CN112695462A - Composite dielectric material with multilayer gradient structure and preparation method thereof - Google Patents
Composite dielectric material with multilayer gradient structure and preparation method thereof Download PDFInfo
- Publication number
- CN112695462A CN112695462A CN202011563575.6A CN202011563575A CN112695462A CN 112695462 A CN112695462 A CN 112695462A CN 202011563575 A CN202011563575 A CN 202011563575A CN 112695462 A CN112695462 A CN 112695462A
- Authority
- CN
- China
- Prior art keywords
- layer
- composite
- ferroelectric polymer
- ceramic filler
- dielectric material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 105
- 239000003989 dielectric material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 86
- 239000000919 ceramic Substances 0.000 claims abstract description 84
- 239000000945 filler Substances 0.000 claims abstract description 84
- 238000009987 spinning Methods 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 18
- 238000010041 electrostatic spinning Methods 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 229910052454 barium strontium titanate Inorganic materials 0.000 claims description 9
- 238000007731 hot pressing Methods 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 229910002113 barium titanate Inorganic materials 0.000 claims description 6
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 4
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 4
- 229920000131 polyvinylidene Polymers 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 25
- 238000009826 distribution Methods 0.000 abstract description 9
- 238000010276 construction Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000001523 electrospinning Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 19
- 230000005684 electric field Effects 0.000 description 14
- 239000000843 powder Substances 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/413—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties containing granules other than absorbent substances
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C15/00—Calendering, pressing, ironing, glossing or glazing textile fabrics
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Laminated Bodies (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
本发明提供一种具有多层梯度结构的复合电介质材料及其制备方法，一种具有多层梯度结构的复合电介质材料，该电介质材料由间隔排列的纯铁电聚合物层和铁电聚合物/介电陶瓷填料复合层组成，电介质材料的总层数为奇数且电介质材料的的外层为铁电聚合物/介电陶瓷填料复合层，介电陶瓷填料在铁电聚合物/介电陶瓷填料复合层中的含量按照从外层到内层梯度递增的规律变化。本发明制备的多层梯度结构的复合电介质材料具有较好的耐高压性能和稳定的储能性能。本发明采用静电纺丝层层构筑的方法制备多层梯度结构的复合电介质材料，结合复合材料多层结构以及介电陶瓷填料梯度分布的特点，多层梯度结构的复合电介质材料将获得全面高效稳定的储能性能。
The invention provides a composite dielectric material with a multi-layer gradient structure and a preparation method thereof, a composite dielectric material with a multi-layer gradient structure, and the dielectric material is composed of spaced pure ferroelectric polymer layers and ferroelectric polymer/ The composition of the dielectric ceramic filler composite layer, the total number of layers of the dielectric material is odd and the outer layer of the dielectric material is a ferroelectric polymer/dielectric ceramic filler composite layer, and the dielectric ceramic filler is in the ferroelectric polymer/dielectric ceramic filler The content in the composite layer changes according to the law of increasing gradient from the outer layer to the inner layer. The composite dielectric material of the multi-layer gradient structure prepared by the invention has good high voltage resistance performance and stable energy storage performance. The invention adopts the layer-by-layer construction method of electrospinning to prepare the composite dielectric material of the multi-layer gradient structure. Combined with the characteristics of the multi-layer structure of the composite material and the gradient distribution of the dielectric ceramic filler, the composite dielectric material of the multi-layer gradient structure will obtain an overall high efficiency and stability. energy storage performance.
Description
Technical Field
The invention belongs to the technical field of dielectric material preparation, and particularly relates to a composite dielectric material with a multilayer gradient structure and a preparation method thereof.
Background
The film capacitor is an important energy storage device with high power density, high charge-discharge efficiency and stable cycle performance, and plays an important role in the modern electronic power system.
The polymer dielectric material has the characteristics of flexibility, light weight and easiness in processing, has excellent high-voltage resistance, and is a main raw material for preparing the film capacitor. However, the energy storage density of the polymer dielectric material is low, so that the further development of the thin-film capacitor is limited, and the development of the novel high-energy-density dielectric material with high efficiency and stability has extremely strong theoretical significance and practical value.
Currently, the synthesis of ferroelectric polymer/dielectric ceramic composite materials is an important means for developing novel dielectric materials with high energy storage density. The method takes the ferroelectric polymer as a matrix and the dielectric ceramic as a filler, combines the advantages of high breakdown voltage of the polymer matrix and high dielectric property of the dielectric ceramic filler, and improves the energy storage property of the material. For example, Li or the like introduces surface-modified barium titanate nanofibers (BaTiO) in polyvinylidene fluoride-hexafluoropropylene (P (VDF-HFP))3NFs) under the voltage condition of 300 MV/m, the energy storage density of the composite material reaches 8.55J/cm3The improvement is more obvious than that of a P (VDF-HFP) matrix. However, due to the great difference in dielectric constant between the dielectric ceramic filler and the polymer matrix, the electric field distribution is not uniform in a polymer/ceramic homogeneous phase composite system, and the material is broken down in advance, thereby limiting the further improvement of the energy storage performance of the composite material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a composite dielectric material with a multilayer gradient structure and a preparation method thereof.
The design and preparation of the multilayer gradient structure polymer/ceramic composite material are expected to solve the problems. Through the design of a multilayer structure in the composite material and the optimization of filler distribution, the breakdown voltage and the dielectric property of the composite dielectric material can be synchronously improved, and further the dielectric energy storage property of the composite dielectric material is greatly improved, so that the composite dielectric material plays an important role in a related electronic power system.
In order to solve the technical problems, the invention adopts the following technical scheme:
the composite dielectric material with the multilayer gradient structure comprises pure ferroelectric polymer layers and ferroelectric polymer/dielectric ceramic filler composite layers which are arranged at intervals, the total number of the layers of the dielectric material is odd, the outer layer of the dielectric material is the ferroelectric polymer/dielectric ceramic filler composite layer, and the content of the dielectric ceramic filler in the ferroelectric polymer/dielectric ceramic filler composite layer is changed according to the rule of increasing gradient from the outer layer to the inner layer.
Preferably, the pure ferroelectric polymer layer is the same thickness as the ferroelectric polymer/dielectric ceramic filler composite layer.
Preferably, the total number of layers of the dielectric material is 5 or 7 or 9.
Preferably, the pure ferroelectric polymer layer is made of any one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene and polyvinylidene fluoride-trifluoroethylene.
Preferably, the dielectric ceramic filler is any one of barium titanate, barium strontium titanate and titanium dioxide.
Preferably, the content of the dielectric ceramic filler in the ferroelectric polymer/dielectric ceramic filler composite layer is 1 wt% to 20 wt%.
The invention also provides a preparation method of the composite dielectric material with the multilayer gradient structure, which comprises the following steps:
preparing a pure ferroelectric polymer solution;
preparing ferroelectric polymer/dielectric ceramic filler mixed solutions with different dielectric ceramic filler contents;
sequentially spinning the pure ferroelectric polymer solution and the ferroelectric polymer/dielectric ceramic filler mixed solution layer by adopting an electrostatic spinning technology to obtain pure ferroelectric polymer layers which are arranged at intervals and ferroelectric polymer/dielectric ceramic filler composite layers with different dielectric ceramic filler contents;
and collecting the prepared electrostatic spinning film by adopting a roller collector, and carrying out hot pressing treatment to obtain the dielectric material.
Preferably, the diameter of the roller collector is 10 cm-15 cm, and the rotating speed is 1500 rpm-2500 rpm.
Preferably, the hot-pressing treatment temperature is 150-200 ℃, and the pressure is 10-20 Mpa.
Preferably, the pure ferroelectric polymer solution and the ferroelectric polymer/dielectric ceramic filler mixed solution use N, N-dimethylformamide as a solvent.
Compared with the prior art, the invention has the beneficial effects that:
(1) the content of the dielectric ceramic filler in the ferroelectric polymer/dielectric ceramic filler composite layer is sequentially increased from outside to inside according to a certain gradient, and the ferroelectric polymer/dielectric ceramic filler composite layer with lower content of the dielectric ceramic filler at the outer layer can effectively avoid current carriers injected from an electrode under the condition of a high-voltage electric field, so that the high-voltage resistance is improved; the ferroelectric polymer/dielectric ceramic filler composite layer with high content of the dielectric ceramic filler of the inner layer can ensure the improvement of the overall dielectric property of the composite material.
(2) The ferroelectric polymer/dielectric ceramic filler composite layers are separated by pure ferroelectric polymer layers, the pure ferroelectric polymer has relatively high resistivity and the interfaces among the layers can effectively limit the development of carrier migration and electric breakdown branches, and further the composite material film is protected from being broken down under high application voltage.
(3) The composite dielectric material with the multilayer gradient structure is prepared by adopting an electrostatic spinning layer-by-layer construction method, and the method can accurately control the thickness of the multilayer structure and the distribution proportion of the filler content. By combining the characteristics of the multilayer structure of the composite material and the gradient distribution of the dielectric ceramic filler, the composite dielectric material with the multilayer gradient structure can obtain comprehensive, efficient and stable energy storage performance, including breakdown performance, energy storage efficiency, energy storage density and cycle performance.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
It will be appreciated by those skilled in the art that the objects and advantages that can be achieved with the present invention are not limited to the specific details set forth above, and that these and other objects that can be achieved with the present invention will be more clearly understood from the detailed description that follows.
Drawings
FIG. 1 is a schematic illustration of a multilayer gradient structured composite dielectric material prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a composite dielectric material of a multi-layered gradient structure prepared in example 1 of the present invention;
FIG. 3 is a schematic view of carrier injection into a composite dielectric material of a multilayer gradient structure prepared in example 1 of the present invention;
FIG. 4 is a schematic diagram of the electrical dendritic development of the multilayer gradient structured composite dielectric material prepared in example 1 of the present invention;
FIG. 5 is a hysteresis loop of a multi-layered gradient composite dielectric material prepared in example 1 of the present invention under an applied electric field;
FIG. 6 is a hysteresis loop of the multi-layered gradient composite dielectric material prepared in example 2 of the present invention under an applied electric field;
fig. 7 shows the hysteresis loop of the multi-layered gradient composite dielectric material prepared in example 3 of the present invention under an applied electric field.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It is to be understood that the processing equipment or apparatus not specifically identified in the following examples is conventional in the art.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
The embodiment of the invention provides a composite dielectric material with a multilayer gradient structure, which consists of pure ferroelectric polymer layers and ferroelectric polymer/dielectric ceramic filler composite layers which are arranged at intervals, wherein the total number of the layers of the dielectric material is odd, the outer layer of the dielectric material is the ferroelectric polymer/dielectric ceramic filler composite layer, and the content of the dielectric ceramic filler in the ferroelectric polymer/dielectric ceramic filler composite layer is changed according to the rule of increasing the gradient from the outer layer to the inner layer. The "inner" direction referred to herein means the direction in which the intermediate layer of dielectric material is located, and the "outer" direction means the direction on both sides of the intermediate layer.
The content of the dielectric ceramic filler in the ferroelectric polymer/dielectric ceramic filler composite layer of the composite dielectric material with the multilayer gradient structure prepared by the invention is sequentially increased from outside to inside according to a certain gradient, and the ferroelectric polymer/dielectric ceramic filler composite layer with lower content of the dielectric ceramic filler at the outer layer can effectively avoid current carriers injected from an electrode under the condition of a high-voltage electric field, thereby improving the high-voltage resistance; the ferroelectric polymer/dielectric ceramic filler composite layer with high content of the dielectric ceramic filler of the inner layer can ensure the improvement of the overall dielectric property of the composite material.
In addition, the ferroelectric polymer/dielectric ceramic filler composite layers are separated by pure ferroelectric polymer layers, the relatively high resistivity of the pure ferroelectric polymer and the interfaces among the layers can effectively limit the development of carrier migration and electric breakdown branches, and further the composite material film is protected from being broken down under high application voltage.
On the other hand, the composite dielectric material with the multilayer gradient structure is prepared by adopting an electrostatic spinning layer-by-layer construction method, and the method can accurately control the thickness of the multilayer structure and the distribution proportion of the filler content. By combining the characteristics of the multilayer structure of the composite material and the gradient distribution of the dielectric ceramic filler, the composite dielectric material with the multilayer gradient structure can obtain comprehensive, efficient and stable energy storage performance, including breakdown performance, energy storage efficiency, energy storage density and cycle performance.
Preferably, the pure ferroelectric polymer layer is the same thickness as the ferroelectric polymer/dielectric ceramic filler composite layer. In the preferred embodiment of the invention, the overall thickness of the finally prepared composite dielectric material with a multilayer gradient structure is kept between 10 and 18 μm, and the thickness of each layer is ensured to be 2 μm. The thicknesses of all layers are kept the same, so that the overall performance of the prepared composite dielectric material with the multilayer gradient structure is improved.
Preferably, the total number of layers of the dielectric material is 5 or 7 or 9, and when the number of layers is less than 5, the layer interface is less and the gradient structure cannot be designed. When the number of layers is more than 9, the thickness of the film material is thick, so that the use of the film material in the field of dielectric energy storage is limited. The specific structural layer number is adjusted according to the application condition of the material. 5 layers of structure A1BA2BA1Wherein the layer B is a pure ferroelectric polymer layer, A1And A2The layer is a ferroelectric polymer/dielectric ceramic filler composite layer. A. the1And A2The content of the dielectric ceramic filler in the layer is changed in an increasing way according to a certain gradient. The structural layer of the dielectric material is designed in a symmetrical structure to be positioned at A of the middle layer2The position is the inner layer, and is located at A2A on both sides1Is the outer layer. Similarly, the 7-layer structure is A1BA2BA2BA1Wherein the layer B is a pure ferroelectric polymer layer, A1And A2The layer is a ferroelectric polymer/dielectric ceramic filler composite layer. A. the1And A2The content of the dielectric ceramic filler in the layer is changed in an increasing way according to a certain gradient. 9 layers of A1BA2BA3BA2BA1Wherein the layer B is a pure ferroelectric polymer layer, A1、A2And A3The layer is a ferroelectric polymer/dielectric ceramic filler composite layer. A. the1、A2And A3The content of the dielectric ceramic filler in the layer is changed in an increasing way according to a certain gradient.
Preferably, the material of the pure ferroelectric polymer layer is any one of polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (P (VDF-HFP)), and polyvinylidene fluoride-trifluoroethylene (P (VDF-TrFE)).
Preferably, the dielectric ceramic filler is barium titanate (BaTiO)3) Barium strontium titanate (BaTi)xO1-x) Titanium dioxide (TiO)2) Any one of them.
Preferably, the content of the dielectric ceramic filler in the ferroelectric polymer/dielectric ceramic filler composite layer is 1 wt% to 20 wt%. The concentration of the dielectric ceramic filler is increased progressively according to the gradient rule that the outer layer is low and the inner layer is high, and the increasing amplitude of the concentration of the dielectric ceramic filler in the adjacent composite layers is not more than 10 wt%; to ensure overall performance, the overall proportion of dielectric ceramic filler in the composite dielectric material is preferably not more than 6 wt%.
The embodiment of the invention also provides a preparation method of the composite dielectric material with the multilayer gradient structure, which comprises the following steps:
(1) preparing a pure ferroelectric polymer solution;
(2) preparing ferroelectric polymer/dielectric ceramic filler mixed solutions with different dielectric ceramic filler contents;
(3) sequentially spinning the pure ferroelectric polymer solution and the ferroelectric polymer/dielectric ceramic filler mixed solution layer by adopting an electrostatic spinning technology to obtain pure ferroelectric polymer layers which are arranged at intervals and ferroelectric polymer/dielectric ceramic filler composite layers with different dielectric ceramic filler contents;
(4) and collecting the prepared electrostatic spinning film by adopting a roller collector, and carrying out hot pressing treatment to obtain the dielectric material.
According to the preparation method, the composite dielectric material with the multilayer gradient structure is prepared by utilizing a method of electrostatic spinning layer-by-layer construction, namely according to a structural design scheme, the ferroelectric polymer and the dielectric ceramic powder which are proportioned are respectively dissolved in N, N-Dimethylformamide (DMF) to prepare spinning solution; and then, carrying out layer-by-layer spinning by utilizing an electrostatic spinning technology, wherein the content of the dielectric ceramic powder filler in the laminated structure is controlled by the proportion of the spinning solution, and the thickness of the laminated structure is determined by the spinning time. The final composite dielectric material with the multilayer gradient structure can be obtained after the prepared electrostatic spinning film is subjected to hot pressing treatment, and preferably, the hot pressing treatment temperature is 150-200 ℃, and the pressure is 10-20 Mpa. Naturally cooling after the hot pressing treatment. In the preferred embodiment of the invention, the overall thickness of the finally prepared composite dielectric material with the multilayer gradient structure is kept between 10 and 18 mu m, and the thickness of each layer is kept consistent.
The composite dielectric material with the multilayer gradient structure is prepared by adopting an electrostatic spinning layer-by-layer construction method, and the method can accurately control the thickness of the multilayer structure and the distribution proportion of the filler content. By combining the characteristics of the multilayer structure of the composite material and the gradient distribution of the dielectric ceramic filler, the composite dielectric material with the multilayer gradient structure can obtain comprehensive, efficient and stable energy storage performance, including breakdown performance, energy storage efficiency, energy storage density and cycle performance.
Preferably, the diameter of the roller collector is 10 cm-15 cm, and the rotating speed is 1500 rpm-2500 rpm. Thus, the oriented arrangement structure of the nano-fibers after spinning can be ensured, and the uniform dispersion of the nano-dielectric ceramic filler is further promoted.
The following is a further description with reference to specific examples.
Example 1
The embodiment 1 of the invention provides a composite dielectric material with a multilayer gradient structure and a preparation method thereof. The structure of the composite dielectric material with the multilayer gradient structure is A1BA2BA2BA1As shown in fig. 1. Wherein A is1The content of barium titanate in the layer is 5 wt%. A2The barium titanate content of the layer was 15 wt%. Before spinning, 0.5 g of P (VDF-HFP) powder is dissolved in 10 mL of DMF solution, stirred overnight until the powder is completely dissolved to prepare a pure ferroelectric polymer solution, and BaTiO with different contents is added into the pure ferroelectric polymer solution3Preparing different BaTiO respectively from nano particles (5 wt% and 15 wt%)3The ferroelectric polymer/dielectric ceramic filler mixed solution with the content is continuously stirredAfter 24h, carrying out ultrasonic treatment for 30 min until BaTiO3And (4) completely dispersing the nano particles to prepare the spinning solution. Spinning the prepared spinning solution layer by using an electrostatic spinning method according to a preset multilayer structure, wherein in order to ensure the uniformity and stability of the structure, a spinning film is collected by a roller, the diameter of the roller is 10cm, the rotating speed is 1800 rpm, the spinning voltage is 15 kV, the spinning speed is 1.0 mL/h, and the spinning time of each layer is 1 h. After the film is prepared, the composite dielectric material with a multilayer gradient structure is obtained after the composite dielectric material is hot-pressed for 10min under the conditions of 10 Mpa and 170 ℃, the section scanning picture of the material is shown in figure 2, the thickness of each layer is 2 microns, and the overall thickness of the film is 14 microns.
Fig. 3 is a schematic view of carrier injection of the structural composite material under a high-voltage electric field condition, and fig. 4 is a schematic view of the development of electric tree inside the material under the high-voltage electric field condition. FIG. 5 is the hysteresis loop of the composite material under the highest withstand voltage electric field, and it can be seen that the material loss is low, and under the electric field strength of 610 MV/m, the energy storage efficiency is 70%, and the energy storage density is 17.55J/cm3。
Example 2
Example 3
Embodiment 3 of the invention provides a composite dielectric material with a multilayer gradient structure and a preparation method thereof, wherein the structure of the multilayer gradient composite material is A1BA2BA3BA2BA1. Wherein A is1The content of barium strontium titanate layer is 1 wt%, A2The content of barium strontium titanate of the layer is 5 wt%. A. the3The content of barium strontium titanate of the layer is 10 wt%. Before spinning, 0.5 g of PVDF powder is dissolved in 10 mL of DMF solution, the mixture is stirred overnight until the PVDF powder is completely dissolved to prepare a pure ferroelectric polymer solution, ferroelectric polymer/dielectric ceramic filler mixed solutions with different barium strontium titanate contents are respectively prepared by adding barium strontium titanate nanoparticles (1 wt%, 5 wt% and 10 wt%) with different contents into the pure ferroelectric polymer solution, the mixture is continuously stirred for 24 hours and then is subjected to ultrasonic treatment for 30 minutes until the barium strontium titanate nanoparticles are completely dispersed, and a spinning solution is prepared. Spinning the prepared spinning solution layer by using an electrostatic spinning method according to a preset multilayer structure, wherein in order to ensure the uniformity and stability of the structure, a spinning film is collected by a roller, the diameter of the roller is 15cm, the rotating speed is 1500 rpm, the spinning voltage is 15 kV, the spinning speed is 1.0 mL/h, and the spinning time of each layer is 1 h. After the film is prepared, the composite dielectric material with a multilayer gradient structure is obtained after the film is hot-pressed for 10min under the conditions of 10 Mpa and 170 ℃, wherein the thickness of each layer is 2 microns, and the overall thickness of the film is 18 microns. Fig. 7 is a hysteresis loop of the composite material under the highest withstand voltage electric field. Under the electric field strength of 580 MV/m, the energy storage efficiency is 68 percent, and the energy storage density is 14.3J/cm3。
The protective scope of the present invention is not limited to the above-described embodiments, and it is apparent that various modifications and variations can be made to the present invention by those skilled in the art without departing from the scope and spirit of the present invention. It is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.
Claims (10)
1. The composite dielectric material with the multilayer gradient structure is characterized by comprising pure ferroelectric polymer layers and ferroelectric polymer/dielectric ceramic filler composite layers which are arranged at intervals, wherein the total number of the layers of the dielectric material is odd, the outer layer of the dielectric material is the ferroelectric polymer/dielectric ceramic filler composite layer, and the content of dielectric ceramic fillers in the ferroelectric polymer/dielectric ceramic filler composite layer is changed according to a rule of increasing gradient from the outer layer to the inner layer.
2. The composite dielectric material with a multi-layered gradient structure of claim 1, wherein the thickness of said pure ferroelectric polymer layer is equal to the thickness of said ferroelectric polymer/dielectric ceramic filler composite layer.
3. The composite dielectric material with a multilayer gradient structure of claim 1, wherein the total number of layers of the dielectric material is 5 layers, 7 layers or 9 layers.
4. The composite dielectric material with a multi-layer gradient structure as claimed in claim 1, wherein the material of the pure ferroelectric polymer layer is any one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, and polyvinylidene fluoride-trifluoroethylene.
5. The composite dielectric material with a multi-layer gradient structure as claimed in claim 4, wherein the dielectric ceramic filler is any one of barium titanate, barium strontium titanate and titanium dioxide.
6. The composite dielectric material with a multi-layered gradient structure as claimed in claim 5, wherein the content of the dielectric ceramic filler in the ferroelectric polymer/dielectric ceramic filler composite layer is 1 wt% to 20 wt%.
7. The method for preparing a composite dielectric material with a multi-layer gradient structure as claimed in any one of claims 1 to 6, comprising the steps of:
preparing a pure ferroelectric polymer solution;
preparing ferroelectric polymer/dielectric ceramic filler mixed solutions with different dielectric ceramic filler contents;
sequentially spinning the pure ferroelectric polymer solution and the ferroelectric polymer/dielectric ceramic filler mixed solution layer by adopting an electrostatic spinning technology to obtain pure ferroelectric polymer layers which are arranged at intervals and ferroelectric polymer/dielectric ceramic filler composite layers with different dielectric ceramic filler contents;
and collecting the prepared electrostatic spinning film by adopting a roller collector, and carrying out hot pressing treatment to obtain the dielectric material.
8. The method of claim 7, wherein the diameter of the roller collector is 10cm to 15cm, and the rotation speed is 1500 rpm to 2500 rpm.
9. The method for preparing the composite dielectric material with the multilayer gradient structure as claimed in claim 7, wherein the hot-pressing temperature is 150 ℃ to 200 ℃, and the pressure is 10 MPa to 20 MPa.
10. The method of claim 7, wherein the pure ferroelectric polymer solution and the ferroelectric polymer/dielectric ceramic filler mixed solution use N, N-dimethylformamide as a solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011563575.6A CN112695462A (en) | 2020-12-25 | 2020-12-25 | Composite dielectric material with multilayer gradient structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011563575.6A CN112695462A (en) | 2020-12-25 | 2020-12-25 | Composite dielectric material with multilayer gradient structure and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112695462A true CN112695462A (en) | 2021-04-23 |
Family
ID=75510665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011563575.6A Pending CN112695462A (en) | 2020-12-25 | 2020-12-25 | Composite dielectric material with multilayer gradient structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112695462A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114388266A (en) * | 2022-01-14 | 2022-04-22 | 西安交通大学 | A kind of high energy storage density wide operating temperature composition gradient structure film and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010090526A (en) * | 2008-09-12 | 2010-04-22 | Toray Ind Inc | Microfine fiber and thermoplastic resin composition containing the same |
| CN108587007A (en) * | 2018-01-17 | 2018-09-28 | 清华大学 | A kind of laminated construction ferroelectric polymers based dielectric film, and its preparation method and application |
| CN108701753A (en) * | 2015-12-25 | 2018-10-23 | 三井化学株式会社 | Piezoelectricity base material, piezoelectricity woven fabric, piezoelectricity knitted fabric, piezo-electric device, force snesor, actuator and Biont information acquisition device |
| CN109280300A (en) * | 2017-07-20 | 2019-01-29 | 清华大学 | A kind of polymer composite material with adjustable filler distribution and orientation and preparation method thereof |
| CN109997238A (en) * | 2016-10-12 | 2019-07-09 | Ntn株式会社 | Piezoelectric element and its manufacturing method |
| CN110284263A (en) * | 2019-06-13 | 2019-09-27 | 上海交通大学 | The preparation method of lamination composite nano fiber |
| CN111472099A (en) * | 2020-04-17 | 2020-07-31 | 成都新柯力化工科技有限公司 | Composite piezoelectric ceramic fiber membrane for road power generation and preparation method thereof |
-
2020
- 2020-12-25 CN CN202011563575.6A patent/CN112695462A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010090526A (en) * | 2008-09-12 | 2010-04-22 | Toray Ind Inc | Microfine fiber and thermoplastic resin composition containing the same |
| CN108701753A (en) * | 2015-12-25 | 2018-10-23 | 三井化学株式会社 | Piezoelectricity base material, piezoelectricity woven fabric, piezoelectricity knitted fabric, piezo-electric device, force snesor, actuator and Biont information acquisition device |
| CN109997238A (en) * | 2016-10-12 | 2019-07-09 | Ntn株式会社 | Piezoelectric element and its manufacturing method |
| CN109280300A (en) * | 2017-07-20 | 2019-01-29 | 清华大学 | A kind of polymer composite material with adjustable filler distribution and orientation and preparation method thereof |
| CN108587007A (en) * | 2018-01-17 | 2018-09-28 | 清华大学 | A kind of laminated construction ferroelectric polymers based dielectric film, and its preparation method and application |
| CN110284263A (en) * | 2019-06-13 | 2019-09-27 | 上海交通大学 | The preparation method of lamination composite nano fiber |
| CN111472099A (en) * | 2020-04-17 | 2020-07-31 | 成都新柯力化工科技有限公司 | Composite piezoelectric ceramic fiber membrane for road power generation and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114388266A (en) * | 2022-01-14 | 2022-04-22 | 西安交通大学 | A kind of high energy storage density wide operating temperature composition gradient structure film and preparation method thereof |
| CN114388266B (en) * | 2022-01-14 | 2024-01-30 | 西安交通大学 | High-energy-storage-density wide-working-temperature component gradient structural film and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104044318B (en) | Polymer-based dielectric energy-storage composite material of a kind of laminated construction and preparation method thereof | |
| CN109666172B (en) | A kind of gradient structure polymer nanocomposite material and its preparation method and application | |
| CN102504449B (en) | A polymer-based composite membrane with high energy storage density and its preparation method | |
| Lin et al. | Enhanced electric displacement induces large energy density in polymer nanocomposites containing core–shell structured BaTiO 3@ TiO 2 nanofibers | |
| CN109486106B (en) | High energy storage density dielectric material and preparation method thereof | |
| CN107901303B (en) | Sandwich-structured high-energy-density polymer-based dielectric composite material and preparation method thereof | |
| US20150062779A1 (en) | Edlc electrode and manufacturing process thereof | |
| CN108998893B (en) | A kind of gradient structure polyvinylidene fluoride composite medium and preparation method thereof | |
| CN111403804A (en) | A kind of polymer matrix composite solid electrolyte film and preparation method thereof | |
| US12163005B2 (en) | Multilayer and flexible capacitors with metal-ion doped TIO2 colossal permittivity material/polymer composites | |
| Siddiqui et al. | Interface modulation in multi-layered BaTiO 3 nanofibers/PVDF using the PVP linker layer as an adhesive for high energy density capacitor applications | |
| Wu et al. | Poly (methyl methacrylate)-based ferroelectric/dielectric laminated films with enhanced energy storage performances | |
| CN105086297A (en) | Electric energy storage dielectric ceramic/polymer composite material and preparing method thereof | |
| Liu et al. | Flexible BaTiO3nf-Ag/PVDF nanocomposite films with high dielectric constant and energy density | |
| CN109097841B (en) | Anisotropic nanofiber polyvinylidene fluoride composite medium and preparation method thereof | |
| Wang et al. | Dielectric nanocomposites with high energy density by doping core-double shell structured fillers | |
| CN110341205B (en) | A kind of multilayer polymer nanocomposite material and preparation method thereof | |
| CN112038480A (en) | Piezoelectric fiber with Swiss roll structure and preparation method and application thereof | |
| CN112695462A (en) | Composite dielectric material with multilayer gradient structure and preparation method thereof | |
| CN108539149A (en) | A kind of graphene composite nitrogen, oxygen codope biomass carbon material and preparation method thereof | |
| CN108866819A (en) | A kind of polymer nanocomposites and preparation method thereof | |
| CN107230803B (en) | Sandwich structure multilayer gel polymer electrolyte for lithium ion battery and preparation method thereof | |
| CN102775626A (en) | Preparation method of high-energy storage density solid dielectric composite material | |
| CN115322413B (en) | A kind of flexible dielectric energy storage material and its preparation method and application | |
| CN108587007B (en) | A kind of laminated construction ferroelectric polymers based dielectric film, and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210423 |