30 mL;
②, cooling the reaction solution to room temperature, centrifuging at 7000r/min for 15min, and removing the supernatant to obtain solid substance, firstly washing the solid substance with distilled water for 3 times, and then washing with absolute ethanol until the pH value of the washing solution is neutral to obtain washed solid substance;
③, adding N, N-dimethylformamide into the cleaned solid matter, performing ultrasound for 4h under the protection of argon and at the ultrasonic power of 300W, centrifuging at the centrifugal speed of 4000r/min for 15min, taking the supernatant, centrifuging at the centrifugal speed of 10000r/min for 10min, and taking the precipitate;
ti as described in step one ①3AlC2The mass to volume ratio of N, N-dimethylformamide described in step one ③ is 3g:100 mL;
④, adding N, N-dimethylformamide into the precipitate obtained in the step one ③ to obtain a two-dimensional layered TiC nanosheet solution with the concentration of 10 mg/mL;
II,
①, placing polyvinylidene fluoride in an oven with the temperature of 80 ℃ for drying treatment for 8h to obtain dried polyvinylidene fluoride;
②, adding dried polyvinylidene fluoride into a two-dimensional layered TiC nanosheet solution with the concentration of 10mg/mL, and stirring and reacting for 8 hours at the temperature of 50 ℃ and the stirring speed of 100r/min to obtain a viscous mixed solution B;
the volume ratio of the mass of the dried polyvinylidene fluoride in the step two ② to the two-dimensional layered TiC nanosheet solution with the concentration of 10mg/mL is 0.9g:10 mL;
③, performing ultrasonic treatment on the viscous mixed solution B for 4 hours under the ultrasonic power of 300W to obtain uniformly dispersed polyvinylidene fluoride-two-dimensional layered TiC nanosheet composite colloid;
④, dripping the uniformly dispersed polyvinylidene fluoride-two-dimensional layered TiC nanosheet composite colloid onto a clean glass substrate, naturally casting the composite colloid into a film, performing heat treatment at the temperature of 75 ℃ for 10 hours, placing the film in distilled water to naturally fall off, and then hanging and airing the film;
⑤, carrying out vacuum heat treatment on the dried film at the temperature of 100 ℃ for 10h to obtain the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property and 10% of titanium carbide nanosheet mass fraction.
And step two ⑤, the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property and 10% of titanium carbide nanosheets by mass is 100 microns thick.
Example three: the preparation method of the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property and 15% of titanium carbide nanosheet mass fraction comprises the following steps:
firstly, preparing a two-dimensional layered TiC nanosheet:
①, mixing Ti3AlC2Adding the mixture into a mixed acid solution, stirring and reacting for 1h at the stirring speed of 200r/min, adding sodium fluoride powder, and reacting for 12h at the temperature of 45 ℃ to obtain a reaction solution;
the mixed acid solution in the first step ① is a mixed solution of 98% by mass of concentrated sulfuric acid and 85% by mass of concentrated phosphoric acid, and the volume ratio of the 98% by mass of concentrated sulfuric acid to the 85% by mass of concentrated phosphoric acid in the mixed acid solution is 9: 1;
as described in step one ①Ti of (A)3AlC2The mass ratio of the mixed acid solution to the mixed acid solution is 3g to 30 mL;
the volume ratio of the mass of the sodium fluoride powder in the first step ① to the volume of the mixed acid solution is 1g:30 mL;
②, cooling the reaction solution to room temperature, centrifuging at 7000r/min for 15min, and removing the supernatant to obtain solid substance, firstly washing the solid substance with distilled water for 3 times, and then washing with absolute ethanol until the pH value of the washing solution is neutral to obtain washed solid substance;
③, adding N, N-dimethylformamide into the cleaned solid matter, performing ultrasound for 4h under the protection of argon and at the ultrasonic power of 300W, centrifuging at the centrifugal speed of 4000r/min for 15min, taking the supernatant, centrifuging at the centrifugal speed of 10000r/min for 10min, and taking the precipitate;
ti as described in step one ①3AlC2The mass to volume ratio of N, N-dimethylformamide described in step one ③ is 4g:100 mL;
④, adding N, N-dimethylformamide into the precipitate obtained in the step one ③ to obtain a two-dimensional layered TiC nanosheet solution with the concentration of 7.5 mg/mL;
II,
①, placing polyvinylidene fluoride in an oven with the temperature of 80 ℃ for drying treatment for 8h to obtain dried polyvinylidene fluoride;
②, adding dried polyvinylidene fluoride into a 7.5mg/mL two-dimensional layered TiC nanosheet solution, and stirring for reacting for 8 hours at the temperature of 50 ℃ and the stirring speed of 100r/min to obtain a viscous mixed solution B;
the volume ratio of the mass of the dried polyvinylidene fluoride in the step two ② to the two-dimensional layered TiC nanosheet solution with the concentration of 7.5mg/mL is 0.425g:10 mL;
③, performing ultrasonic treatment on the viscous mixed solution B for 4 hours under the ultrasonic power of 300W to obtain uniformly dispersed polyvinylidene fluoride-two-dimensional layered TiC nanosheet composite colloid;
④, dripping the uniformly dispersed polyvinylidene fluoride-two-dimensional layered TiC nanosheet composite colloid onto a clean glass substrate, naturally casting the composite colloid into a film, performing heat treatment at the temperature of 75 ℃ for 10 hours, placing the film in distilled water to naturally fall off, and then hanging and airing the film;
⑤, carrying out vacuum heat treatment on the dried film at the temperature of 100 ℃ for 10h to obtain the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property and 15% of titanium carbide nanosheet mass fraction.
And step two ⑤, the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property and 15% of titanium carbide nanosheets by mass has a thickness of 100 microns.
Example four: the preparation method of the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property and 20% of titanium carbide nanosheet mass fraction comprises the following steps:
firstly, preparing a two-dimensional layered TiC nanosheet:
①, mixing Ti3AlC2Adding the mixture into a mixed acid solution, stirring and reacting for 1h at the stirring speed of 200r/min, adding sodium fluoride powder, and reacting for 12h at the temperature of 45 ℃ to obtain a reaction solution;
the mixed acid solution in the first step ① is a mixed solution of 98% by mass of concentrated sulfuric acid and 85% by mass of concentrated phosphoric acid, and the volume ratio of the 98% by mass of concentrated sulfuric acid to the 85% by mass of concentrated phosphoric acid in the mixed acid solution is 9: 1;
ti as described in step one ①3AlC2The mass ratio of the mixed acid solution to the mixed acid solution is 3g to 30 mL;
the volume ratio of the mass of the sodium fluoride powder in the first step ① to the volume of the mixed acid solution is 1g:30 mL;
②, cooling the reaction solution to room temperature, centrifuging at 7000r/min for 15min, and removing the supernatant to obtain solid substance, firstly washing the solid substance with distilled water for 3 times, and then washing with absolute ethanol until the pH value of the washing solution is neutral to obtain washed solid substance;
③, adding N, N-dimethylformamide into the cleaned solid matter, performing ultrasonic treatment for 3-5 h under the protection of argon and at the ultrasonic power of 300W, centrifuging for 15min at the centrifugal speed of 4000r/min, taking the supernatant, centrifuging for 10min at the centrifugal speed of 10000r/min, and taking the precipitate;
ti as described in step one ①3AlC2The mass to volume ratio of N, N-dimethylformamide described in step one ③ is 3g:100 mL;
④, adding N, N-dimethylformamide into the precipitate obtained in the step one ③ to obtain a two-dimensional layered TiC nanosheet solution with the concentration of 10 mg/mL;
II,
①, placing polyvinylidene fluoride in an oven with the temperature of 80 ℃ for drying treatment for 8h to obtain dried polyvinylidene fluoride;
②, adding dried polyvinylidene fluoride into a two-dimensional layered TiC nanosheet solution with the concentration of 10mg/mL, and stirring and reacting for 8 hours at the temperature of 50 ℃ and the stirring speed of 100r/min to obtain a viscous mixed solution B;
the volume ratio of the mass of the dried polyvinylidene fluoride in the step two ② to the two-dimensional layered TiC nanosheet solution with the concentration of 10mg/mL is 0.4g:10 mL;
③, performing ultrasonic treatment on the viscous mixed solution B for 4 hours under the ultrasonic power of 300W to obtain uniformly dispersed polyvinylidene fluoride-two-dimensional layered TiC nanosheet composite colloid;
④, dripping the uniformly dispersed polyvinylidene fluoride-two-dimensional layered TiC nanosheet composite colloid onto a clean glass substrate, naturally casting the composite colloid into a film, performing heat treatment at the temperature of 75 ℃ for 10 hours, placing the film in distilled water to naturally fall off, and then hanging and airing the film;
⑤, carrying out vacuum heat treatment on the dried film at the temperature of 100 ℃ for 10h to obtain the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property and 20% of titanium carbide nanosheet mass fraction.
And step two ⑤, the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property and 20% of titanium carbide nanosheets by mass is 100 microns thick.
Comparative example: the polyvinylidene fluoride is prepared by the following steps:
①, placing polyvinylidene fluoride in an oven with the temperature of 80 ℃ for drying treatment for 8h to obtain dried polyvinylidene fluoride;
②, adding dried polyvinylidene fluoride into N, N-dimethylformamide, and stirring and reacting for 8 hours at the temperature of 50 ℃ and the stirring speed of 100r/min to obtain a polyvinylidene fluoride solution;
the volume ratio of the mass of the dried polyvinylidene fluoride in the step ② to the volume of the N, N-dimethylformamide is 0.95g:10 mL;
④, subjecting the polyvinylidene fluoride solution to ultrasonic treatment at the ultrasonic power of 300W for 4h to obtain uniformly dispersed polyvinylidene fluoride colloid;
⑤, dripping the uniformly dispersed polyvinylidene fluoride colloid onto a clean glass substrate, naturally casting the polyvinylidene fluoride colloid into a film, carrying out heat treatment at the temperature of 75 ℃ for 10 hours, placing the film in distilled water to naturally fall off, and hanging and airing the film;
⑥, carrying out vacuum heat treatment on the dried film at the temperature of 100 ℃ for 10h to obtain polyvinylidene fluoride;
the thickness of the polyvinylidene fluoride in the second step ⑥ is 100 μm.
FIG. 1 is an SEM image of a high-dielectric-property polyvinylidene fluoride titanium carbide nanosheet composite material with 5% by mass of titanium carbide nanosheets prepared in the first example;
as can be seen from FIG. 1, when the mass fraction of the titanium carbide nanosheets in the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property is 5%, the titanium carbide nanosheets are coated by polymer molecular chains, and are relatively uniformly dispersed in the polyimide, so that no obvious agglomeration phenomenon exists.
FIG. 2 is an SEM image of a high-dielectric-property polyvinylidene fluoride titanium carbide nanosheet composite material with 15% by mass of titanium carbide nanosheets prepared in example III;
as can be seen from fig. 2, when the mass fraction of the titanium carbide nanosheets in the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property is 15%, the titanium carbide nanosheets are coated by polymer molecular chains, and the titanium carbide nanosheets begin to be locally agglomerated in the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property.
Fig. 3 is a dielectric constant curve, in fig. 3, a is a dielectric constant of pure polyvinylidene fluoride prepared in a comparative example, B is a dielectric constant of a high dielectric property polyvinylidene fluoride titanium carbide nanosheet composite material with a titanium carbide nanosheet mass fraction of 5% prepared in the first example, C is a dielectric constant of a high dielectric property polyvinylidene fluoride titanium carbide nanosheet composite material with a titanium carbide nanosheet mass fraction of 10% prepared in the second example, D is a dielectric constant of a high dielectric property polyvinylidene fluoride titanium carbide nanosheet composite material with a titanium carbide nanosheet mass fraction of 15% prepared in the third example, and E is a dielectric constant of a high dielectric property polyvinylidene fluoride titanium carbide nanosheet composite material with a titanium carbide nanosheet mass fraction of 20% prepared in the fourth example.
As can be seen from fig. 3, with the increase of the content of the titanium carbide nanosheets in the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property, the dielectric constant of the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property is significantly increased, and when the mass fraction of the titanium carbide nanosheets in the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property is 20%, the dielectric constant of the composite material reaches 19.1, which is about 2.5 times of the dielectric constant of pure polyvinylidene fluoride, and the dielectric property is significantly improved.

Claims (10)

1. A preparation method of a polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property is characterized by comprising the following steps:
firstly, preparing a two-dimensional layered TiC nanosheet:
①, mixing Ti3AlC2Adding the mixture into a mixed acid solution, stirring and reacting for 0.5 to 2 hours at a stirring speed of 100 to 300r/min, adding sodium fluoride powder, and reacting for 10 to 14 hours at a temperature of between 35 and 50 ℃ to obtain a reaction solution;
the mixed acid solution in the first step ① is a mixed solution of 98% by mass of concentrated sulfuric acid and 85% by mass of concentrated phosphoric acid, and the volume ratio of the 98% by mass of concentrated sulfuric acid to the 85% by mass of concentrated phosphoric acid in the mixed acid solution is 9: 1;
ti as described in step one ①3AlC2The volume ratio of the mass of the mixed acid solution (2 g-4 g) to the mixed acid solution is 30 mL;
the volume ratio of the mass of the sodium fluoride powder and the mixed acid solution in the step one ① is (0.5 g-2 g) 30 mL;
②, cooling the reaction solution to room temperature, centrifuging at the speed of 6000-8000 r/min for 10-20 min, and removing the supernatant to obtain a solid substance, wherein the solid substance is washed by distilled water for 2-4 times, and then washed by absolute ethyl alcohol until the pH value of the washing solution is neutral to obtain a washed solid substance;
③, adding N, N-dimethylformamide into the cleaned solid matter, then performing ultrasonic treatment for 3 to 5 hours under the protection of argon and the ultrasonic power of 100 to 500W, then performing centrifugation for 10 to 20 minutes at the centrifugation speed of 3000 to 4000r/min, then taking the supernatant, then performing centrifugation for 10 minutes at the centrifugation speed of 10000r/min, and then taking the precipitate;
ti as described in step one ①3AlC2The volume ratio of the mass of the N, N-dimethylformamide in the step one ③ is (2 g-4 g) to 100 mL;
④, adding N, N-dimethylformamide into the precipitate obtained in the step one ③ to obtain a two-dimensional layered TiC nanosheet solution with the concentration of 5-10 mg/mL;
II,
①, placing polyvinylidene fluoride in an oven with the temperature of 70-90 ℃ for drying treatment for 6-9 h to obtain dried polyvinylidene fluoride;
②, adding dried polyvinylidene fluoride into a two-dimensional layered TiC nanosheet solution with the concentration of 5-10 mg/mL, and stirring and reacting for 7-9 h at the temperature of 45-55 ℃ and the stirring speed of 100r/min to obtain a viscous mixed solution B;
the volume ratio of the mass of the dried polyvinylidene fluoride in the step two ② to the two-dimensional layered TiC nanosheet solution with the concentration of 5 mg/mL-10 mg/mL (0.4 g-0.95 g) is 10 mL;
③, performing ultrasonic treatment on the viscous mixed solution B for 3 to 5 hours under the ultrasonic power of 100 to 500W to obtain uniformly dispersed polyvinylidene fluoride-two-dimensional layered TiC nanosheet composite colloid;
④, dripping the uniformly dispersed polyvinylidene fluoride-two-dimensional layered TiC nanosheet composite colloid onto a clean glass substrate, naturally casting the composite colloid into a film, performing heat treatment at the temperature of 70-80 ℃ for 8-12 h, placing the film in distilled water to naturally fall off, and then hanging and drying the film;
⑤, carrying out vacuum heat treatment on the dried film at the temperature of 90-100 ℃ for 8-12 h to obtain the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property and 10-20% of titanium carbide nanosheets by mass fraction;
the thickness of the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property, with the mass fraction of the titanium carbide nanosheets being 10-20% in the second step ⑤, is 100-150 micrometers.
2. The preparation method of the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric properties as claimed in claim 1, wherein Ti is added in step one ①3AlC2Adding the mixture into mixed acid solution, stirring and reacting for 0.5-1 h at the stirring speed of 100-200 r/min, adding sodium fluoride powder, and reacting for 10-12 h at the temperature of 45-50 ℃ to obtain reaction liquid.
3. The method for preparing polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric properties as claimed in claim 1, wherein the Ti in step one ①3AlC2The volume ratio of the mass of (2 g-3 g) to the mixed acid solution is 30 mL.
4. The preparation method of the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric properties as claimed in claim 1, wherein the volume ratio of the mass of the sodium fluoride powder to the mixed acid solution in step one ① is (0.5 g-1 g):30 mL.
5. The method of claim 1, wherein the polyvinylidene fluoride with high dielectric properties is carbonizedThe preparation method of the titanium nano-sheet composite material is characterized in that the Ti in the step I ①3AlC2The ratio of the mass of (2g to 3g) to the volume of N, N-dimethylformamide described in the first ③ is 100 mL.
6. The preparation method of the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property as claimed in claim 1, wherein in step one ④, N-dimethylformamide is added to the precipitate obtained in step one ③ to obtain a two-dimensional layered TiC nanosheet solution with a concentration of 5 mg/mL-7.5 mg/mL.
7. The preparation method of the polyvinylidene fluoride titanium carbide nanosheet composite material with the high dielectric property as claimed in claim 1, wherein in step two ①, polyvinylidene fluoride is placed in an oven at a temperature of 80-90 ℃ for drying treatment for 6-8 h to obtain dried polyvinylidene fluoride.
8. The preparation method of the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property as claimed in claim 1, wherein the volume ratio of the mass of the dried polyvinylidene fluoride in step two ② to the two-dimensional layered TiC nanosheet solution with the concentration of 5 mg/mL-10 mg/mL is (0.4 g-0.75 g):10 mL.
9. The preparation method of the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property as claimed in claim 1, wherein in step two ④, uniformly dispersed polyvinylidene fluoride-two-dimensional layered TiC nanosheet composite colloid is dripped onto a clean glass substrate to enable the polyvinylidene fluoride-two-dimensional layered TiC nanosheet composite colloid to be naturally cast into a film, then the film is subjected to heat treatment at the temperature of 70-75 ℃ for 8-10 h, then the film is placed in distilled water to enable the film to naturally fall off, and then the film is hung and dried in the air.
10. The preparation method of the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property according to claim 1, wherein in step two ⑤, the dried film is subjected to vacuum heat treatment at a temperature of 95-100 ℃ for 8-10 h to obtain the polyvinylidene fluoride titanium carbide nanosheet composite material with high dielectric property, wherein the mass fraction of the titanium carbide nanosheets is 10-20%.
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