CN113024974B - One-dimensional TiO2Polyvinylidene fluoride composite film doped with nanowire hybrid structure and preparation method thereof - Google Patents
One-dimensional TiO2Polyvinylidene fluoride composite film doped with nanowire hybrid structure and preparation method thereof Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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Abstract
The invention discloses a one-dimensional TiO2The polyvinylidene fluoride composite film doped with nano-wire hybrid structure and its preparation method are characterized by that said hybrid structure is one-dimensional TiO2The outside of the nanowire is wrapped with Fe3O4Fine particles, modified with EDA, one-dimensional TiO2The doping amount of the nanowire hybrid structure in the composite film is 1-20 vol%, and the preparation method comprises the step of synthesizing TiO2@Fe3O4A step of nanowires; TiO22@Fe3O4Performing organic modification on the nanowire by using ethylenediamine; adding TiO into the mixture2@Fe3O4Mixing the @ EDA nanowire, the dimethylformamide and the polyvinylidene fluoride powder, stirring for reaction, vacuumizing, dropping on horizontal conductive glass, paving, quickly vacuumizing, heating and drying, continuing to raise the temperature to 205 ℃, keeping the temperature for 10 minutes, putting into ice water, quenching, cleaning and drying; the advantages are low filling quantity, high energy storage density, high breakdown field strength and high charge and discharge efficiency.
Description
Technical Field
The invention belongs to the field of dielectric capacitors, and particularly relates to one-dimensional TiO2A polyvinylidene fluoride composite film doped with a nanowire hybrid structure and a preparation method thereof.
Background
With the rapid development of high and new industries, polymer-based dielectric film capacitors as electronic components with high dielectric and high energy storage are widely applied to the fields of new energy automobiles, pulse weapon systems, micro medical equipment and the like. A number of earlier studies have shown that both high energy storage and high efficiency of polymer-based dielectric thin film capacitors are often impossible to achieve, because in the initial studies, in order to increase the dielectric constant of the composite thin film, high dielectric nano-or micro-sized ceramic and metal particles are filled into the polymer matrix, and when the volume fraction of doping is high (> 50 vol.%), the dielectric properties of the composite thin film can be significantly increased. And the efficiency of the composite film is greatly reduced due to the problems of filler agglomeration, large leakage loss and the like caused by high filling amount.
With the progress of experimental equipment and experimental methods, especially the wide application of the electrostatic spinning technology, the one-dimensional nano linear high dielectric filler becomes a hot point of research in the future. : the one-dimensional nanowire-shaped high-dielectric filler has the advantages that: (1) due to the high length-diameter ratio and the smaller specific surface area of the one-dimensional nanowire filler, the dielectric property is improved, and the tortuosity of a breakdown path is increased, so that the breakdown field strength is improved. (2) Functionalized organic modification; not only effectively improves the compatibility between the filler and the polymer matrix, but also plays a role of a buffer layer, reduces the leakage loss and enhances the interface polarization. (3) The 'synergistic effect' brought by the one-dimensional nano-wire with the special structure; the special structure can simultaneously have the advantages of more than two inorganic fillers, and the overall performance of the composite material is greatly improved. (4) TiO22The nano-wire as a common semiconductor material has higher dielectric constant, lower dielectric loss and good conductivity, and provides a foundation for reducing the overall conductivity of the composite material and improving the breakdown field strength.
The polymer-based dielectric composite material used as an important constituent material in the capacitor has to have the advantages of high dielectric constant, high energy storage density, good flexibility, large operable electric field and the like, so that the traditional dielectric composite material cannot meet the current actual requirements. Conventional dielectric polymers such as biaxially oriented polypropylene (BOPP), Polyimide (PI), epoxy resin (EP), Polystyrene (PS), etc. which are commonly used, although they have an ultra-high breakdown field strength (> 500 MV/m), they cannot be applied to the high energy storage field due to their low dielectric constant (< 4). Polyvinylidene fluoride (PVDF) and copolymers P (VDF-HFP), P (VDF-TrFE-CTFE), P (VDF-CTFE) and the like thereof have higher dielectric constant and flexibility, so that the PVDF becomes the first choice for a high-performance dielectric material matrix. However, polymer-based dielectric composites intended to achieve high energy storage density are far from adequate depending on the dielectric constant of the polymer matrix. Therefore, the addition of high dielectric fillers to polymer matrices is recognized by many researchers and is a hot spot in research.
The energy storage performance of the composite film is mainly represented by energy storage density and charge-discharge efficiency. The magnitude of the energy storage density is determined by the dielectric constant of the composite material and the breakdown electric field intensity, and the charge-discharge efficiency is the ratio of the discharge energy density to the total energy density. At present, the method for improving the dielectric property of the composite material mainly fills the insulating ceramic filler with high dielectric constant into the polymer matrix or simultaneously adds the conductive and insulating ceramic nano filler. Due to the addition of the high-dielectric ceramic nano filler, the dielectric property of the composite material is obviously improved, the energy storage density is improved, but with the increase of the content of the filler, the dispersibility of the filler in a matrix is reduced, and the phenomena of defects and agglomeration are also increased, so that the breakdown field strength is reduced sharply, and the flexibility of the material is damaged. Although the composite material prepared by utilizing the advantages of various materials can improve the energy storage density, the biggest defect is that the charge-discharge efficiency is low, because the various fillers are difficult to realize uniform dispersion in a polymer matrix and are easy to agglomerate and intertwine, the loss and the leakage current of the composite material are increased, and the energy storage efficiency is obviously reduced.
Disclosure of Invention
The invention aims to provide a one-dimensional TiO with low filling amount, high energy storage density, high breakdown field strength and high charge-discharge efficiency2Nano-wire hybrid structure doped polyvinylidene fluoride composite film and nano-wire hybrid structure doped polyvinylidene fluoride composite filmA preparation method.
The technical scheme adopted by the invention for solving the technical problems is as follows: one-dimensional TiO2Polyvinylidene fluoride composite film doped with nano-wire hybrid structure, the one-dimensional TiO2The nano-wire hybrid structure is one-dimensional TiO2The outside of the nanowire is wrapped with Fe3O4Fine particles, modified with EDA, said one-dimensional TiO2The doping amount of the nanowire hybrid structure in the composite film is 1-20 vol%.
Preferably, the one-dimensional TiO2The doping amount of the nanowire hybrid structure in the composite film is 1 vol%, 2 vol%, 3 vol% or 4 vol%.
The above one-dimensional TiO2The preparation method of the polyvinylidene fluoride composite film doped with the nanowire hybrid structure comprises the following steps:
(1) synthesis of TiO2Nanowire and method of manufacturing the same
A. Adding 1-5g of titanium dioxide nanoparticles into a 10M sodium hydroxide solution, performing ultrasonic treatment for 30-60 minutes, uniformly mixing and stirring for 1-5 hours under magnetic stirring, transferring the mixed solution into a high-pressure reaction kettle with Teflon, reacting for 12-24 hours at 150-250 ℃, washing a product to be neutral after the reaction is finished, and drying to obtain a sodium titanate nanowire;
B. soaking the sodium titanate nanowire in 0.2M HCl for 4-6 hours, washing and drying to obtain H2Ti3O7Nanowire of H2Ti3O7The nano wire is put into a high-temperature box type furnace for annealing for 2 to 5 hours, and the collected product is TiO2A nanowire;
(2) synthesis of TiO2@Fe3O4Nanowire:
A. 1-5g of TiO2Adding nanowires, 0.01 g of polyvinylpyrrolidone (PVP) and 150ml of deionized water into a three-neck flask, placing the three-neck flask in an ultrasonic cleaner for ultrasonic treatment for 20-40 minutes, and stirring for 3-5 hours to form a solution A;
B. 0.16g of FeCl was taken3·6H2O and 0.32g FeSO4·7H2Dissolving O in 50ml water in a small beakerStirring at low speed to obtain a uniform mixed solution B;
C. dropwise adding the mixed solution B into the solution A in a water bath kettle at 50-70 deg.C until the solution turns from milky white to light brown, stirring for 1-3 hr, collecting the product, cleaning, centrifuging, and vacuum drying to obtain TiO2@Fe3O4A nanowire;
（3）TiO2@Fe3O4ethylenediamine organic modification of nanowires
Taking 1-5g of TiO2@Fe3O4Adding the nanowire and 30mL of 0.02M ethylenediamine hydrochloride solution into a three-neck flask, performing ultrasonic treatment for 20-40 minutes in a water bath kettle at 50-80 ℃, stirring for 12 hours, collecting a product, cleaning, centrifuging and drying in vacuum to obtain TiO2@Fe3O4@ EDA nanowires;
(4) preparation of composite films
Adding TiO into the mixture2@Fe3O4Mixing the @ EDA nanowire, Dimethylformamide (DMF) and polyvinylidene fluoride (PVDF) powder, stirring for reaction for 12-18 hours, vacuumizing, dripping on horizontal conductive glass, paving, quickly vacuumizing, heating and drying excess solvent at 60 ℃, continuously heating to 205 ℃, keeping the temperature for 10 minutes, putting the film into ice water for quenching, cleaning and drying to obtain the one-dimensional TiO2Polyvinylidene fluoride composite film doped with nanowire hybrid structure, wherein the TiO is2@Fe3O4The doping amount of the @ EDA nanowire in the composite film is 1-20 vol%.
Preferably, in the step (1) A, the titanium dioxide nanoparticles are added into the sodium hydroxide solution, and the magnetic stirring speed is 300-700 r/min; and (2) annealing temperature of the high-temperature box type furnace in the step (1) B is 60-80 ℃.
Preferentially, the low-speed stirring speed in the step (2) B is 100-200 r/min; and (3) in the step (2) C, the rotation speed of centrifugal collection is 5000-7000 r/min, and the temperature of vacuum drying is 60-80 ℃.
Preferably, the drying temperature of the film in the step (3) is 60-80 ℃.
Compared with the prior artThe invention has the advantages that: the invention relates to one-dimensional TiO2Polyvinylidene fluoride composite film doped with nanowire hybrid structure and preparation method thereof, and one-dimensional TiO doped polyvinylidene fluoride composite film2@Fe3O4The @ EDA hybrid structure can effectively improve the dielectric, anti-breakdown and energy storage properties of the filled PVDF-based nano composite film. The experimental result shows that the one-dimensional TiO is2@Fe3O4The PVDF-based multiphase composite film filled with the @ EDA hybrid structure has excellent dielectric and energy storage properties, and shows that the overall performance of the composite material can be greatly improved by utilizing the advantages of various dielectric materials through the microstructure design of the nanofiller. The preparation of the composite film material with low filling amount, high energy storage and high efficiency is successfully realized by using the metal-insulating nano filler, the preparation process flow is simple and convenient, and the wide application can be realized.
Drawings
FIG. 1 shows (a) TiO2@Fe3O4The microtopography of @ EDA nanowires, (b) frozen sections of 1 vol% and 2 vol% composite film for (c), and surface map of 2 vol% composite film for (d);
FIG. 2 is TiO2Nanowire and TiO2@Fe3O4X-ray diffraction patterns of @ EDA nanowires;
FIG. 3 shows different contents of TiO2@Fe3O4The energy storage density of the @ EDA composite film;
FIG. 4 shows different contents of TiO2@Fe3O4The charge-discharge efficiency of the @ EDA composite film;
FIG. 5 is a Weibull distribution of composite films of different fillers at a volume fraction of 2%;
FIG. 6 shows different contents of TiO2@Fe3O4The dielectric constant and dielectric loss of the @ EDA composite film at different frequencies.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Detailed description of the preferred embodiments
Example 1
One-dimensional TiO2Polyvinylidene fluoride composite film doped with nanowire hybrid structure, wherein one-dimensional TiO2The nano-wire hybrid structure is one-dimensional TiO2The outside of the nanowire is wrapped with Fe3O4Fine particles, modified with EDA, the above one-dimensional TiO2The doping amount of the nanowire hybrid structure in the composite film is 1-20 vol%. The preparation method comprises the following steps:
1. synthesis of TiO2Nanowire:
(1) adding 2g of titanium dioxide nanoparticles into a 10M sodium hydroxide solution, performing ultrasonic treatment for 30 minutes, then uniformly mixing and stirring for 4 hours at a magnetic stirring speed of 300-700 r/min, transferring the mixed solution into a high-pressure reaction kettle with Teflon, reacting for 24 hours at 200 ℃, washing a product until the pH value is approximately equal to 7 after the reaction is finished, and drying to obtain a sodium titanate nanowire;
(2) soaking the sodium titanate nanowire in 0.2M HCl for 4-6 hours, washing and drying to obtain H2Ti3O7Nanowire of H2Ti3O7The nanowire is put into a high-temperature box type furnace to be annealed at the temperature of 60-80 ℃ for 2-5 hours, and the product is collected, namely TiO2A nanowire;
2. synthesis of TiO2@Fe3O4Nanowire:
(1) 150ml of deionized water, 0.01 g of polyvinylpyrrolidone (PVP) and 2g of TiO2Adding the nano-wire into a three-neck flask; placing the three-neck flask in an ultrasonic cleaner for ultrasonic treatment for 30 minutes, and then mechanically stirring at a low speed of 100-200 r/min for 4 hours to form a solution A;
(2) 0.16g of FeCl was taken3·6H2O and 0.32g FeSO4·7H2Placing the O into a small beaker, adding 50ml of water for dissolving, and stirring at a low speed to obtain a uniform mixed solution B;
(3) adding the mixed solution B into the solution A dropwise with a separating funnel in a water bath at 50-70 deg.C, controlling flow rate and time of the liquid, changing the mixed solution from milky white to light brown, stirring for 1-3 hr, collecting the product, cleaning, and centrifuging at rotation speed5000-7000 r/min; ) Vacuum drying (at the temperature of 60-80 ℃) to obtain TiO2@Fe3O4A nanowire;
3、TiO2@Fe3O4ethylenediamine organic modification of nanowires
Taking 3g of TiO2@Fe3O4Adding the nanowire and 30mL of 0.02M ethylenediamine hydrochloride solution into a three-neck flask, performing ultrasonic treatment for 30 minutes in a water bath at 55 ℃, stirring for 12 hours, collecting a product, cleaning, centrifuging and drying in vacuum to obtain TiO2@Fe3O4@ EDA nanowires;
4. preparation of nanocomposite films
(1) Weighing 0g, 0.025g, 0.05g, 0.075g, 0.1g TiO2@ Fe3O4@ EDA nanowires are respectively placed in 20 ml small beakers, 5 ml of Dimethylformamide (DMF) is added into each beaker, after the sealing and the ultrasonic treatment are carried out for 1 hour, 1g of polyvinylidene fluoride (PVDF) powder and 5 ml of Dimethylformamide (DMF) are added under the mechanical stirring, and the stirring is carried out for 12 to 18 hours to prepare mixed solutions with corresponding volume fractions (0 vol.%, 1 vol.%, 2 vol.%, 3 vol.%, 4 vol.%); the prepared TiO2@ Fe3O4@ EDA nanowire material is measured by a drainage method to obtain density, then the volume of the added material is obtained by calculation and converted into corresponding volume fraction content, and the volume fraction can visually express the space proportion component of the doped material in the composite medium;
(2) vacuumizing the mixed solution until no bubbles escape in a vacuum box, dropping the mixed solution on horizontal conductive glass, paving the solution by using a scraper, quickly vacuumizing, heating and drying excess solvent at 60 ℃, continuously heating to 205 ℃, keeping the temperature for 10 minutes, putting the film into ice water for quenching, and then drying.
Example 2
The difference from the above example 1 is that:
step (1) Synthesis of TiO2In the nanowire: adding 1g of titanium dioxide nano-particles into 10M sodium hydroxide solution, carrying out ultrasonic treatment for 30 minutes, and then uniformly mixing and stirring for 5 hours under magnetic stirringThen, transferring the mixed solution into a high-pressure reaction kettle with Teflon, reacting for 24 hours at 150 ℃, after the reaction is finished, washing the product to be neutral, and drying to obtain the sodium titanate nanowire;
step (2) Synthesis of TiO2@Fe3O41g of TiO in the nanowire2Adding nanowires, 0.01 g of polyvinylpyrrolidone (PVP) and 150ml of deionized water into a three-neck flask, placing the three-neck flask in an ultrasonic cleaner for ultrasonic treatment for 20 minutes, and stirring for 5 hours to form a solution A;
step (3) TiO2@Fe3O41 gTiO is taken out in ethylenediamine organic modification of nano-wire2@Fe3O4Adding the nanowire and 30mL of 0.02M ethylenediamine hydrochloride solution into a three-neck flask, performing ultrasonic treatment for 40 minutes in a water bath at 50 ℃, stirring for 12 hours, collecting a product, cleaning, centrifuging and drying in vacuum to obtain TiO2@Fe3O4@ EDA nanowires.
Example 3
The difference from the above example 1 is that:
step (1) Synthesis of TiO2In the nanowire: adding 5g of titanium dioxide nanoparticles into a 10M sodium hydroxide solution, performing ultrasonic treatment for 60 minutes, uniformly mixing and stirring for 1 hour under magnetic stirring, transferring the mixed solution into a high-pressure reaction kettle with Teflon, reacting for 12 hours at 250 ℃, washing a product to be neutral after the reaction is finished, and drying to obtain a sodium titanate nanowire;
step (2) Synthesis of TiO2@Fe3O45g of TiO in the nanowire2Adding nanowires, 0.01 g of polyvinylpyrrolidone (PVP) and 150ml of deionized water into a three-neck flask, placing the three-neck flask in an ultrasonic cleaner for ultrasonic treatment for 40 minutes, and stirring for 3 hours to form a solution A;
step (3) TiO2@Fe3O4Obtaining 5g TiO from ethylenediamine organic modification of nano wire2@Fe3O4Adding nanowire and 30mL of 0.02M ethylenediamine hydrochloride solution into a three-neck flask, and ultrasonically treating in a water bath at 80 deg.CStirring for 12 hours for 20 minutes, collecting the product, washing, centrifuging and drying in vacuum to obtain TiO2@Fe3O4@ EDA nanowires.
Second, result analysis
FIG. 1 (a) shows a hybrid structure of TiO2@Fe3O4The @ EDA nanowire has a high aspect ratio and is in TiO2@Fe3O4Different amounts of Fe are attached to the surface of the @ EDA nanowire3O4And (3) microparticles. FIGS. 1(b) and 1(c) are frozen sectional views of 1 vol% and 2 vol% composite films, respectively. It can be observed that the thickness of the composite film is about 12 μm, the whole body between the polymer matrix and the nano-filler is very tight, the filler is uniformly dispersed in the polymer, and no clearly discernable agglomeration and holes exist, which indicates that the TiO after organic modification2@Fe3O4The compatibility between the @ EDA nanowire and the polymer is effectively improved, and the interface interaction inside the film is enhanced. FIG. 1 (d) is a surface view of a 2 vol% composite film, and it can be seen from the surface of the composite film in FIG. 1 (d) that TiO with a high aspect ratio is present2@Fe3O4The @ EDA nanowire is randomly dispersed and compact in the matrix, which proves that the preparation of the nano composite film is very successful, and provides a foundation for obtaining high energy storage density and high breakdown field strength.
As shown in FIG. 2, it can be seen from XRD diffraction pattern of the filler that Fe is attached to the surface3O4Micronized TiO2@Fe3O4@ EDA nanowire with TiO2In comparison with the nanowire, Fe is clearly seen3O4Characteristic peak of (1), and face centered cubic Fe3O4The crystal PDF card JCPDS 75-0033 is completely consistent. Furthermore, TiO2@Fe3O4Peak position of @ EDA and TiO2No deviation indicates that the composite filler with the hybrid structure does not change the crystal structures of the two substances.
FIG. 3 shows different contents of TiO2@Fe3O4The energy storage density of the @ EDA composite film can be significantly improved when 1 vol.% of the hybrid structured nanofiller is added to the polymeric PVDFThe energy storage density of the composite film reaches 13.64J/cm when the filling amount of the material is 2 vol%3Compared with the 7.11J/cm of a pure PVDF film, the thickness of the film is improved by nearly one time.
FIG. 4 shows different contents of TiO2@Fe3O4The charge and discharge efficiency of the @ EDA composite film is obviously improved when the hybrid structure nano filler with the content of 1 vol.% and 2 vol.% is added into the PVDF polymer, the charge and discharge efficiency of the composite film is 69.4% and 63.5% respectively, and is improved by 63.0% compared with that of the pure PVDF film.
FIG. 5 shows different contents of TiO2@Fe3O4The results of linear fitting of the weibull distribution of the @ EDA composite film. Selecting more than ten different area points for each sample to carry out pressurization test, sequencing and linearly fitting the breakdown field intensity obtained by the test, and finally obtaining the Weibull distribution diagram of the composite film. The figure visually depicts the breakdown field intensity dispersion degree and the Weibull modulus beta of the composite film when the volume fraction of different nanowire fillers is 2%, and the comparison shows that the breakdown strength of the organically modified composite film is more stable, the breakdown electric field values of almost all test points are more than 350 kV/mm, and the Weibull modulus beta reaches 29.98 and 33.97; this is all superior to unmodified composite films.
FIG. 6 is a graph of doping with different volume fractions of TiO2@Fe3O4The dependence of the dielectric property of the composite film of the @ EDA nanowire on frequency. By observation, nano TiO can be obtained2The dielectric constant of the composite film increased with increasing filler volume fraction, and at 4% filler volume fraction, the dielectric constant of the sample at 1 kHz was 23.60, which is almost 2.4 times that of pure PVDF (9.85). This result is mainly due to the use of TiO in the hybrid structured nanofiller2，Fe3O4Due to the difference of the conductivity between the composite film and PVDF, the space charge transmission path of the composite film is blocked under the condition of an external electric field, so that the interface polarization effect is enhanced, and the dielectric constant of the composite film is increased. The dielectric loss of all samples is controlled in a mode of reverse observationLess than 0.044, the better overall insulation is shown, which provides possibility for high breakdown strength of the nano composite film.
The above description is not intended to limit the present invention, and the present invention is not limited to the above examples. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the true spirit and scope of the invention.
Claims (6)
1. One-dimensional TiO2The polyvinylidene fluoride composite film doped with the nanowire hybrid structure is characterized in that: the one-dimensional TiO2The nano-wire hybrid structure is one-dimensional TiO2The outside of the nanowire is wrapped with Fe3O4The particles are modified by EDA, and the one-dimensional TiO2The doping amount of the nanowire hybrid structure in the composite film is 1-4 vol%.
2. A one-dimensional TiO according to claim 12The polyvinylidene fluoride composite film doped with the nanowire hybrid structure is characterized in that: the one-dimensional TiO2The doping amount of the nanowire hybrid structure in the composite film is 1 vol%, 2 vol%, 3 vol% or 4 vol%.
3. The one-dimensional TiO of claim 12The preparation method of the polyvinylidene fluoride composite film doped with the nanowire hybrid structure is characterized by comprising the following steps:
(1) synthesis of TiO2Nanowire and method of manufacturing the same
A. Adding 1-5g of titanium dioxide nanoparticles into 10M sodium hydroxide solution, performing ultrasonic treatment for 30-60 minutes, uniformly mixing and stirring for 1-5 hours under magnetic stirring, transferring the mixed solution into a high-pressure reaction kettle with Teflon, reacting for 12-24 hours at 150-250 ℃, washing a product to be neutral after the reaction is finished, and drying to obtain a sodium titanate nanowire;
B. soaking the sodium titanate nanowire in 0.2M HCl for 4-6 hours, washing and drying to obtain H2Ti3O7Nanowire of H2Ti3O7The nano wire is put into a high-temperature box type furnace for annealing for 2 to 5 hours, and the collected product is TiO2A nanowire;
(2) synthesis of TiO2@Fe3O4Nanowire:
A. 1-5g of TiO2Adding nanowires, 0.01 g of polyvinylpyrrolidone and 150ml of deionized water into a three-neck flask, placing the three-neck flask in an ultrasonic cleaner for ultrasonic treatment for 20-40 minutes, and stirring for 3-5 hours to form a solution A;
B. 0.16g of FeCl was taken3·6H2O and 0.32g FeSO4·7H2Placing the O into a small beaker, adding 50ml of water for dissolving, and stirring at a low speed to form a uniform mixed solution B;
C. dropwise adding the mixed solution B into the solution A in a water bath kettle at 50-70 deg.C until the solution turns from milky white to light brown, stirring for 1-3 hr, collecting the product, cleaning, centrifuging, and vacuum drying to obtain TiO2@Fe3O4A nanowire;
(3)TiO2@Fe3O4ethylenediamine organic modification of nanowires
Taking 1-5g of TiO2@Fe3O4Adding the nanowire and 30mL of 0.02M ethylenediamine hydrochloride solution into a three-neck flask, performing ultrasonic treatment for 20-40 minutes in a water bath kettle at 50-80 ℃, stirring for 12 hours, collecting a product, cleaning, centrifuging and drying in vacuum to obtain TiO2@Fe3O4@ EDA nanowires;
(4) preparation of composite films
Adding TiO into the mixture2@Fe3O4Mixing the @ EDA nanowire, dimethylformamide and polyvinylidene fluoride powder, stirring for reacting for 12-18 hours, vacuumizing, dripping on horizontal conductive glass, paving, quickly vacuumizing, heating to 60 ℃ to dry excessive solvent, continuously heating to 205 ℃, keeping the temperature for 10 minutes, putting the film into ice water for quenching, cleaning and drying to obtain the one-dimensional TiO2Polyvinylidene fluoride composite film doped with nanowire hybrid structure, in which TiO2@Fe3O4The doping amount of the @ EDA nanowire in the composite film is 1-4 vol%.
4. A one-dimensional TiO compound according to claim 32The preparation method of the polyvinylidene fluoride composite film doped with the nanowire hybrid structure is characterized by comprising the following steps of: in the step (1), titanium dioxide nanoparticles are added into a sodium hydroxide solution, and the magnetic stirring speed is 300-700 r/min; and (2) annealing temperature of the high-temperature box type furnace in the step (1) B is 60-80 ℃.
5. A one-dimensional TiO compound according to claim 32The preparation method of the polyvinylidene fluoride composite film doped with the nanowire hybrid structure is characterized by comprising the following steps of: in the step (2) B, the low-speed stirring speed is 100-200 r/min; in the step (2) C, the rotation speed of centrifugal collection is 5000-7000 r/min, and the temperature of vacuum drying is 60-80 ℃.
6. A one-dimensional TiO compound according to claim 32The preparation method of the polyvinylidene fluoride composite film doped with the nanowire hybrid structure is characterized by comprising the following steps of: and (4) drying the film at the temperature of 60-80 ℃.
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