CN109762278B - Two-dimensional nanosheet-polymer flexible composite film and preparation method thereof - Google Patents
Two-dimensional nanosheet-polymer flexible composite film and preparation method thereof Download PDFInfo
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Abstract
The invention provides a two-dimensional nanosheet-polymer flexible composite film and a preparation method thereof2(Nb,Ta)3O10The polymer is prepared from one or more than one of polyvinylidene fluoride, polyvinylidene fluoride-trifluoroethylene, polyvinylidene fluoride-hexafluoropropylene, epoxy resin, polypropylene and polyimide, and the preparation process comprises the following steps: high-temperature sintering synthesis of KCa2Nb3O10A material; synthesis of HCa by proton exchange reaction2Nb3O10·1.5H2An O material; stripping into two-dimensional nanosheets; and preparing the flexible composite film product by a casting method. According to the invention, the polymer matrix composite with excellent performance is obtained under the condition of a lower inorganic matter addition amount by adding the two-dimensional nanosheet into the polymer matrix, so that the composite retains the good flexibility of the polymer matrix, and the breakdown field strength of the composite film is improved.
Description
Technical Field
The invention relates to the technical field of dielectric composite material manufacturing, in particular to a two-dimensional nanosheet-polymer flexible composite film and a preparation method thereof.
Background
With the rapid development of high and new technology industries such as internet of things, big data, new energy automobiles, intelligent terminals and the like, the global capacitor market is rapidly growing, and has expanded from 173 billion dollars in 2012 to 209 billion dollars in 2017. Capacitors made of different dielectric materials are derived according to different application scene requirements, and ceramic capacitors, aluminum electrolytic capacitors, tantalum electrolytic capacitors and film capacitors are widely applied in the market at present. Ceramic dielectrics are widely used because of their high dielectric constant, but their disadvantages such as being brittle, having large loss, and not being used in Printed Circuit Boards (PCBs) cannot be ignored. In the face of the trend of capacitor miniaturization, flexibility and non-activation, a single inorganic ceramic dielectric material cannot meet the requirement. Polymer dielectric materials are widely used in film capacitors because of their characteristics of good flexibility, low mass, easy processing, and easy fabrication into films in large areas. Wherein, the inorganic ceramic material has very high dielectric constant, but the breakdown field strength under the high-voltage condition is lower; while organic polymer materials have a higher breakdown field strength but a lower dielectric constant. Therefore, organic-inorganic composite dielectric materials having good flexibility, small mass, easy processing, and low cost have received much attention. The inorganic ceramic material is added into the polymer matrix, so that the dielectric constant of the polymer matrix is obviously improved, and the polymer matrix has high breakdown field strength. In the field of electrical engineering, the polymer-based composite dielectric material is a good high-voltage cable terminal stress cone material; in the field of mechano-electronics, the polymer-based composite dielectric material has good compatibility with an organic circuit board, and is widely used in an embedded circuit board. In addition, along with the development of national smart grid and new energy industry, high-power and large-capacity capacitors have become important demands of new energy markets, and polymer-based composite films have become important components of high-power components due to high breakdown field strengths.
The existing research is mainly to add ceramic particles with high dielectric constant into polymer matrix to improve the relative dielectric constant of polymer matrix composite material, and the commonly used ceramic particles are barium titanate (BaTiO)3) Titanium dioxide (TiO)2) Zirconium dioxide (ZrO)2) And the like. However, the proposal has obvious problems that the dielectric constant of the composite material can be improved only by adding high inorganic ceramic particles, and the volume fraction of the inorganic ceramic particles is generally more than 50 percent, which greatly reduces the flexibility of the composite material. In addition, the addition of too much inorganic component causes defects to decrease the breakdown field strength of the composite film. Therefore, it is necessary to solve the problems in the prior artAnd (5) carrying out improvement.
Disclosure of Invention
The invention aims to provide a two-dimensional nanosheet-polymer flexible composite film and a preparation method thereof, and the polymer-based composite material with excellent performance is obtained under the condition of low inorganic matter addition amount by adding the two-dimensional nanosheet into a polymer matrix, so that the composite material retains the good flexibility of the polymer matrix, and the breakdown field strength of the composite film is improved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a two-dimensional nanosheet-polymer flexible composite film is prepared from two-dimensional nanosheets and a polymer matrix.
According to the above scheme, the two-dimensional nano-sheet is made of (Ca, Sr) with perovskite structure2(Nb,Ta)3O10Any one or more than one material in the system.
According to the scheme, the length and the width of the two-dimensional nanosheet are both 0.1-1 μm, the thickness is 1-2nm, and the thickness of the two-dimensional nanosheet-polymer flexible composite film is 1-100 μm.
According to the scheme, the polymer is prepared from one or more of Polyvinylidene fluoride (PVDF), Polyvinylidene fluoride-trifluoroethylene (PVDF-TrFE), Polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), Epoxy resin (Epoxy, EP), polypropylene (PP) and Polyimide (PI).
According to the scheme, the mass fraction of the two-dimensional nanosheet is 0.1-20%, and the mass fraction of the polymer is 80-99.9%.
A preparation method of a two-dimensional nanosheet-polymer flexible composite film comprises the following steps:
1) preparation of (Ca, Sr) having perovskite Structure2(Nb,Ta)3O10Two-dimensional nanosheets;
2) the two-dimensional nano sheet and the polymer are compounded to form a film.
According to the above scheme, the Ca2Nb3O10The preparation of the two-dimensional nano sheet adopts liquid phase strippingThe method comprises the following steps:
1) high-temperature sintering synthesis of KCa2Nb3O10Materials: mixing and grinding raw materials of potassium carbonate, calcium carbonate and niobium pentoxide according to a molar ratio of 1:2:3 for 30-60min, and then sintering at the temperature of 1000-1300 ℃ for 10-15 h;
2) synthesis of HCa by proton exchange reaction2Nb3O10·1.5H2O material: synthesized KCa2Nb3O10Mixing the material and nitric acid with the concentration of 1-10 mol/L according to the molar ratio of 1:1, placing the mixture on an oscillator, carrying out proton exchange reaction for 48-72h, filtering, and washing off residual nitric acid on the surface of the obtained sample by using ultrapure water with the resistivity of more than 18 MOmega;
3) precursor material HCa2Nb3O10·1.5H2Stripping O into two-dimensional nanosheets: the synthesized HCa2Nb3O10·1.5H2O material and tetrabutyl ammonium hydroxide solution (TBAOH, molecular formula is C)16H37NO) in a 1:1 molar ratio (i.e., TBA)+:H+And (1: 1), shaking on a mechanical oscillator for 10 days for stripping, and obtaining the two-dimensional nanosheet.
According to the scheme, the composite film is prepared by adopting a casting process and comprises the following steps:
1) ultrasonically dispersing the two-dimensional nano-sheet into an organic solvent N, N-Dimethylformamide (DMF) solution to form a stable suspension, then adding a polymer matrix, and stirring for 24-48h until the two-dimensional nano-sheet is fully dissolved;
2) and casting the mixture of the polymer and the two-dimensional nanosheets into a film with a required thickness, drying at 40-80 ℃, and collecting the obtained composite film.
The invention has the beneficial effects that:
1) the two-dimensional nanosheet is prepared by a liquid phase stripping method, has the structural characteristics of inorganic perovskite type, and has obvious polarization characteristic, so that the two-dimensional nanosheet has higher dielectric constant;
2) the high dielectric constant of the two-dimensional nanosheet can reduce the specific gravity of the inorganic filler in the composite material without influencing the improvement of the composite dielectric property, so that the composite film retains good mechanical flexibility;
3) the two-dimensional nanosheets are uniformly dispersed in the polymer matrix, so that the breakdown field intensity of the composite film is improved, and the application of the composite film in the aspect of high-voltage energy storage is facilitated;
4) according to the novel composite film manufacturing process, the two-dimensional nanosheet with the high dielectric constant and the polymer with the high breakdown field strength are compounded, and the prepared composite film has excellent mechanical properties and electrical properties and is expected to be widely applied to the field of composite dielectric materials.
Drawings
Figure 1 is an AFM image of two-dimensional nanoplatelets of example 1 of the present invention;
FIG. 2 is a graph of dielectric constant and dielectric loss as a function of frequency for the products of inventive example 1, example 2, and comparative example 1;
FIG. 3 is a graph showing the relationship between the electric potential shift of the products of example 1 of the present invention and comparative example 1 as a function of an applied electric field;
FIG. 4 is a sectional scanning electron microscope topography of a finished product of example 1 of the present invention.
Detailed Description
The technical solution of the present invention is described below with reference to the accompanying drawings and examples.
Example 1, see fig. 1-4:
the invention provides a two-dimensional nanosheet-polymer flexible composite film, and a preparation method thereof, wherein the preparation method comprises the following steps:
1) preparation of HCa having perovskite Structure2Nb3O10Two-dimensional nanosheet:
a) 1.4558g of potassium carbonate (K) are weighed out2CO3) 4.0164g calcium carbonate (CaCO)3) And 8.000g niobium pentoxide (Nb)2O5) Grinding in agate mortar for 60min, and calcining at 1200 deg.C for 12 hr to obtain KCa2Nb3O10A sample;
b) weighing 2.5g of synthesized KCa2Nb3O10The powder was placed in a cone containing 100ml of nitric acid (5mol/L)In the bottle, fixing the conical flask on a small oscillator for oscillation for 72h, filtering after the proton exchange reaction is finished, washing off residual nitric acid on the surface of the obtained sample by using ultrapure water (the resistivity is more than 18M omega), and obtaining the two-dimensional nanosheet precursor material HCa2Nb3O10·1.5H2O sample;
c) weighing 1.0g of synthesized two-dimensional nanosheet precursor material HCa2Nb3O10·1.5H2Placing the O powder in a conical flask filled with 250ml of tetrabutylammonium hydroxide solution (TBAOH), fixing the conical flask on an oscillator, and oscillating for 10 days to obtain an emulsion after the two-dimensional nanosheets are stripped;
2) compounding the two-dimensional nanosheets and the polymer to form a film:
d) measuring 1ml of emulsion after stripping two-dimensional nanosheets, freeze-drying to obtain a two-dimensional nanosheet floc, ultrasonically dispersing the two-dimensional nanosheet floc to 4ml of DMF solution to form a stable suspension, adding 0.396g of PVDF, stirring for 36h until the PVDF is fully dissolved, putting the obtained solution into a vacuum drying oven, standing for 20min, and promoting the discharge of bubbles;
e) and (3) casting a mixture of PVDF and the two-dimensional nanosheets into a film with a required thickness, then placing the film in a drying oven, standing for 12h at 40 ℃ (which is beneficial to evaporation of a solvent), then preserving heat for 10min at 200 ℃, and then placing the film in ice water for quenching to obtain the two-dimensional nanosheet-polymer flexible composite film with 1% of two-dimensional nanosheet filler.
Example 2, see figure 2:
the raw materials and the preparation process of the present example are basically the same as those of example 1, except that: and d), weighing 2ml of emulsion obtained after the two-dimensional nanosheets are stripped in the step d), wherein the finished product is the two-dimensional nanosheet-polymer flexible composite film with the two-dimensional nanosheet filler accounting for 2%.
Comparative example 1, see fig. 2 to 3:
weighing 0.5244g (mass fraction of 10%) of PVDF, dissolving in 5ml of DMF solution, stirring for 24h, placing the obtained solution in a vacuum drying oven, standing for 20min to promote the discharge of bubbles, and then carrying out tape casting treatment; then placing the synthesized film into a drying oven, and standing for 12h at 40 ℃ (beneficial to evaporation of the solvent); and then the PVDF film is subjected to heat preservation for 10min at the temperature of 200 ℃, and then is put into ice water for quenching to obtain the pure PVDF film.
AFM characterization is carried out on the stripped two-dimensional nanosheets obtained in the step c) of the embodiment 1, and the results are shown in FIG. 1, wherein the thickness of the two-dimensional nanosheets is 1.84nm, and the length and the width of the two-dimensional nanosheets are 0.2-0.5 μm.
The products of the embodiment 1, the embodiment 2 and the comparative embodiment 1 are tested, the relationship between the dielectric constant and the dielectric loss along with the frequency change is shown in fig. 2, the dielectric constant of the flexible PVDF film without the two-dimensional filler is 10-11, and the dielectric constant of the two-dimensional nanosheet-polymer flexible composite film prepared by adding the two-dimensional filler is obviously increased. When the mass fraction of the added two-dimensional filler is 1 wt%, the dielectric constant of the flexible composite film is between 12 and 13; when the mass fraction of the two-dimensional filler is 2 wt%, the dielectric constant of the flexible composite film is 13-14 (100 Hz). In the aspect of dielectric loss, when the mass fraction of the added two-dimensional filler is 1%, the dielectric loss of the flexible composite film is consistent with that of a pure PVDF film; when the mass fraction of the added two-dimensional filler is 2%, the dielectric loss of the flexible composite film is slightly higher than that of a pure PVDF film.
FIG. 3 shows the relationship between the electric potential shift of the products of example 1 and comparative example 1, and the electric potential shift of the flexible PVDF film to which no two-dimensional filler was added was 5.5mC/cm at an applied electric field strength of 500kV/mm2And the electric displacement of the two-dimensional nano-sheet-polymer flexible composite film added with 1 percent of two-dimensional filler is 6.5mC/cm2. Therefore, the remanent polarization strength of the two-dimensional nanosheet-polymer flexible composite film prepared by adding the two-dimensional filler is higher than that of a pure PVDF film, which is beneficial to improving the energy storage density of the film.
The cross-sectional morphology of the product in example 1 is shown in a Scanning Electron Microscope (SEM) figure 4, and the thickness of the prepared two-dimensional nanosheet-polymer flexible composite film is 10 μm.
Example 3:
the raw materials and the preparation process of the present example are basically the same as those of example 1, except that: the polymer is PVDF-HFP.
Example 4:
the raw materials and the preparation process of the present example are basically the same as those of example 1, except that: the polymer is EP.
Example 5:
the raw materials and the preparation process of the present example are basically the same as those of example 1, except that: the polymer is PP.
Example 6:
the raw materials and the preparation process of the present example are basically the same as those of example 1, except that: the polymer is a mixture of PP, PI and EP according to the molar ratio of 1:1: 1.
The above embodiments are only used for illustrating but not limiting the technical solutions of the present invention, and although the above embodiments describe the present invention in detail, those skilled in the art should understand that: modifications and equivalents may be made thereto without departing from the spirit and scope of the invention and any modifications and equivalents may fall within the scope of the claims.
Claims (2)
1. A two-dimensional nanosheet-polymer flexible composite film is characterized by being prepared from two-dimensional nanosheets and a polymer matrix;
the two-dimensional nano sheet is made of (Ca, Sr) with a perovskite structure2(Nb, Ta)3O10Any one or more than one material in the system;
the length and the width of the two-dimensional nanosheet are both 0.1-1 mu m, the thickness is 1-2nm, and the thickness of the two-dimensional nanosheet-polymer flexible composite film is 1-100 mu m;
the mass fraction of the two-dimensional nano-sheet is 0.1-20%, and the mass fraction of the polymer is 80-99.9%;
the preparation method of the two-dimensional nanosheet-polymer flexible composite film comprises the following steps:
1) preparation of (Ca, Sr) having perovskite Structure2(Nb, Ta)3O10The two-dimensional nanosheet adopts a liquid phase stripping method and comprises the following steps:
high-temperature sintering synthesis of KCa2Nb3O10Materials: the raw material potassium carbonateMixing and grinding calcium carbonate and niobium pentoxide for 30-60min according to the mol ratio of 1:2:3, and then sintering at the temperature of 1000-1300 ℃ for 10-15 h;
synthesis of HCa by proton exchange reaction2Nb3O10·1.5H2O material: synthesized KCa2Nb3O10Mixing the material and nitric acid with the concentration of 1-10 mol/L according to the molar ratio of 1:1, placing the mixture on an oscillator, carrying out proton exchange reaction for 48-72h, filtering, and washing off residual nitric acid on the surface of the obtained sample by using ultrapure water with the resistivity of more than 18 MOmega;
precursor material HCa2Nb3O10·1.5H2Stripping O into two-dimensional nanosheets: the synthesized HCa2Nb3O10·1.5H2Mixing the O material and the tetrabutylammonium hydroxide solution according to a molar ratio of 1:1, and oscillating on a mechanical oscillator for 10 days to strip to obtain a two-dimensional nanosheet;
2) the two-dimensional nanosheet and the polymer are compounded to form a film, and the film is prepared by adopting a tape casting process, and comprises the following steps:
ultrasonically dispersing the two-dimensional nanosheets into an organic solvent N, N-dimethylformamide solution to form a stable suspension, then adding a polymer matrix, and stirring for 24-48h until the two-dimensional nanosheets are fully dissolved;
and casting the mixture of the polymer and the two-dimensional nanosheets into a film with a required thickness, drying at 40-80 ℃, and collecting the obtained composite film.
2. The two-dimensional nanosheet-polymer flexible composite film of claim 1, wherein the polymer is prepared from one or more of polyvinylidene fluoride, polyvinylidene fluoride-trifluoroethylene, and polyvinylidene fluoride-hexafluoropropylene.
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| CN107901303A (en) * | 2017-10-09 | 2018-04-13 | 南通洪明电工科技有限公司 | A kind of sandwich structure high energy storage density polymer-based dielectric composite material and preparation method thereof |
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| CN107901303A (en) * | 2017-10-09 | 2018-04-13 | 南通洪明电工科技有限公司 | A kind of sandwich structure high energy storage density polymer-based dielectric composite material and preparation method thereof |
| CN109705502A (en) * | 2018-12-29 | 2019-05-03 | 中国科学技术大学 | A kind of polymer matrix composite and preparation method thereof |
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