CN112185703A - High-breakdown and high-energy-density two-dimensional composite sandwich structure polymer-based dielectric energy storage material and preparation method and application thereof - Google Patents
High-breakdown and high-energy-density two-dimensional composite sandwich structure polymer-based dielectric energy storage material and preparation method and application thereof Download PDFInfo
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- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 7
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 7
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- H01G4/00—Fixed capacitors; Processes of their manufacture
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Abstract
The invention relates to a two-dimensional composite with high breakdown and high energy storage densityA sandwich structure polymer-based dielectric energy storage material and a preparation method and application thereof are provided, wherein the preparation method comprises the following steps: firstly, preparing a BNNS dispersion liquid and a mixed dispersion liquid of SNNS and BNNS, respectively adding PVDF and PMMA, and heating and stirring to obtain a BNNS sol and a composite sol; then, BNNS/BP is used as an intermediate layer, xBNNS/yD-SNNS/BP is used as an upper layer and a lower layer, a composite film with a sandwich structure is prepared by adopting a layer-by-layer tape casting method, and the dielectric energy storage material is obtained after post-treatment; the obtained dielectric energy storage material can be applied to the fields of electronic information, renewable energy conversion, hybrid electric vehicles, smart power grids and the like. Compared with the prior art, the preparation method is simple, the cost is low, and the obtained organic-inorganic composite dielectric energy storage material has excellent energy storage performance which is 660 MV.m‑1Under the breakdown voltage, the discharge energy storage density is as high as 30.5J cm‑3The charge-discharge efficiency was 70.9%.
Description
Technical Field
The invention belongs to the technical field of organic-inorganic composite energy storage materials, and relates to a high-breakdown high-energy-density two-dimensional composite sandwich structure polymer-based dielectric energy storage material, and a preparation method and application thereof.
Background
With the continuous development of human civilization, the energy consumption is continuously increased, so that the service life of non-renewable energy sources such as fossil fuel is continuously shortened, according to the analysis and calculation of world reserves, the service life of coal for human is only 200 years, and the service life of petroleum is 50 years. In addition, the combustion of fossil fuel increases the emission of carbon dioxide, and the greenhouse effect is increasingly intensified, resulting in a series of natural disasters. Therefore, the development and utilization of renewable energy sources has become a major means of replacing fossil fuels worldwide. One of the major problems with the use of renewable energy sources is the efficient conversion and storage of energy. According to different energy storage principles, energy storage technologies can be divided into electrochemical energy storage, electrical energy storage, electromagnetic energy storage, thermal energy storage and mechanical energy storage. Among a plurality of energy storage devices, the capacitor has the largest power density and the fastest charge-discharge rate, can convert intermittent renewable energy sources such as wind energy, tidal energy and the like to the greatest extent, and has wide application prospects in the fields of electronic information, aerospace, smart power grids, hybrid electric vehicles and the like. Compared with energy storage devices such as fuel cells and super capacitors, the lower energy storage density of the dielectric capacitor cannot meet the requirements of miniaturization, light weight and integration of electronic devices. Therefore, the development of high energy storage dielectric capacitors has become a focus and focus of research in this field.
The research on solid dielectric energy storage materials has mainly focused on four categories: ceramics, polymers, organic-inorganic composites anda glass-ceramic. Common ceramic dielectric materials have high dielectric constant, but have low breakdown field strength and are difficult to process due to poor flexibility; the breakdown field strength of polymers is high, but the dielectric constant is small, for example, the breakdown field strength of PVDF is as high as 600MV m-1However, the dielectric constant is only about 10, which severely limits the energy storage density. Therefore, the organic-inorganic composite dielectric material obtained by compounding the ceramic dielectric material and the polymer through a certain process combines the advantages of the ceramic dielectric material and the polymer dielectric material, obtains higher dielectric constant and breakdown field strength, and further realizes the improvement of energy storage density. The size of the ceramic filler has a very large influence on the dielectric constant and the breakdown strength of the composite material. Currently, most research is focused on the composition of nanoparticles and nanowires. Generally, the one-dimensional nanowires have a larger aspect ratio than the nanoparticles, which is beneficial for increasing the local electric field, reducing the surface energy, and promoting the dispersibility of the filler in the polymer matrix. Lin et al composite titanium dioxide coated barium titanate nanofibers in PVDF at 360MV · m-1Under the external electric field, 10.94 J.cm is obtained-3The energy storage density of (1). Compared with the nanofiber, the two-dimensional nano filler has a larger length-diameter ratio, and can theoretically more effectively improve the energy storage performance of the composite material. Li et al introduced two-dimensional ultrathin Boron Nitride Nanosheet (BNNS) in polymer matrix to obviously improve breakdown field strength, energy storage density and charge-discharge efficiency of composite material at 650 MV.m-1Under the electric field of (2), 20.3 J.cm was obtained-3The energy storage density and the charging and discharging efficiency are as high as 78 percent. This is due to the high aspect ratio of BNNS creating an efficient conduction barrier that limits charge transport to the electrode and prevents the growth of electrical trees during breakdown. However, BNNS has a lower dielectric constant than PVDF, only 3-5, and thus improves the breakdown performance of the composite material only in one way, and the polarization performance is limited. Pan et al prepared a two-dimensional sodium niobate template as a filler by a molten salt method and introduced into PVDF at 400MV m-113.5 J.cm was obtained-3The energy storage density of (1). The sodium niobate template is thicker, so that the improvement of the energy storage performance of the composite dielectric material is limited. Other thingsThe ferroelectric ceramic materials such as barium titanate, strontium titanate, titanium dioxide and the like are difficult to synthesize two-dimensional nano materials meeting the requirements, so that the development of the ultrathin ferroelectric two-dimensional nano filler becomes a new way for further improving the energy storage performance of the composite dielectric material at present.
Disclosure of Invention
The invention aims to provide a high-breakdown and high-energy-storage-density two-dimensional composite sandwich-structure polymer-based dielectric energy storage material, and a preparation method and application thereof, which are used for solving the technical problem that the high dielectric breakdown strength and the high energy storage density of the conventional dielectric energy storage material cannot be considered at the same time.
The purpose of the invention can be realized by the following technical scheme:
a two-dimensional composite sandwich structure polymer-based dielectric energy storage material comprises an xBNNS/BP composite material middle layer and an xBNNS/yD-SNNS/BP composite material upper and lower layers, wherein x and y are 0-2.0 wt%; the thickness ratio of the upper layer, the middle layer and the lower layer is (0.5-1.5) to 1 (0.5-1.5), BNNS is a hexagonal boron nitride nano-sheet, SNNS is a strontium niobate nano-sheet, and BP is a mixed polymer material of polyvinylidene fluoride (PVDF) and polymethyl methacrylate (PMMA).
The phase composition of PVDF is remarkably changed by introducing PMMA into the PVDF, and a BP matrix of a high-beta ferroelectric phase is obtained; the breakdown strength of a BP matrix is greatly improved by introducing BNNS, the leakage conduction is reduced, the residual polarization intensity is reduced, the energy storage density and the charge-discharge efficiency are improved, and the introduction of SNNS increases the dielectric constant of the BNNS/BP composite material, thereby being beneficial to improving the maximum polarization intensity of the composite material and further improving the energy storage density. In addition, the breakdown resistance of the material is improved by taking the xBNNS/BP composite material as an intermediate layer, and the polarization performance can be effectively improved by taking the xBNNS/yD-SNNS/BP composite material as an upper layer and a lower layer.
A preparation method of a two-dimensional composite sandwich structure polymer-based dielectric energy storage material comprises the following steps:
1) preparing a mixed dispersion liquid of SNNS and BNNS, then adding polyvinylidene fluoride and polymethyl methacrylate, and heating and stirring to obtain a composite sol; preparing a BNNS dispersion liquid, then adding polyvinylidene fluoride and polymethyl methacrylate, and heating and stirring to obtain a BNNS sol;
2) the dielectric energy storage material is prepared by taking BNNS sol and composite sol as raw materials, preparing an xBNNS/yD-SNNS/BP composite film with a sandwich structure by adopting a layer-by-layer tape casting method, and performing post-treatment.
Further, in step 1), the preparation method of the SNNS comprises the following steps:
a1, mixing niobium pentoxide with a potassium hydroxide solution, and reacting at 160-200 ℃ for 6-16h to obtain a potassium niobate solution;
a2, mixing the potassium niobate solution with the strontium nitrate solution, reacting for 60-84h at the temperature of 220-260 ℃, and then centrifuging, washing and drying to obtain the SNNS.
Furthermore, the feeding ratio of the niobium pentoxide solution to the potassium hydroxide solution to the strontium nitrate solution is 0.2-0.3g:15-25mL:15-25mL, and the concentration of the potassium hydroxide solution is 1-5 mol.L-1The concentration of the strontium nitrate solution is 0.05-0.3 mol.L-1。
Further, in step 1), the BNNS is prepared by a method comprising: adding hexagonal boron nitride into isopropanol, carrying out ultrasonic treatment for 36-60h, then sequentially carrying out centrifugation, washing and drying processes to obtain the hexagonal boron nitride nanosheet,
wherein the mass-volume ratio of the hexagonal boron nitride to the isopropanol is 1-5g:300 mL.
Further, in step 1), the solvent in the dispersion liquid comprises N, N-Dimethylformamide (DMF); the mass ratio of the polyvinylidene fluoride to the polymethyl methacrylate is (2-6) to 1; in the heating and stirring process, the heating temperature is 40-60 ℃, and the stirring time is 20-28 h.
Further, in step 1), the strontium niobate nanosheet is a dopamine organic surface function-modified strontium niobate nanosheet, and the preparation method thereof comprises: dispersing SNNS in a Tris-HCl buffer solution, mixing with a dopamine hydrochloride aqueous solution at 40-60 ℃, stirring for 3-8h, and then sequentially centrifuging, washing and drying to obtain the dopamine organic surface function modified strontium niobate nano-sheet, which is recorded as D-SNNS.
Furthermore, the feeding ratio of the SNNS, the Tris-HCl buffer solution and the dopamine hydrochloride aqueous solution is 0.5-2.5g:50-150mL:10-30mL, and the concentration of the Tris-HCl buffer solution is 0.04-0.06 mol.L-1The concentration of the dopamine hydrochloride aqueous solution is 4-6 g.L-1。
Further, in the step 2), the post-treatment sequentially comprises vacuum drying at 65-80 ℃ for 20-28h, heating at 180-220 ℃ for 5-20min and quenching in ice water, and vacuum drying again at 65-80 ℃ for 20-28 h.
An application of a two-dimensional composite sandwich structure polymer-based dielectric energy storage material in the fields of renewable energy conversion, electronic information, hybrid electric vehicles and smart grids.
Compared with the prior art, the invention has the following characteristics:
1) compared with pure PVDF, the introduction of PMMA promotes the transformation of alpha phase to beta phase in PVDF, improves the instability of the PVDF polar structure, ensures that the maximum potential shift of a mixed polymer matrix BP is stably increased along with the increase of an external electric field, and has the maximum breakdown strength as high as 460MV m when the mass ratio of PVDF to PMMA is 4:1-1Maximum potential shift of 7.8 μ C · cm-2；
2) By compounding the non-ferroelectric two-dimensional BNNS and the ferroelectric two-dimensional SNNS and constructing a sandwich structure, the dielectric strength and the maximum potential shift of a polymer matrix are greatly improved, and the high-breakdown high-energy-density two-dimensional composite sandwich structure polymer-based dielectric energy storage material is prepared, wherein the dielectric strength and the maximum potential shift of the polymer matrix are respectively 660MV · m when the compounding amount of the SNNS is 0.5 wt.%-1The potential shift under the external electric field is up to 11.65 mu C cm-2The residual potential shift is only 1.15 mu C cm-2And the energy storage density reaches 30.5 J.cm-3。
Drawings
FIG. 1 is a schematic crystal structure and XRD spectrum of SNNS synthesized by hydrothermal method in example 3;
FIG. 2 is a graph of comparative infrared spectra of PVDF and BP used in example 3;
FIG. 3 is a graph showing the D-E curves of PVDF and BP used in example 3 and the change in electric displacement under different applied electric fields;
FIG. 4 is a graph showing the effect of the BNNS loading on the dielectric properties of xBNNS/BP thin film in example 4;
FIG. 5 is a D-E plot of a single layer 1.5 wt.% BNNS/BP film of example 4;
FIG. 6 is a dielectric spectrum of the polymer-based dielectric energy storage material with two-dimensional composite sandwich structure in example 5;
FIG. 7 is a Weibull distribution diagram of dielectric breakdown of the polymer-based dielectric energy storage material with two-dimensional composite sandwich structure in example 5;
FIG. 8 is a D-E plot of the polymer-based dielectric energy storage material with two-dimensional composite sandwich structure in example 5;
fig. 9 shows the energy storage density and the charge-discharge efficiency of the polymer-based dielectric energy storage material with the two-dimensional composite sandwich structure in example 5 under different applied voltages.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A two-dimensional composite sandwich structure polymer-based dielectric energy storage material comprises a BNNS/BP composite material middle layer and an xBNNS/yD-SNNS/BP composite material upper layer and a lower layer, wherein x and y are 0-2.0 wt.%.
The preparation method of the dielectric energy storage material comprises the following steps:
1) preparing SNNS by a two-step hydrothermal method: dispersing niobium pentoxide in 1-5 mol.L-1Reacting in a potassium hydroxide solution at the temperature of 160-; under the condition of continuous stirring adding 0.05-0.3 mol.L-1Dropwise adding a strontium nitrate solution into a potassium niobate solution, controlling the filling volume of a reaction container to be 75-85%, reacting at the temperature of 220-260 ℃ for 60-84h to obtain a white precipitate, and then sequentially performing the processes of centrifugation, suction filtration, washing and drying to obtain the SNNS; wherein the niobium pentoxide and the potassium hydroxide are dissolvedThe feeding ratio of the solution to the strontium nitrate solution is 0.2-0.3g:15-25mL:15-25 mL;
2) preparation of D-SNNS: adding SNNS into Tris-HCl buffer solution, ultrasonically dispersing for 1-3h, and dropwise adding 4-6 g.L-1D-SNNS is obtained by sequentially carrying out centrifugation, washing and drying processes on a dopamine hydrochloride aqueous solution which is stirred for 3-8 hours at 40-60 ℃ to coat a layer of dopamine hydrochloride on the surface of SNNS through an autopolymerization process; wherein the feeding ratio of the SNNS, the Tris-HCl buffer solution and the dopamine hydrochloride aqueous solution is 0.5-2.5g, 50-150mL and 10-30 mL;
3) preparing BNNS by a liquid phase stripping method: dispersing hexagonal boron nitride in isopropanol, ultrasonically stripping at the tip for 36-60h, controlling the ultrasonic power at 150-250W, and then sequentially performing centrifugation, washing and drying processes to obtain the hexagonal boron nitride nanosheet, wherein the mass-volume ratio of the hexagonal boron nitride to the isopropanol is 1-5g:300 mL;
4) preparing D-SNNS and BNNS composite sol: ultrasonically dispersing D-SNNS and BNNS in DMF, adding PVDF and PMMA in a mass ratio of (2-6):1, heating and stirring at 40-60 ℃ for 20-28h, and performing vacuum treatment for 8-15min to discharge bubbles to obtain composite sol;
5) preparation of BNNS sol: ultrasonically dispersing BNNS in DMF, adding PVDF and PMMA in a mass ratio of (2-6):1, heating and stirring at 40-60 ℃ for 20-28h, and performing vacuum treatment for 8-15min to discharge bubbles to obtain BNNS sol;
6) preparing a dielectric energy storage material by a layer-by-layer tape casting method: BNNS sol and composite sol are used as raw materials, a layer-by-layer tape casting method is adopted to heat at 80 ℃ and blade-coat each layer of sol on ITO conductive glass to prepare an xBNNS/yD-SNNS/BP composite film with a sandwich structure, the thickness ratio of an upper layer, a middle layer and a lower layer is controlled to be (0.5-1.5):1 (0.5-1.5), then vacuum drying is carried out for 20-28h at 65-80 ℃, heating is carried out for 5-20min at 180-220 ℃, the film is placed in ice water for quenching, vacuum drying is carried out for 20-28h at 65-80 ℃, and then the dielectric energy storage material is obtained.
An application of a two-dimensional composite sandwich structure polymer-based dielectric energy storage material in the fields of renewable energy conversion, electronic information, hybrid electric vehicles and smart grids.
The following examples are given in detail to illustrate the embodiments and specific procedures of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1:
the preparation method is used for preparing the dopamine organic surface functionalized strontium niobate nanosheet and carrying out structural characterization on the dopamine organic surface functionalized strontium niobate nanosheet. The preparation method comprises the following steps:
1) 0.26g of niobium pentoxide was ultrasonically dispersed in 20mL of 3 mol. L-1Transferring the potassium hydroxide solution into a 50mL hydrothermal kettle, and reacting at 180 ℃ for 10h to obtain a clear potassium niobate solution;
2) under the condition of continuous stirring, 20mL of 0.2 mol.L-1Dropwise adding a strontium nitrate solution into a potassium niobate solution (namely the filling volume of a hydrothermal kettle is 80%), reacting for 72 hours at 240 ℃ to obtain a white precipitate, and then sequentially performing centrifugation, suction filtration, washing and drying processes to obtain the SNNS;
3) 1.5g of SNNS was added to 100mL of Tris-HCl buffer solution and ultrasonically dispersed for 2 hours, after which 20mL of 5 g.L was added dropwise-1And (3) the dopamine hydrochloride aqueous solution is stirred for 5 hours at 50 ℃ to coat a layer of dopamine hydrochloride on the surface of the SNNS through an autopolymerization process, and then the D-SNNS is obtained after the processes of centrifugation, washing and drying in sequence.
The characterization results were as follows:
FIG. 1 shows the crystal structure and XRD diffraction pattern of SNNS prepared in step 1), wherein the crystal structure is a sandwich layered structure with Sr ion layers as expression2+(SrNb2O7)2-The distortion of NbO octahedral units makes SNNS ferroelectric at room temperature. The Nb ions are displaced in NbO octahedrons, so that a dipole moment exists in the direction of the c axis of the perovskite layer. The results of XRD demonstrate that SNNS was successfully synthesized by two hydrothermal reactions, with no impurity phases.
Example 2:
this example was used to prepare BNNS by liquid phase exfoliation, the preparation method comprising:
adding 3g of hexagonal boron nitride powder into 300mL of isopropanol, ultrasonically stripping the tip for 48h at the ultrasonic power of 200W, and then sequentially performing the processes of centrifugation, suction filtration, washing and drying to obtain the hexagonal boron nitride nanosheet.
Example 3:
this example was used to prepare a mixed polymer material BP of PVDF and PMMA, and examine the effect of PMMA on PVDF performance. The preparation method comprises the following steps:
adding 2.4g of PVDF and 0.6g of PMMA into 10mL of DMF, heating and stirring at 50 ℃ for 24h, and then carrying out vacuum treatment for 10min to discharge bubbles, thus obtaining BP.
The material performance characterization results are as follows:
FIG. 2 shows the IR spectrum of pure PVDF and BP according to the ferroelectric phase at 1275cm-1And an alpha non-ferroelectric phase at 764cm-1The characteristic peaks show that when PVDF and PMMA are mixed at a mass ratio of 4:1, the β ferroelectric phase in BP is significantly increased and the α non-ferroelectric phase is almost disappeared.
FIG. 3 shows the D-E curve of pure PVDF and BP under the maximum breakdown field strength and the variation of maximum electric displacement and residual electric displacement with the applied electric field. As can be seen from the figure, the maximum potential shift is increased at 300MV · m along with the applied electric field due to the instability of the polarity structure of PVDF per se-1The increase then slows, but the maximum potential shift of BP steadily increases with increasing applied electric field, so that BP obtains a higher maximum potential shift than pure PVDF at the same applied high field. In addition, the introduction of PMMA also improves the electrical breakdown strength of BP to reach 460 MV.m-1At this time, the maximum potential shift was 7.8. mu.C · cm-2。
Example 4:
this example is used to prepare a single-layer xBNNS/BP dielectric energy storage material, and examine the influence of the BNNS recombination amount (the mass percentage of BNNS relative to BP) on the dielectric constant and loss of the material, wherein the preparation method of the single-layer xBNNS/BP dielectric energy storage material comprises the following steps:
1) ultrasonically dispersing the BNNS prepared in example 2 in 10mL of DMF, then adding 2.4g of PVDF and 0.6g of PMMA, heating and stirring at 50 ℃ for 24h, and performing vacuum treatment for 10min to discharge bubbles to obtain BNNS sol;
2) and (2) coating the BNNS sol on ITO conductive glass by a casting machine at 80 ℃, wherein the coating thickness is 3 mu m, then sequentially carrying out vacuum drying at 70 ℃ for 24h, heating at 200 ℃ for 10min, placing in ice water for quenching, and carrying out vacuum drying at 70 ℃ for 24h again to obtain the single-layer xBNNS/BP dielectric energy storage material.
The material performance characterization results are as follows:
FIG. 4 shows the dielectric constant and loss of a single layer xBNNS/BP as a function of the BNNS recombination amount at 1 kHz. As can be seen from the figure, as the composite amount of BNNS increases, the dielectric constant and the loss gradually decrease because the dielectric constant of BNNS is lower, but the better insulation performance thereof causes the loss of the film to also gradually decrease with the increase of the composite amount, and at x of 1.5 wt.%, the loss decreases to 0.029, while at the composite amount of 2.0 wt.%, the loss increases because the organic-inorganic phase interface structure defects increase due to the large amount of composite. And from this, the optimum complexing amount of BNNS was 1.5 wt.%.
As shown in FIG. 5, which is a D-E curve of a single layer of 1.5 wt.% BNNS/BP, it can be seen that the introduction of BNNS greatly improves the breakdown resistance of the BP polymeric matrix, with a maximum breakdown strength as high as 660MV m-1The maximum potential shift reaches 10.77 mu C-cm-2The residual potential shift is only 0.97 mu C cm-2。
Example 5:
in this example, the D-SNNS in example 1 and the BNNS in example 2 were used to prepare a composite sol of D-SNNS and BNNS, and the preparation method includes:
ultrasonically dispersing 0.5 wt.% of D-SNNS and 1.5 wt.% of BNNS in 10mL of DMF, then adding 2.4g of PVDF and 0.6g of PMMA, heating and stirring at 50 ℃ for 24h, and then carrying out vacuum treatment for 10min to discharge air bubbles, thus obtaining the composite sol.
Example 6:
in this embodiment, the BNNS sol in embodiment 4 and the composite sol in embodiment 5 are used as raw materials to prepare a two-dimensional composite sandwich-structured polymer-based dielectric energy storage material, wherein the preparation method comprises:
taking 1.5 wt.% of BNNS/BP as an intermediate layer, taking 1.5 wt.% of BNNS/0.5 wt.% of D-SNNS/BP as an upper outer layer and a lower outer layer, heating and blade-coating all layers of sol on ITO conductive glass (the thickness of each layer is 3 mu m) by adopting a layer-by-layer tape casting method at 80 ℃ to prepare a 1.5 wt.% of BNNS/0.5 wt.% of D-SNNS/BP composite film with a sandwich structure, then sequentially carrying out vacuum drying at 70 ℃ for 24h, heating at 200 ℃ for 10min and placing in ice water for quenching, and carrying out vacuum drying at 70 ℃ for 24h again to obtain the dielectric energy storage material.
The material performance characterization results are as follows:
as shown in fig. 6, which is the spectrum of the dielectric energy storage material in the present embodiment, it can be seen that the dielectric constant of the dielectric energy storage material at 1kHz is increased to 9.5 at a D-SNNS recombination amount of 0.5 wt%;
FIG. 7 is a Weibull distribution diagram of the dielectric breakdown of the dielectric energy storage material in this example, and it can be seen that the maximum breakdown strength of the material reaches 664.45MV m-1Shape factor 15.94;
as shown in FIG. 8, which is a D-E curve of the dielectric energy storage material in this example, it can be seen that the combination of 0.5 wt.% SNNS does not cause a decrease in breakdown strength, while the maximum polarization is increased to 11.64 μ C-cm compared to a single layer of 1.5 wt.% BNNS/BP-2；
FIG. 9 shows the discharge energy density and the charge/discharge efficiency of the dielectric energy storage material in this embodiment, and it can be seen from the graph that the dielectric energy storage material is 660MV · m-1Under the external electric field, the higher energy storage density of 30.5J cm is obtained-3The charge-discharge efficiency was 70.9%.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The two-dimensional composite sandwich structure polymer-based dielectric energy storage material is characterized by comprising an xBNNS/BP composite material middle layer and an xBNNS/yD-SNNS/BP composite material upper and lower layers, wherein x and y are 0-2.0 wt%; BNNS is a hexagonal boron nitride nanosheet, SNNS is a strontium niobate nanosheet, and BP is a mixed polymer material of polyvinylidene fluoride and polymethyl methacrylate.
2. The preparation method of the two-dimensional composite sandwich structure polymer-based dielectric energy storage material according to claim 1, wherein the method comprises the following steps:
1) preparing a mixed dispersion liquid of SNNS and BNNS, then adding polyvinylidene fluoride and polymethyl methacrylate, and heating and stirring to obtain a composite sol; preparing a BNNS dispersion liquid, then adding polyvinylidene fluoride and polymethyl methacrylate, and heating and stirring to obtain a BNNS sol;
2) the dielectric energy storage material is prepared by taking BNNS sol and composite sol as raw materials, preparing an xBNNS/yD-SNNS/BP composite film with a sandwich structure by adopting a layer-by-layer tape casting method, and performing post-treatment.
3. The method for preparing the polymer-based dielectric energy storage material with the two-dimensional composite sandwich structure according to claim 2, wherein in the step 1), the method for preparing the SNNS comprises the following steps:
a1, mixing niobium pentoxide with a potassium hydroxide solution, and reacting at 160-200 ℃ for 6-16h to obtain a potassium niobate solution;
a2, mixing the potassium niobate solution with the strontium nitrate solution, reacting for 60-84h at the temperature of 220-260 ℃, and then centrifuging, washing and drying to obtain the SNNS.
4. The method of claim 3, wherein the polymer-based dielectric energy storage material has a two-dimensional composite sandwich structureThe preparation method is characterized in that the feeding ratio of the niobium pentoxide solution to the potassium hydroxide solution to the strontium nitrate solution is 0.2-0.3g:15-25mL:15-25mL, and the concentration of the potassium hydroxide solution is 1-5 mol.L-1The concentration of the strontium nitrate solution is 0.05-0.3 mol.L-1。
5. The preparation method of the two-dimensional composite sandwich structure polymer-based dielectric energy storage material according to claim 2, wherein in the step 1), the strontium niobate nanosheet is a dopamine organic surface function-modified strontium niobate nanosheet, and the preparation method comprises: dispersing SNNS in a Tris-HCl buffer solution, mixing with a dopamine hydrochloride aqueous solution at 40-60 ℃, stirring for 3-8h, and then sequentially centrifuging, washing and drying to obtain the dopamine organic surface function modified strontium niobate nano-sheet, which is recorded as D-SNNS.
6. The method for preparing the two-dimensional composite sandwich structure polymer-based dielectric energy storage material of claim 5, wherein the feeding ratio of the SNNS, the Tris-HCl buffer solution and the dopamine hydrochloride aqueous solution is 0.5-2.5g:50-150mL:10-30mL, and the concentration of the Tris-HCl buffer solution is 0.04-0.06 mol.L-1The concentration of the dopamine hydrochloride aqueous solution is 4-6 g.L-1。
7. The method for preparing the polymer-based dielectric energy storage material with the two-dimensional composite sandwich structure according to claim 2, wherein the BNNS preparation method in step 1) comprises: adding hexagonal boron nitride into isopropanol, carrying out ultrasonic treatment for 36-60h, and then sequentially carrying out centrifugation, washing and drying processes to obtain the hexagonal boron nitride nanosheet;
wherein the mass-volume ratio of the hexagonal boron nitride to the isopropanol is 1-5g:300 mL.
8. The method for preparing the polymer-based dielectric energy storage material with the two-dimensional composite sandwich structure according to claim 2, wherein in the step 1), the mass ratio of the polyvinylidene fluoride to the polymethyl methacrylate is (2-6): 1; in the heating and stirring process, the heating temperature is 40-60 ℃, and the stirring time is 20-28 h.
9. The method as claimed in claim 2, wherein the post-treatment of step 2) comprises vacuum drying at 65-80 ℃ for 20-28h, heating at 180-220 ℃ for 5-20min, quenching in ice water, and vacuum drying again at 65-80 ℃ for 20-28 h.
10. The application of the two-dimensional composite sandwich structure polymer-based dielectric energy storage material as claimed in claim 1 in the fields of renewable energy conversion, electronic information, hybrid electric vehicles and smart grids.
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