CN115160713B - Preparation method and application of nanoparticle with continuously tunable physical properties - Google Patents
Preparation method and application of nanoparticle with continuously tunable physical properties Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a nanoparticle with continuously tunable physical properties, and belongs to the technical field of composite material interface property regulation and control. The invention solves the technical problem that the existing inorganic particles can not realize continuous physical property tuning. According to the invention, graphene Oxide (GO) is used as a flexible shell material, the nano composite particles with a core-shell structure are formed on the surfaces of nano barium titanate particles through structural design cladding, and the tuning of the conductivity of the nano composite particles can be realized by changing the number and the types of oxygen-containing functional groups on the surfaces of the GO, namely, the insulation property of the oxidized state is adjusted to the reduced graphene state. The composite film is prepared by mixing nano particles with different conductivities and polymers with ferroelectric characteristics, and the composite material with different interface physical characteristics can be obtained, wherein the highest dielectric constant of the composite film is increased by 54.9% compared with PVDF, the energy storage density is increased by 78.2%, and the dielectric loss is kept in a lower range.
Description
Technical Field
The invention relates to a preparation method and application of a nanoparticle with continuously tunable physical properties, and belongs to the technical field of interface property regulation and control of composite materials.
Background
Along with the progress of technology, higher requirements are put on high-performance energy storage devices of advanced electronic, electric vehicles and power systems. The current energy storage technologies commonly used include a battery, a super capacitor and a dielectric capacitor, and compared with the former two technologies, the dielectric capacitor has high power density, and the subtle-level discharge speed is very suitable for grid frequency modulation and vehicle acceleration, but the low energy density limits the further reduction of the volume and the mass of the capacitor, so that the miniaturization, the light weight and the high efficiency process of the energy storage equipment are hindered. In the research of improving the energy storage density of the dielectric medium, the scholars at home and abroad mostly adopt a method of adding a second phase, and the research of inorganic particle/polymer composite materials as the high-performance energy storage dielectric medium is greatly progressed. However, in the process of further exploring the energy storage mechanism, the inorganic particles cannot realize continuous physical property tuning, so that the interface property of the composite material is composed of two variables of the physical property of the component material and the interaction between the matrix and the component, and a single variable cannot be peeled off. It is therefore necessary to provide a method for preparing nanoparticles with continuously tunable physical properties and the use thereof.
Disclosure of Invention
The invention provides a preparation method and application of nano particles with continuously tunable physical properties, and aims to solve the problem that the existing inorganic particles cannot realize continuous tuning of physical properties, so that the interface properties of a composite material comprise two variables of physical properties of a component material and interaction between a matrix and the component, and a single variable cannot be stripped.
The technical scheme of the invention is as follows:
it is an object of the present invention to provide a method for preparing nanoparticles with continuously tunable physical properties, comprising the steps of:
s1, mixing graphene oxide and barium titanate nano particles with deionized water, and performing ultrasonic dispersion at 0-5 ℃ for 20-40 min to obtain a dispersion liquid; placing the dispersion liquid into an atomizing cup of an ultrasonic atomizer, oscillating the dispersion liquid into small liquid drops by ultrasonic waves, then entering a high-temperature area of a tube furnace under the drive of carrier gas, rapidly drying at 500-600 ℃, then carrying out suction filtration on a receiving film of a receiver, and taking down particles to obtain spherical nano particles which are marked as M-BTO@GO;
s2, placing M-BTO@GO into hydroiodic acid steam, and reacting for 10-120 min at 80-100 ℃ to obtain high-conductivity nano particles, namely H-BTO@GO;
s3, mixing M-BTO@GO or H-BTO@GO with toluene and azodiisobutyronitrile, reacting for 2-4 hours under the protection of inert gas, filtering and washing the toluene after the reaction, drying the precipitate for 6-24 hours under the vacuum condition of 50 ℃, adding the obtained product into NaOH methanol solution, refluxing for 48 hours at 60 ℃, washing with ultrapure water after the completion, adding hydrochloric acid solution for acidification, washing with ultrapure water again to be neutral, and obtaining the low-conductivity nano-particles, namely L-BTO@GO.
Further defined, the graphene oxide in S1 has a lateral dimension of 2 μm to 20 μm, a thickness of 1nm to 20nm, and a diameter of 80nm to 200nm.
Further defined, the ultrasonic dispersion frequency in S1 is 300W.
Further defined, the S1 tubular furnace has a double temperature zone with a length of 40cm to 80cm.
Further defined, the specific operation procedure of S2 is:
(1) preparing an empty beaker, adding a hydriodic acid solution, and preheating to 80-100 ℃;
(2) placing the M-BTO@GO nano particles prepared in the step (1) on a bracket by using parchment paper (as shown in fig. 10, the bracket consists of supporting legs and a bearing surface, wherein the bearing surface is a round hollowed-out plate with the diameter of 80mm and the thickness of 10mm, the supporting legs are columnar bodies with the diameter of 5mm and the length of 70 mm), and then placing the bracket with the particles in a beaker in the step (1), and covering a cover to enable the M-BTO@GO nano particles to react in hydroiodic acid steam for 10min to 2h; then placing the bracket with the particles in an empty beaker, flushing with ultrapure water until the bracket is neutral, and obtaining the nano particles with high conductivity, which are marked as H-BTO@GO.
Further defined, the concentration of the hydroiodic acid solution in step (1) is 15wt% to 30wt%.
Further defined, the material of the bracket in the step (2) is polytetrafluoroethylene.
Further defined, the ratio of M-BTO@GO to the hydroiodic acid solution in the step (2) is 1mg (2-4) ml.
Further defined, the specific operation procedure of S3 is:
(1) preparing a three-neck flask, adding 1mg of H-BTO@GO nano particles, 1ml of toluene and 100-500 mg of azodiisobutyronitrile, mixing, preheating to 70 ℃, filling inert protective gas into the three-neck flask, and reacting for 2-4 hours;
(2) after the reaction is finished, filtering and washing with excessive toluene, and vacuum drying the obtained product for 6-24 hours at 50 ℃;
(3) then adding the obtained product into a methanol solution of sodium hydroxide with the concentration of 6-10 mol/L, and refluxing at 60 ℃ for 48 hours;
(4) after the reaction is finished, washing with ultrapure water, then adding hydrochloric acid solution for acidification, washing with ultrapure water again until the solution is neutral, and then vacuum drying for 6-24 hours at 50 ℃ to obtain the low-conductivity core-shell structure nano composite particles, which are marked as L-BTO@GO.
Further defined, the ratio of the product used for the reaction in step (3) to the methanol solution of sodium hydroxide is 1mg: (1-2 mL).
Further defined, the concentration of the hydrochloric acid solution in the step (4) is 0.1mol/L to 2mol/L.
The second object of the invention is to prepare nano particles with continuously tunable physical properties by adopting the method, wherein the nano particles are BTO@GO nano particles with different conductivities, and particularly M-BTO@GO, H-BTO@GO or L-BTO@GO.
The third object of the present invention is to apply the above nanoparticle with continuously tunable physical properties to prepare a composite material with continuously tunable interface physical properties, the preparation method is as follows:
and mixing the BTO@GO nano particles with different conductivities with a high polymer substance and a solvent, spin-coating and drying to obtain the composite film with different interface characteristics.
Further defined, the polymeric material is PVDF, P (VDF-HFP), P (VDF-TrFE) or P (VDF-TrFE-CTFE).
Further defined, the solvent is DMF, DMAc, or NMP.
Further defined, the preparation of the composite film is specifically performed according to the following steps:
(1) taking a single-neck flask, and ultrasonically dispersing BTO@GO nano particles (M-BTO@GO, H-BTO@GO or L-BTO@GO) in DMF;
(2) a single-neck flask is taken, PVDF powder is dispersed in DMF, and magnetic stirring is carried out for 1-6 h until the solution is transparent;
(3) mixing the solutions in the step (1) and the step (2), and magnetically stirring for 30-120 min again to obtain a mixed solution to be spin-coated;
(4) 1 ml-2 ml of the solution is dripped on a silicon wafer, the spin coating temperature is set to be at room temperature, the speed is 3000rpm, and the time is 30 seconds;
(5) after the completion, the silicon wafer coated with the solution is placed in a baking oven at 60 ℃ and dried for 10 hours;
(6) and (3) stripping the film from the silicon wafer to obtain the BTO@GO/PVDF composite film.
Further defined, the concentration of the mixed solution to be spin-coated is 75mg/ml to 150mg/ml.
According to the invention, graphene Oxide (GO) is used as a flexible shell material, the nano composite particles with a core-shell structure are formed on the surfaces of nano barium titanate particles through structural design cladding, and the tuning of the conductivity of the nano composite particles can be realized by changing the number and the types of oxygen-containing functional groups on the surfaces of the GO, namely, the insulation property of the oxidized state is adjusted to the reduced graphene state. Compared with the prior art, the application has the following beneficial effects:
(1) According to the invention, the graphene is modified to prepare the nano particles with different interface characteristics on the premise of unchanged components, so that a simple, universal and effective technology is provided for detecting the influence mechanism of single variable of the interface characteristics on the energy storage performance of the composite material, and a theoretical foundation is laid for further exploring the high energy storage density energy storage technology.
(2) According to the preparation method, the curling of the graphene oxide and the preparation of the graphene oxide coated nano particles are realized through an aerogel method, the formation of the graphene oxide wrinkled shrinking balls can be obviously distinguished through a scanning electron microscope picture, the existence of nano particles in a shell layer can be distinguished through transmission, the preparation method of the core-shell structure nano particles with tunable physical characteristics is realized, and the preparation method of the core-shell structure particles through the aerogel method is simple, controllable in structure, expandable and good in application prospect.
(3) The L-BTO@GO nano particles prepared by the method provided by the invention are prepared from carboxyl and macromolecule-CF 2 The groups form hydrogen bond interaction, and the conductivity of the graphene is greatly reduced due to the existence of carboxyl functional groups, so that the composite film obtained by compositing the graphene with polyvinylidene fluoride-based polymer substances has better insulativity.
(4) The functional groups on the surfaces of the H-BTO@GO nano particles prepared by the method are mostly removed, the interaction force between the H-BTO@GO nano particles and a polymer matrix is extremely weak, but the conductivity of graphene is greatly improved, so that the conductivity of a composite film can be improved by compositing the graphene with polyvinylidene fluoride polymer substances.
(5) The M-BTO@GO nanoparticle prepared by the method provided by the invention has the functional group number between L-BTO@GO and H-BTO@GO, has moderate conductivity, and has weak interaction force with a high polymer matrix.
(3) The BTO@GO nano particles prepared by the method have different interface states and interface characteristics, have a larger breakthrough in terms of dielectric properties, compared with PVDF, the dielectric constant of the BTO@GO/PVDF composite film is obviously increased by 54.9%, the highest dielectric constant is obviously increased in terms of polarization intensity, the energy storage density is also greatly improved by 78.2%, the energy storage efficiency is improved, the paradox between the energy storage density and the energy storage efficiency is broken, and the simultaneous improvement of the two is realized.
(4) The BTO@GO nano particle prepared by the method provided by the invention can realize conductivity of 80-4600S m -1 The regulation and control of the range, the quantity of the functional groups and the interaction force between the functional groups and the polymer matrix are changed, so that the regulation and control of dielectric property and energy storage property are realized, the general rule that the interface property influences the energy storage property is found, and the interface characteristic is realized on the premise that the interface material is unchangedThe tuning of the property lays a foundation for detecting the relation between the interface characteristic and the energy storage characteristic of the polymer composite material.
Drawings
Fig. 1 is a SEM photograph of a core-shell structure of graphene oxide coated nano barium titanate particles;
FIG. 2 is a TEM photograph of a core-shell structure of graphene oxide coated nano barium titanate particles;
FIG. 3 is a graph showing the dielectric constant of a BTO@GO/PVDF composite film prepared by the method of embodiment 1 as a function of frequency;
FIG. 4 is a graph showing dielectric loss versus frequency for a BTO@GO/PVDF composite film prepared by the method of specific example 1;
FIG. 5 is a graph showing the dielectric constant of a BTO@GO/PVDF composite film prepared by the method of embodiment 2 as a function of frequency;
FIG. 6 is a graph of dielectric loss versus frequency for a BTO@GO/PVDF composite film prepared by the method of embodiment 2;
FIG. 7 is a graph of dielectric constant and dielectric loss as a function of conductivity for a BTO@GO/PVDF composite film;
FIG. 8 is a graph showing the change of polarization intensity of a BTO@GO/PVDF composite film with the electric field intensity;
FIG. 9 is a graph showing the change of discharge energy density of a BTO@GO/PVDF composite film with the strength of an electric field;
fig. 10 is a schematic view of a stent structure.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
Specific embodiment case 1:
the embodiment provides a preparation method of BTO@GO nano particles, which comprises the following steps:
firstly, mixing 40mg of barium titanate nano particles with the average particle size of 80nm with 20ml of deionized water, performing ultrasonic dispersion for 40min at the temperature of 0 ℃ and the ultrasonic power of 300W, then adding 40mg of graphene oxide with the transverse dimension of 2 mu m and the thickness of 2nm, and performing ultrasonic dispersion for 20min at the temperature of 0 ℃ and the ultrasonic power of 300W to obtain a dispersion liquid. Then, the dispersion liquid obtained in the previous step is placed in an atomizing cup of an ultrasonic atomizer, the dispersion liquid is vibrated into small liquid drops by ultrasonic waves, then the small liquid drops enter a high-temperature area of a tube furnace under the drive of carrier gas (high-purity nitrogen), the small liquid drops are dried rapidly at 600 ℃, the lamellar nano materials are curled in the rapid drying process, spherical nano particles are wrapped and then are pumped and filtered on a PTFE film of a receiver, and the particles are taken down, so that the spherical nano particles are obtained and marked as M-BTO@GO-1. The M-BTO@GO-1 microstructure was characterized and the results are shown in FIGS. 1 and 2.
The specific operation process of the second step is as follows:
(1) preparing an empty beaker, adding 50ml of a 22.5wt% hydriodic acid solution, and preheating to 100 ℃;
(2) placing 20mg of the M-BTO@GO-1 nano particles prepared in the first step on a bracket shown in fig. 10, placing the bracket with the particles in a beaker in the step (1), covering a cover, and reacting the M-BTO@GO-1 nano particles in hydroiodic acid steam for 2 hours; then placing the bracket with the particles in an empty beaker, flushing with ultrapure water until the bracket is neutral, and obtaining the nano particles with high conductivity, which are marked as H-BTO@GO-1.
The specific operation process of the third step is as follows:
(1) preparing a three-neck flask, adding 10mg of H-BTO@GO-1 nano particles, 10ml of toluene and 2g of azobisisobutyronitrile, uniformly mixing, preheating to 70 ℃, filling inert gas (nitrogen) into the three-neck flask for protection, and reacting for 4 hours;
(2) after the reaction is finished, filtering and washing with excessive toluene, and vacuum drying the obtained product for 24 hours at 50 ℃;
(3) then 8mg of the obtained product is weighed and added into 8ml of 10mol/L sodium hydroxide methanol solution, and reflux is carried out for 48 hours at 60 ℃;
(4) after the reaction is finished, washing with ultrapure water, then adding 5ml of hydrochloric acid solution with the concentration of 0.1mol/L for acidification, washing with ultrapure water again until the solution is neutral, and then vacuum drying for 24 hours at 50 ℃ to obtain the low-conductivity core-shell structure nano composite particles, which are marked as L-BTO@GO-1.
Conductivity tests were performed on M-BTO@GO-1, H-BTO@GO-1 and L-BTO@GO-1 obtained in example 1, and the results are shown in Table 1 below:
table 1:
| sample of | Conductivity (S/m) |
| M-BTO@GO-1 | 200 |
| |
4600 |
| |
80 |
The polyvinylidene fluoride-based composite film was prepared by using M-BTO@GO-1, H-BTO@GO-1 or L-BTO@GO-1 obtained in specific example 1, and the specific operation procedure is as follows:
(1) taking a single-neck flask, and ultrasonically dispersing 3.2mgM-BTO@GO-1 nano particles in 5ml of DMF;
(2) another single-neck flask was taken, 2g of PVDF powder was dispersed in 10ml of DMF, and magnetically stirred for 6h until the solution was transparent;
(3) mixing the solutions in the step (1) and the step (2), and magnetically stirring for 120min again to obtain a mixed solution to be spin-coated with the concentration of 133 mg/ml;
(4) 1 ml-2 ml of the solution is dripped on a silicon wafer, the spin coating temperature is set to be at room temperature, the speed is 3000rpm, and the time is 30 seconds;
(5) after spin coating is finished, the silicon wafer coated with the solution is placed in a baking oven at 60 ℃ and dried for 10 hours;
(6) and (3) stripping the film from the silicon wafer to obtain the M-BTO@GO/PVDF-1 composite film.
According to the operation process, M-BTO@GO-1 is replaced by H-BTO@GO-1 and L-BTO@GO-1, and H-BTO@GO/PVDF-1 and L-BTO@GO/PVDF-1 are prepared and obtained respectively.
And performing performance characterization on the obtained M-BTO@GO@GO/PVDF-1, H-BTO@GO/PVDF-1 and L-BTO@GO/PVDF-1 composite films. As shown in fig. 3, as the frequency increases, the dielectric constants of all samples show a tendency to decrease and then increase, because the polarization rate of the dipoles in the film gradually does not follow the change rate of the external electric field as the frequency increases. As shown in fig. 4, the dielectric loss was kept low and did not change much, although the second phase filler was added, as shown in fig. 4.
Specific embodiment case 2:
the embodiment provides a preparation method of BTO@GO nano particles, which comprises the following steps:
firstly, mixing 20mg of barium titanate nano particles with the average particle size of 200nm with 40ml of deionized water, performing ultrasonic dispersion for 40min at the temperature of 0 ℃ and the ultrasonic power of 300W, then adding 20mg of graphene oxide with the transverse dimension of 5 mu m and the thickness of 2nm, and performing ultrasonic dispersion for 20min at the temperature of 0 ℃ and the ultrasonic power of 300W to obtain a dispersion liquid. Then, the dispersion liquid obtained in the previous step is placed in an atomizing cup of an ultrasonic atomizer, the dispersion liquid is vibrated into small liquid drops by ultrasonic waves, then the small liquid drops enter a high-temperature area of a tube furnace under the drive of carrier gas (high-purity nitrogen), the small liquid drops are dried rapidly at 500 ℃, the lamellar nano materials are curled in the rapid drying process, spherical nano particles are wrapped and then are pumped and filtered on a PTFE film of a receiver, and the particles are taken down, so that the spherical nano particles are obtained and marked as M-BTO@GO-2.
The specific operation process of the second step is as follows:
(1) preparing an empty beaker, adding 50ml of a 22.5wt% hydriodic acid solution, and preheating to 100 ℃;
(2) placing 30mg of the M-BTO@GO-2 nano particles prepared in the first step on a bracket shown in fig. 10, placing the bracket with the particles in a beaker in the step (1), covering a cover, and reacting the M-BTO@GO-1 nano particles in hydroiodic acid steam for 60min; then placing the bracket with the particles in an empty beaker, flushing with ultrapure water until the bracket is neutral, and obtaining the nano particles with high conductivity, which are marked as H-BTO@GO2.
The specific operation process of the third step is as follows:
(1) preparing a three-neck flask, adding 20mg of H-BTO@GO2 nano particles, 20ml of toluene and 4g of azodiisobutyronitrile, uniformly mixing, preheating to 70 ℃, filling inert gas (nitrogen) into the three-neck flask for protection, and reacting for 4 hours;
(2) after the reaction is finished, filtering and washing with excessive toluene, and vacuum drying the obtained product for 24 hours at 50 ℃;
(3) then 15mg of the obtained product is weighed and added into 30ml of 10mol/L sodium hydroxide methanol solution, and reflux is carried out for 48 hours at 60 ℃;
(4) after the reaction is finished, washing with ultrapure water, then adding 5ml of hydrochloric acid solution with the concentration of 0.1mol/L for acidification, washing with ultrapure water again until the solution is neutral, and then vacuum drying for 24 hours at 50 ℃ to obtain the low-conductivity core-shell structure nano composite particles, which are marked as L-BTO@GO-2.
Conductivity tests were performed on M-BTO@GO-2, H-BTO@GO-2 and L-BTO@GO-2 obtained in example 2, and the results are shown in Table 2 below:
the polyvinylidene fluoride-based composite film is prepared by using M-BTO@GO2, H-BTO@GO2 or L-BTO@GO2 obtained in the specific embodiment 2, and the specific operation process is as follows:
(1) taking a single-neck flask, and ultrasonically dispersing 3.2mgM-BTO@GO-2 nano particles in 5ml of DMF;
(2) another single-neck flask was taken, 2g of PVDF powder was dispersed in 10ml of DMF, and magnetically stirred for 6h until the solution was transparent;
(3) mixing the solutions in the step (1) and the step (2), and magnetically stirring for 120min again to obtain a mixed solution to be spin-coated with the concentration of 133.3 mg/ml;
(4) 1 ml-2 ml of the solution is dripped on a silicon wafer, the spin coating temperature is set to be at room temperature, the speed is 3000rpm, and the time is 30 seconds;
(5) after spin coating is finished, the silicon wafer coated with the solution is placed in a baking oven at 60 ℃ and dried for 10 hours;
(6) and (3) stripping the film from the silicon wafer to obtain the M-BTO@GO@GO/PVDF-2 composite film.
And respectively replacing M-BTO@GO-2 with H-BTO@GO-2 and L-BTO@GO-2 according to the operation process, and respectively preparing and obtaining H-BTO@GO/PVDF-2 and L-BTO@GO/PVDF-2.
And performing performance characterization on the obtained M-BTO@GO@GO/PVDF-2, H-BTO@GO/PVDF-2 and L-BTO@GO/PVDF-2 composite films. As shown in fig. 5, as the frequency increases, the dielectric constants of all samples show a tendency to decrease and then increase, because the polarization rate of the dipoles in the film gradually does not follow the change rate of the external electric field as the frequency increases. As shown in fig. 6, the dielectric loss was kept low and did not increase significantly, as shown in fig. 6, although the second phase filler was added.
In summary, since the polarization characteristic of the composite film is dominant by the frequency dependent characteristic of the dielectric properties, the trend of the dielectric constant of the composite film with the conductivity at 1kHz is summarized, and as shown in fig. 7, as the conductivity increases, the dielectric constant of the composite film gradually increases, which means that the interfacial polarization intensity increases with the increase of the conductivity, as shown in fig. 7. Specifically, the highest dielectric constant of the composite film can reach 14.02, which is increased by 54.9% compared with PVDF, and the dielectric loss is kept in a lower range. The invention can ensure lower dielectric loss and realize the great improvement of dielectric constant.
To investigate the energy storage properties of the composite films, we performed ferroelectric property tests on different composite films, the polarization intensity was varied with the electric field as shown in FIG. 8 (80 S.m -1 Representative are L-BTO@GO/PVDF-1 and L-BTO@GO/PVDF-2, 100 S.m -1 Represented by M-BTO@GO/PVDF-2, 200 S.m -1 Represents M-BTO@GO/PVDF-1, 1500 S.m -1 Representative is H-BTO@GO/PVDF-2, 4600 S.m -1 Representative is H-BTO@GO/PVDF-1), the energy storage density as a function of electric field is shown in FIG. 9 (80 S.m therein -1 Representative are L-BTO@GO/PVDF-1 and L-BTO@GO/PVDF-2, 100 S.m -1 Represented by M-BTO@GO/PVDF-2, 200 S.m -1 Represents M-BTO@GO/PVDF-1, 1500 S.m -1 Representative is H-BTO@GO/PVDF-2, 4600 S.m -1 Representative is H-BTO@GO/PVDF-1). As can be seen from FIG. 8, the polarization intensity of the thin film gradually increased with the increase of the conductivity of the BTO@GO nanoparticles under the same electric field intensity, and the electric field intensity was 300 MV.m -1 When the polarization intensity is up to 7.16 mu C.m -2 The improvement is 60.7% compared with PVDF. Similarly, as can be seen from FIG. 9, the energy storage density of the composite film was 300 MV.m in electric field strength -1 Also, a significant increase from 4.35 J.cm of PVDF was achieved -3 The temperature is increased to 7.75 J.cm -3 . It is worth noting that the conductivity of the filler is greatly changed after modification treatment, but no great space charge accumulation is caused in the composite film, so that the breakdown field strength of the composite film is not greatly reduced, and the dielectric property and the energy storage property of the composite film are simultaneously improved. Therefore, as the conductivity of the BTO@GO nano particles increases, the dielectric property difference between GO and PVDF increases, and the interface polarization is knownThe strength is gradually increased, so that the overall polarization strength of the film is increased, and the polarization strength and the energy storage density are greatly increased. In addition, due to good conductivity of GO, electrons are more likely to migrate along the GO surface rather than entering the PVDF matrix through the interface, and the breakdown field strength of the final composite film is also kept in a higher range.
While the invention has been described in terms of preferred embodiments, it is not intended to be limited thereto, but rather to enable any person skilled in the art to make various changes and modifications without departing from the spirit and scope of the present invention, which is therefore to be limited only by the appended claims.
Claims (4)
1. A method for preparing low-conductivity nano-particles, which is characterized by comprising the following steps:
s1, mixing graphene oxide and barium titanate nano particles with deionized water, and performing ultrasonic dispersion at 0-5 ℃ for 20-40 min to obtain a dispersion liquid; placing the dispersion liquid into an atomizing cup of an ultrasonic atomizer, oscillating the dispersion liquid into small liquid drops by ultrasonic waves, then entering a high-temperature area of a tube furnace under the drive of carrier gas, rapidly drying at 500-600 ℃, then carrying out suction filtration on a receiving film of a receiver, and taking down particles to obtain spherical nano particles, wherein the spherical nano particles are marked as M-BTO@GO;
s2, placing M-BTO@GO into hydroiodic acid steam, and reacting for 10-120 min at 80-100 ℃ to obtain high-conductivity nano particles, namely H-BTO@GO;
the concentration of the hydroiodic acid in the S2 is 15-30 wt%; the ratio of M-BTO@GO to hydroiodic acid is 1mg (2-4) ml;
s3, mixing M-BTO@GO or H-BTO@GO, toluene and azodiisobutyronitrile, reacting for 2-4 hours under the protection of inert gas, filtering and washing by using toluene after the reaction is finished, drying a precipitate for 6-24 hours under the vacuum condition at 50 ℃, adding the obtained product into NaOH methanol solution, refluxing for 48 hours at 60 ℃, washing by using ultrapure water after the completion, adding hydrochloric acid solution for acidification, washing to neutrality by using ultrapure water again, and obtaining low-conductivity nano particles which are marked as L-BTO@GO;
the proportion of M-BTO@GO or H-BTO@GO, toluene and azobisisobutyronitrile in S3 is 1mg:1mL: (100-500 mg); the concentration of the NaOH methanol solution in the S3 is 6mol/L to 10mol/L; the concentration of the hydrochloric acid solution in the S3 is 0.1 mol/L-2 mol/L.
2. The method for preparing the low-conductivity nanoparticles according to claim 1, wherein the graphene oxide in S1 has a lateral dimension of 2 μm to 20 μm, a thickness of 1nm to 20nm, and a diameter of 80nm to 200nm.
3. The method for preparing the composite material by using the low-conductivity nano particles is characterized in that the method is to mix the L-BTO@GO prepared in the method in claim 1 with a high polymer substance and a solvent, spin-coat and dry the mixture to obtain the composite film.
4. A method of preparing a composite material using low conductivity nanoparticles according to claim 3, wherein the polymer is PVDF, P (VDF-HFP), P (VDF-TrFE) or P (VDF-TrFE-CTFE) and the solvent is DMF, DMAc or NMP.
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