CN109306142B - Novel dielectric composite material - Google Patents

Novel dielectric composite material Download PDF

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CN109306142B
CN109306142B CN201811147071.9A CN201811147071A CN109306142B CN 109306142 B CN109306142 B CN 109306142B CN 201811147071 A CN201811147071 A CN 201811147071A CN 109306142 B CN109306142 B CN 109306142B
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罗行
张斗
陈盛
周科朝
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Yunfan New Materials Group Co ltd
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Central South University
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Abstract

The invention belongs to the field of dielectric composite materials, and particularly relates to a novel dielectric composite material. The technical scheme is as follows: a dielectric composite material is a ceramic nanowire/polymer composite material, and according to the volume percentage, in the dielectric composite material, the ceramic nanowire accounts for 1-10%, and the polymer accounts for 90-99%; the ceramic nanowires are orderly arranged in any direction in the dielectric composite material. According to the invention, the ceramic nanowires in the slurry are directionally arranged by adopting a 3D printing technology, and the distribution direction of the nanowires is regulated and controlled, so that the performance of the composite material is effectively improved.

Description

Novel dielectric composite material
Technical Field
The invention belongs to the field of dielectric composite materials, and particularly relates to a novel dielectric composite material.
Background
In recent years, in order to alleviate the problems of environmental pollution, energy shortage and the like caused by fossil energy, renewable energy technologies such as solar cells, lithium cells, capacitors and the like are rapidly developed, wherein the capacitors have the advantages of high charging and discharging speed, good stability, low cost and the like compared with energy storage devices such as lithium cells and the like, and are suitable for being applied to high-power electronic equipment. However, the high-power capacitor has the defect of over-low energy density. Therefore, how to increase the energy density of the capacitor is a bottleneck in the research in this field.
To increase the energy density of a dielectric material, it is necessary to increase the relative permittivity and breakdown field resistance thereof. Ferroelectric ceramics typically have thousands of high dielectric constants but low breakdown fields, whereas polymers have high breakdown fields but dielectric constants typically as low as 10 or less, and clearly either single component ceramics or polymers are not ideal dielectric materials. Ceramic/polymer dielectric composites are considered to be one of the most potential dielectric materials at present due to the combination of high dielectric constant of ceramics and high breakdown field resistance, low loss and flexibility of polymers. Spherical ferroelectric ceramic particles, e.g. BaTiO3，Pb(Zr1-xTix)O3(PZT) and Pb (Mg)1/3Nb2/3)O3–PbTiO3(PMN-PT) and the like are often selectively filled into polymer matrices due to their high dielectric constant and mature preparation process, and the content is usually as high as 50 vol.%. After the high-content ceramic filler is added, the dielectric constant of the composite is obviously increased, but the high-content ceramic filler not only introduces defects such as holes and cracks in the composite, but also destroys the flexibility of the composite, so that the high dielectric constant is usually at the expense of the breakdown-resistant electric field value of the sacrificial material, and the improvement of the energy density of the composite is limited.
Researches prove that the problems can be effectively overcome by adopting one-dimensional ceramic nanowires to replace zero-dimensional spherical nanoparticles as filling phases. Since the ceramic nanowire/polymer has a low percolation threshold, the peak of the dielectric constant can be achieved by adding less than 10 vol.% of the ceramic nanowire, and the ceramic nanowire is more easily dispersed uniformly in the polymer matrix than the ceramic nanoparticle, thereby maintaining the advantage of high breakdown field resistance of the polymer matrix. In addition, the ceramic nanowire with high aspect ratio has larger dipole moment than the spherical ceramic nanoparticle, and can effectively improve the dielectric constant of the composite under the same conditions, so the nanowire becomes a current research hotspot in the field.
However, the current research on the ceramic nanowires is still limited to adjusting the synthesis process thereof, such as changing the system and content of the ceramic nanowires and adjusting the aspect ratio thereof, and the energy density value of the composite is greatly improved compared with the composite filled with spherical ceramic particles, but the composite is still in a bottleneck stage of continuously improving the difficulty. Therefore, the current conventional thinking needs to be changed to overcome the current bottleneck and to improve the energy density of the composite to a greater extent.
The professor team of Henry A.Sodano university of Michigan changes the arrangement of PZT nanowires in the compound by adopting a stretching method, and proves that in a PVDF matrix, compared with the irregular distribution, when the PZT nanowires are distributed in parallel to an electric field, the energy density of the compound can be more effectively improved under the condition of the same electric field and the same PZT nanowire content. Titanium dioxide (TiO) is synthesized by Zhai Wei professor team of Tongji university2) Nanowire array and polyvinylidene fluoride (PVDF) -based dielectric composite material prepared by taking the nanowire array as filler, and the polyvinylidene fluoride (PVDF) -based dielectric composite material has a phase contrast ratio under the action of an electric field (340kV/mm) parallel to the growth direction of the nanowiresTiO2The composite with randomly distributed nanowires has obviously improved discharge energy density (10.62J/cm)3). BaTiO prepared by professor of Jiangyulin university of Huazhong science and technology by adopting tape casting method3The energy storage density of the compound with directionally arranged nanowires is greatly improved (10.8J/cm) under a lower electric field (240kV/mm)3). Pennsylvania state university c.a. randall et al reported that montmorillonite nanosheets were orderly dispersed in Polyethylene (PE), and both the dielectric constant and the breakdown field resistance of the composites were significantly improved compared to randomly distributed composites. Therefore, the adjustment and control of the distribution form of the ceramic nano-structure in the composite is one of effective methods for improving the energy density of the composite under the conditions of not changing a ceramic system and increasing the filling amount.
However, the existing methods have some defects. The main disadvantages of the biaxial stretching method are: the nonuniform and inconsistent property in the composite material causes different deformation of the composite material under the action of the same stretching force, so that the change of the arrangement direction of the internal nanowires cannot be consistent, and meanwhile, the internal structure tissue of the composite material is easily damaged by biaxial stretching, thereby seriously affecting the performance of the composite material. The casting method is very rough in process, the nanowires are oriented by the shearing force of the film scraping plate, the shearing force is small in action, acting forces in the thickness direction of fluid are different, the nanowire orientation effect is not obvious, and in addition, casting process parameters such as speed and force cannot be accurate, so that experiments cannot be repeated and consistent every time. The hydrothermal method for preparing the nanowire array has harsh process conditions and high cost, and only small samples can be prepared.
Therefore, the dielectric composite material with the orderly controllable ceramic nanowire arrangement mode is provided, and not only has important industrial production value, but also has important scientific research guidance significance for the research of the nanowires in other fields.
Disclosure of Invention
It is an object of the present invention to provide a novel dielectric composite.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a dielectric composite material is a ceramic nanowire/polymer composite material, and according to the volume percentage, in the dielectric composite material, the ceramic nanowire accounts for 1-10%, and the polymer accounts for 90-99%;
the ceramic nanowires are orderly arranged in any direction in the dielectric composite material.
Accordingly, a dielectric composite prepared by the steps of:
(1) preparing ceramic nanowire/polymer slurry, wherein the ceramic nanowire accounts for 1-10% and the polymer accounts for 90-99% in percentage by volume; the slurry is in a shear thinning phenomenon within a shear rate range of 0.1-1001/s;
(2) removing air bubbles from the slurry;
(3) and extruding the slurry from a slurry extruding device with the caliber of a discharge port of 10-200 mu m to obtain a characteristic linear fluid, and controlling the motion track of the discharge port to enable the slurry to form a required structure, thereby obtaining the dielectric composite material.
Preferably, the ceramic nanowires in step (1) are modified by a fluoropolymer.
Preferably, the fluorine-containing polymer is a mesogen-jacketed liquid crystal polymer with different end groups containing fluorine.
Preferably, the polymer matrix is polyvinylidene fluoride and/or polyvinylidene fluoride copolymer.
Preferably, in the step (2), the bubbles in the slurry are removed by using ultrasonic vibration.
Preferably, the slurry extruding device in the step (3) is a 3D printer.
Correspondingly, the dielectric composite material prepared by the method for regulating and controlling the arrangement direction of the ceramic nanowires in the composite material.
Preferably, the dielectric composite material is a three-dimensional structure, and the relative angle between each layer of the three-dimensional structure is 0-90 degrees.
The invention has the following beneficial effects:
1. according to the invention, the ceramic nanowires in the slurry are directionally arranged by adopting a 3D printing technology (3D direct writing forming technology), and the distribution direction of the nanowires is regulated and controlled, so that the dielectric composite material with high energy storage density is provided. The invention has been initiated in at least two places: firstly, the 3D printing technology and the arrangement of the ceramic nanowires are organically combined for the first time, so that the ceramic nanowires are arranged at low cost and high efficiency, and the prepared dielectric composite material can be expanded into a composite structure of a three-dimensional dielectric composite material with any shape from a conventional two-dimensional dielectric composite material film; meanwhile, the prior method only can enable the ceramic nanowires to be arranged in parallel, the invention realizes the controllability of the arrangement of the ceramic nanowires in the direction for the first time, and can realize the arrangement at any angle according to the requirement.
The traditional casting method and spin-coating method are used for preparing the dielectric composite material, and the nano wires cannot be arranged at all; other methods for arranging nanowires, such as a stretching method, can be used to arrange nanowires to a certain extent only after the dielectric composite material is prepared, and thus, the shape, thickness, flatness, size and the like of the dielectric composite material cannot be effectively controlled, and the nanowires can be arranged only in a single direction (stretching direction).
The invention creatively applies the 3D direct-writing forming technology to the preparation of the ceramic/polymer compound, can regulate and control the ordered arrangement direction of the ceramic nanowires in the polymer matrix, is opposite to the prior single arrangement direction, can realize the random angle arrangement of the nanowires in the dielectric compound material, can control a series of parameters of the dielectric compound material such as shape, thickness, flatness, size and the like, provides reference for the related research field related to the oriented arrangement of the nanowires at present, and also provides a new method for preparing the dielectric compound material.
2. When the slurry is prepared, the problems of agglomeration, uneven dispersion and the like of the ceramic nanowires are easy to occur, and the problem of dispersibility is perfectly solved by coating the fluorine-containing modifier on the surface of the barium titanate nanowires in situ by using a RAFT active polymerization method.
3. The invention also determines the qualified ranges of the viscosity and the elastic quantity of the slurry. In the preparation process of the slurry, the viscosity and the elastic modulus need to be strictly controlled, and the slurry cannot be smoothly extruded when the viscosity is too high; if the viscosity is too low, the elastic modulus is too low, and the printed lines cannot keep cylindrical shapes and flow to two sides, so that the direction of the nanowires is changed, and the purpose of the invention cannot be realized. Therefore, the formulation and preparation process of the slurry is of great importance.
Drawings
FIG. 1 is a schematic representation of the acceptable ranges of slurry viscosity and bulk modulus;
FIG. 2 is a schematic illustration of a dielectric composite printed in a laboratory using the present invention;
FIG. 3 is a schematic view of a dielectric composite printed at different angular arrangements using the present invention;
FIG. 4 is a comparative schematic view of composite materials prepared in comparative example and example.
Detailed Description
Common ceramic nanowires (e.g., BaTiO)3、TiO2、Pb(Zr1-xTix)O3、Ba1-xSrxTiO3、Pb(Mg1/3Nb2/3)O3-PbTiO3、Na0.5Bi0.5TiO3Etc.) can be arranged by using the method provided by the invention to obtain the arranged nanowires, and then the novel dielectric composite material required by the invention is prepared.
The specific operation method of the invention is as follows: the total amount of the ceramic nanowire and the polymer is 1 percent, and the ceramic nanowire accounts for 1 to 10 percent by volume percentage; the polymer accounts for 90-99%. Because the ceramic nanowires and the polymer are both solids, a flowable slurry is prepared by taking a solvent as a medium. The concrete method can add the polymer into the solvent, after dissolving, add the ceramic nanowire, stir and mix to get the slurry of suspension liquid ultrasonically; or adding the ceramic nanowires into a solvent, ultrasonically stirring, mixing, uniformly dispersing, then adding the polymer, and uniformly mixing to obtain suspension slurry. The solvent is any one of a mixed solution formed by acetone and N, N-dimethylformamide according to any mixing ratio, N-dimethylformamide and N, N-dimethylacetamide; the amount of the polymer is 4-12% of the mass of the solvent. As shown in fig. 1, the final prepared slurry viscosity pass criteria are: the shear thinning phenomenon is obvious in the shear rate range of 0.1-100 (1/s). The shear thinning phenomenon: meaning that the viscosity of the fluid decreases with increasing shear rate or shear stress.
In order to improve the dispersion degree of the ceramic nanowires in the composite material, the ceramic nanowires can be modified by fluorine-containing polymers. The fluorine-containing polymer is a mesogen-jacketed liquid crystal polymer with different end groups containing fluorine, and specifically can be as follows: one of polyvinyl terephthalic acid bis (p-trifluoromethoxyphenol), polyvinyl terephthalic acid bis (p-pentafluoromethoxyphenol), polyvinyl terephthalic acid bis (p-hexafluoromethoxyphenol) and polyvinyl terephthalic acid bis (p-heptafluoromethoxyphenol).
As shown in fig. 2, the slurry is charged into a barrel, and bubbles in the slurry are removed by means of ultrasonics or the like. The device comprises a slurry extrusion device, wherein the caliber of a discharge port of the slurry extrusion device is 10-200 mu m, and the actual caliber can be adjusted as required. The charging barrel is connected with a pressure device, preferably an air compressor, the internal pressure of the charging barrel is adjusted, slurry is extruded from a discharge port to obtain characteristic linear fluid, the motion track of the discharge port is controlled to obtain a sample, the sample is transferred into an oven to be dried for 24 hours at the temperature of 80 ℃, a solvent is removed, and the sample is shaped to obtain the required dielectric composite material.
The more preferable scheme is that the 3D printer is directly used, the slurry is loaded into a storage bin of the 3D printer, the caliber of a raw material discharge port of the 3D printer is adjusted to the required caliber, a three-dimensional structure direct-writing program of a control end is set, and the raw material is extruded from the discharge port. The X-Y axis moves according to the track set by the program to obtain a first layer structure. Subsequently, the Z-axis motor drives the conveying device to accurately move upwards to the height determined by the structural scheme, the second layer forming is carried out on the first layer structure, and the alignment angle of the upper layer ceramic nanowire and the lower layer ceramic nanowire can be changed through a preset second layer printing program (the angle can be adjusted according to actual needs and can be 0-90 degrees). And printing to the required layer number by analogy, and obtaining the dielectric composite material.
As shown in fig. 3, when a 3D printer is used to form a film, the running track of the discharge port can be more efficiently controlled by setting a program, and the regular shape of the desired dielectric composite film and the arrangement direction of the ceramic nanowires can be conveniently and rapidly obtained. Moreover, the 3D printer can be used for obtaining the dielectric composite film, obtaining various dielectric composite materials with three-dimensional shapes according to needs, and controlling angles among different layers of the three-dimensional shapes according to actual needs.
The 3D printer used herein is a model number Desktop Robot DR-2200N machine available from Nordson corporation. In actual work, the movement precision of the 3D printer is more than or equal to 200 mu m, and the aim of the invention can be better achieved.
The following procedure was followed to prepare a completely new BaTiO3the/P (VDF-CTFE) dielectric composite material is taken as an example, and the effect of the scheme is further shown by a comparative example and an example.
Comparative example: preparation of BaTiO by conventional method3(VDF-CTFE) COMPOSITE MATERIAL
1. In-situ modified BaTiO3Nanowire and method of manufacturing the same
(1) Mixing 10g of BaTiO3The nanowires were dispersed in 100ml of 30 wt% H2O2And performing medium ultrasonic treatment for 30min, and then performing reflux stirring for 6h in an oil bath at 105 ℃. After the reaction is finished, centrifugally separating the product, and using deionized water to carry out BaTiO3Washing the nanowire, then centrifuging, washing again, repeating for 2-3 times, and then adding BaTiO3The nano wire is placed in a vacuum drying oven at 80 ℃ for drying for 24h to obtain hydroxylated BaTiO3Nanowires (hereinafter abbreviated as BT-OH).
(2) 10g of BT-OH is added into 100ml of THF, and the mixture is ultrasonically shaken for 30 min. 7.5g of (3-aminopropyl) dimethylethoxysilane (r-APS for short) were added under nitrogen protection2Reacting for 24 hours at 80 ℃ under protection. After the reaction is finished, performing centrifugal separation on the product, dispersing the separated product by using THF (tetrahydrofuran), then centrifuging, re-dispersing, repeating for 2-3 times, and then performing vacuum drying on the obtained product at 80 ℃ for 24 hours to obtain the surface aminated BaTiO3Nanowire (hereinafter abbreviated as BT-NH)2)。
(3) Mixing CPDB (1.6g,5.7mmol), N, N' -dicyclohexylcarbonylImine (1.2g,5.8mmol), 2-mercaptothiazoline (0.74g,6.2mmol), 4-dimethylaminopyridine (0.024g,0.2mmol) and 10ml dry CH2Cl2The mixture was added to a single-necked flask and stirred at room temperature for 12 hours. After the reaction was completed, the liquid in the single-necked flask was filtered, the filtrate was collected and the solvent was removed by a rotary evaporator, the obtained product was purified by column chromatography, the solution of the red fraction was collected, and the solvent was removed by a rotary evaporator, thereby obtaining activated CPDB, hereinafter abbreviated as CPDB-NHS.
(4) Mixing 10g BT-NH2Adding into a single-mouth bottle, adding 50ml THF solvent, and performing ultrasonic treatment for 30min to obtain BT-NH2The dispersion is uniform. 1.8g of CPDB-NHS was dissolved in 50ml of THF in advance as RAFT reagent. The dispersed BT-NH is added2And dripping the mixed system of THF and the RAFT reagent into the RAFT reagent, stirring and reacting for 12h at room temperature, carrying out centrifugal separation on the product after the reaction is finished, dispersing the separated product again by using THF, then centrifuging, re-dispersing, repeating for 2-3 times, and then carrying out vacuum drying on the obtained product for 24h at 60 ℃ to obtain the BaTiO with the CPDB grafted on the surface3Nanowires (hereinafter abbreviated as BT-CPDB).
(5) Grafting fluorine-containing liquid crystal polymer to the surface of BT-CPDB nanoparticles by RAFT polymerization, wherein the specific process comprises the following steps: BT-CPDB (1.3g), vinyl terephthalic acid bis (p-trifluoromethoxyphenol) ester (TFMPCS) (0.523g,1.3mmol), AIBN (2.6mg,0.015mmol) and chlorobenzene (8.8g) were added to a clean glass test tube in sequence, then the test tube was subjected to an air-blowing and nitrogen-blowing cycle five times to remove air from the test tube, finally the test tube was capped with an alcohol burner under vacuum, then placed in an oil bath at 80 ℃ and magnetically stirred, and after 6 hours of reaction, the test tube was placed in an ice-water bath to terminate the polymerization reaction. The tube was broken to admit air, the mixed solution was diluted with 10ml of THF and centrifuged, and the resulting product was dispersed with THF and centrifuged again, and this was repeated 3 times. Finally, the obtained product is placed in a vacuum drying oven at 60 ℃ for drying for 24h to obtain PTFMPCS modified BaTiO3Nanowires (hereinafter abbreviated as BT-6F).
2. Preparation of BaTiO3(VDF-CTFE) COMPOSITE MATERIAL
Respectively weighing 0.0635g, 0.0866g, 0.177g and 0.274g of BT-6F, adding the weighed materials into 12.5g of DMF solvent (the volume ratio of the nanowires in the composite material is respectively 1.5%, 2.5%, 5% and 7.5%), ultrasonically dispersing for 10min, adding 1.2g of P (VDF-CTFE) resin, ultrasonically dispersing for two days, ball-milling for two days, pouring the dispersed suspension on a glass sheet, casting the suspension in one direction by a scraper, blowing and drying the suspension for 24h and vacuum drying the suspension for 24h at 80 ℃ to obtain a composite material film, and then hot-pressing the composite material film into compact composite films under the conditions of 160 ℃ and 15MPa to obtain four groups of unaligned composite materials as a comparative example 1. The four sets of comparative examples 1 were subjected to nanowire arrangement by a drawing method, respectively, as comparative example 2.
Example (b): preparation of BaTiO by the scheme3(VDF-CTFE) COMPOSITE MATERIAL
1. Step 1 in-situ modification of BaTiO3The scheme of the nanowires was the same as the comparative example. Compared with a comparative example, the composite membrane is prepared by adopting a 3D direct writing technology in the embodiment, and the specific steps are as follows:
0.0635g, 0.0866g, 0.177g and 0.274g of PTFMPCS modified BaTiO were weighed out separately3The nanowires were added into 12.5g of dmf solvent (the volume ratio of the nanowires in the composite material was 1.5%, 2.5%, 5% and 7.5%, respectively), ultrasonically dispersed for 10min, then 1.2g of p (VDF-CTFE) resin was added, ultrasonically dispersed, and ball-milled for two days to obtain uniformly dispersed suspension slurry, which was used as each set of examples.
The slurry of each embodiment is respectively transferred into a barrel, an air compressor is connected to adjust the pressure, a slurry extrusion device arranged on a Z axis obtains characteristic linear fluid, and then a three-dimensional structure direct-writing program of a control end is set. The X-Y axis moves according to the track set by the program to obtain a first layer structure. And then, the Z-axis motor drives the conveying device to accurately move upwards to the height and the angle determined by the structural scheme, and the second layer of molding is carried out on the first layer of structure to obtain a second layer of structure. The required number of layers and shape can be obtained by continuously constructing according to actual requirements. In this example, for comparison, only the first layer structure was prepared and used as the composite material for each set of examples for comparison of properties.
2. And (3) performance testing: and respectively clamping the comparative example composite material and the embodiment composite material between two metal mask plates, and sputtering symmetric gold electrodes by using a magnetron sputtering instrument. An Agilent 4294A precision impedance analyzer and a ferroelectric analyzer TF2000E are adopted to characterize the dielectric constant, the dielectric loss, the breakdown-resistant electric field and the energy density of the composite material film.
The electron microscope scanning images of the composite materials prepared in comparative example 1 and example are shown in fig. 4 (the volume ratio of the nanowires in the composite material is 5%). Specific performance comparison results are shown in table 1.
TABLE 1 comparison of composite Properties of comparative examples and examples
Figure BDA0001817034900000091
Figure BDA0001817034900000101

Claims (7)

1. A dielectric composite characterized by: the dielectric composite material is a ceramic nanowire/polymer composite material, and according to the volume percentage, the ceramic nanowire accounts for 1-10% of the dielectric composite material, and the polymer accounts for 90-99%; the ceramic nanowires are orderly arranged in any direction in the dielectric composite material;
the dielectric composite material is prepared by the following steps:
(1) preparing ceramic nanowire/polymer slurry, wherein the ceramic nanowire accounts for 1-10% and the polymer accounts for 90-99% in percentage by volume; the slurry is in a shear thinning phenomenon within a shear rate range of 0.1-1001/s;
(2) removing air bubbles from the slurry;
(3) extruding the slurry from a slurry extruding device with the caliber of a discharge port of 10-200 mu m to obtain a characteristic linear fluid, and controlling the motion track of the discharge port to enable the slurry to form a required structure, thereby obtaining the dielectric composite material;
modifying the ceramic nanowire by using a fluorine-containing polymer in the step (1); the fluorine-containing polymer is a mesogen-jacketed liquid crystal polymer with different end groups containing fluorine.
2. A dielectric composite material according to claim 1, wherein: the polymer is a thermoplastic polymer.
3. A dielectric composite material according to claim 2, wherein: the polymer is polyvinylidene fluoride and/or polyvinylidene fluoride copolymer.
4. A dielectric composite material according to claim 1, wherein: the ceramic nanowire comprises BaTiO3、TiO2、Pb(Zr1-xTix)O3、Ba1-xSrxTiO3、Pb(Mg1/3Nb2/3)O3-PbTiO3、Na0.5Bi0.5TiO3Ceramic nanowires.
5. A dielectric composite material according to claim 1, wherein: in the step (2), bubbles in the slurry are removed by using ultrasonic oscillation.
6. A dielectric composite material according to claim 1, wherein: and (3) the slurry extruding device is a 3D printer.
7. A dielectric composite material according to claim 6, wherein: the dielectric composite material is of a three-dimensional structure, and the relative angle between each layer of the three-dimensional structure is 0-90 degrees.
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