CN106883432B - Composite ferroelectric thick film and preparation method thereof - Google Patents
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Abstract
The invention relates to a composite ferroelectric thick film and a preparation method thereof, wherein the composite ferroelectric thick film comprises PbZrO with a chemical general formula of x wt%3- (100-x) materials of wt% PVDF; wherein, 0<x is less than or equal to 20. The composite ferroelectric thick film of the invention is prepared by introducing PbZrO3The nanofiber improves the saturation polarization value, so that the energy storage density is correspondingly improved. X wt% PbZrO under the action of external electric field3The (100-x) wt% PVDF ferroelectric thick film can obtain larger polarization difference value, thereby being beneficial to the increase of energy storage density and the improvement of energy storage efficiency.
Description
Technical Field
The invention relates to the technical field of electronic functional materials and devices, in particular to a composite ferroelectric thick film and a preparation method thereof.
Background
With the development of miniaturization and integration of electronic circuits, people have made new demands on electronic components. Energy storage capacitors, one of the key components of microelectronic devices, are required to have high energy storage density and stable energy storage performance. Ferroelectric dielectric materials have been widely studied and used as energy storage materials by researchers in various countries because of their excellent dielectric properties. With the multifunction and miniaturization of electronic devices, the nano-size control, performance optimization and new material exploration of perovskite-type oxides, which are important components in many components, are also deepened.
Polyvinylidene fluoride and PbZrO with high length-diameter ratio and good dispersibility3Preparation of PVDF/PbZrO by mixing nano-fibers3Compared with the traditional PVDF thick film, the composite thick film has great advantages in the aspects of energy storage density, energy storage efficiency and the like.
Therefore, how to improve the energy storage density, energy storage efficiency and stability of the composite ferroelectric thick film and to prepare the ferroelectric thick film is a problem that needs to be solved urgently by those skilled in the art.
Disclosure of Invention
It is an object of the present invention to provide a composite ferroelectric thick film.
A composite ferroelectric thick film according to the present invention comprises PbZrO having a chemical formula of x wt%3- (100-x) materials of wt% PVDF; wherein, 0<x≤20。
The composite ferroelectric thick film of the invention is prepared by introducing PbZrO3The nanofiber improves the saturation polarization value, so that the energy storage density is correspondingly improved. X wt% PbZrO under the action of external electric field3The (100-x) wt% PVDF ferroelectric thick film can obtain larger polarization difference value, thereby being beneficial to the increase of energy storage density and the improvement of energy storage efficiency.
In addition, the composite ferroelectric thick film according to the above embodiment of the present invention may further have the following additional technical features:
further, the thickness of the composite ferroelectric thick film is 10-15 μm.
Further, the composite ferroelectric thick film is colloidal.
Another object of the present invention is to provide a method for preparing the above composite ferroelectric thick film.
The preparation method of the composite ferroelectric thick film comprises the following steps: s101: obtaining PbZrO by adopting electrostatic spinning process3Nano-fiber, and then subjecting the PbZrO to a first heat treatment process3The nano-fiber is heat treated and then the heat treated PbZrO is ground3Nano-fiber to obtain PbZrO3A nanofiber powder; s102: dissolving the PVDF in an N, N-dimethylformamide solution, carrying out ultrasonic treatment to obtain the N, N-dimethylformamide solution of the PVDF, and then carrying out the PbZrO3Dispersing nano-fiber powder into the N, N-dimethylformamide solution of PVDF to obtain a mixed colloid, performing ultrasonic treatment on the mixed colloid, and stirring to obtain x wt% of PbZrO3- (100-x) wt% of PVDF stable colloid, wherein x is more than 0 and less than or equal to 20, the mass concentration of PVDF in the N, N-dimethylformamide solution of PVDF is 0.05g/m L-0.15 g/m L, and x wt% of PbZrO is3- (100-x) wt% PVDF stabilizing colloid, said x wt% PbZrO3- (100-x) the concentration of the PVDF is 1.2 mol/L-1.6 mol/L, wherein the weight average molecular weight of the PVDF is 800000-850000, and S103, the x weight percent PbZrO is coated on the ITO conductive glass bottom electrode by adopting a spin coating process3- (100-x) wt% PVDF stabilizing colloid, to obtain x wt% PbZrO3- (100-x) wt% PVDF wet gel film; s104: applying a second heat treatment process to the x wt% PbZrO3- (100-x) wt% PVDF wet gel film is heat treated to obtain a composite ferroelectric thick film.
Further, in the step S101, the PbZrO is3The preparation process of the nanofiber specifically comprises the following steps: mixing and stirring lead acetate and acetic acid, adding zirconium n-propoxide after the lead acetate is completely dissolved, and adding lactic acid and ethylene glycol after stirring to obtain PbZrO3Colloid, then adding to said PbZrO3Adding polyvinylpyrrolidone into the colloid, and then using an electrostatic spinning machine to spin the PbZrO3The mixture of the colloid and the polyvinylpyrrolidone is subjected to electrostatic spinning to obtain PbZrO3A nanofiber; wherein the molar ratio of lead acetate, zirconium n-propoxide, lactic acid and ethylene glycol is 1: 1: 1:1, PbZrO3The mass ratio of the colloid to the polyvinylpyrrolidone is 2: 3; wherein the weight average molecular weight of the polyvinylpyrrolidone is: 1000000-1500000.
Further, the first heat treatment process specifically operates as follows: the PbZrO is mixed3The temperature of the nano-fiber is raised from room temperature to 730-780 ℃, andpreserving the heat for 55-65 min at the temperature of 730-780 ℃, and then cooling the temperature to the room temperature.
Further, the temperature increase rate at the time of the temperature increase operation is: 10 ℃/min; the cooling rate when the cooling operation is performed is: 10 ℃/min.
Further, the second heat treatment process specifically operates as follows: mixing the x wt% of PbZrO3The PVDF wet gel film with the weight percent of (100-x) is insulated for 30min to 35min at the temperature of 75 ℃ to 85 ℃, then is insulated for 55min to 65min at the temperature of 195 ℃ to 205 ℃, and then is put into ice water for rapid cooling, wherein x is more than 0 and less than or equal to 20.
Further, after the step S104, the method further includes the following steps: and repeating the step S103 and the step S104 in sequence to obtain a composite ferroelectric thick film with a preset thickness.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is an XRD pattern of a composite ferroelectric thick film of the present invention;
FIG. 2 is a P-E spectrum of a composite ferroelectric thick film of the present invention at a field strength of 3000 kV/cm;
FIG. 3 is a graph showing the variation of the energy storage density and the energy storage efficiency of the composite ferroelectric thick film of the present invention at a field strength of 600kV/cm to 3000 kV/cm.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and not restrictive, of the invention.
Example b
Example b presents a thick composite ferroelectric film having a thickness of 15 μm comprising 5 wt% PbZrO3-95% by weight of PVDF.
The method of making a composite ferroelectric thick film of embodiment b, comprising the steps of:
(1) adding lead acetate into acetic acid to obtain an acetic acid solution with lead acetate concentration of 0.8 mol/L, and adding the solution into the acetic acid solutionStirring at 115 ℃ for 15min until the lead acetate is dissolved and boiling. After the solution is cooled to room temperature, adding zirconium n-propoxide into the solution according to the molar ratio of 1:1 of lead acetate to zirconium n-propoxide, and stirring for 40min by using a constant-temperature magnetic stirrer to obtain a stable colloid. Adding lactic acid and ethylene glycol into the solution, and stirring for 30min by a constant-temperature magnetic stirrer to obtain stable PbZrO3And (3) colloid. Then the PbZrO is subjected to3Adding polyvinylpyrrolidone into the colloid, and then using an electrostatic spinning machine to spin the PbZrO3The mixture of the colloid and the polyvinylpyrrolidone is subjected to electrostatic spinning to obtain PbZrO3And (3) nano fibers. Wherein the molar ratio of lead acetate, zirconium n-propoxide, lactic acid and ethylene glycol is 1: 1: 1:1, PbZrO3The mass ratio of the colloid to the polyvinylpyrrolidone is 2: 3. Then the PbZrO is mixed3The temperature of the nano-fiber is increased from room temperature to 780 ℃ at the temperature increasing rate of 10 ℃/min, the temperature is kept at 730 ℃ for 65min, then the temperature is reduced to room temperature at the temperature decreasing rate of 10 ℃/min, and the PbZrO after heat treatment is ground3Nano-fiber to obtain PbZrO3Nanofiber powder, wherein the polyvinylpyrrolidone has a weight average molecular weight of 1000000.
(2) According to PVDF and said PbZrO3The mass ratio of the nanofiber powder is 95: 5, dissolving the PVDF in an N, N-dimethylformamide solution, performing ultrasonic treatment to obtain the N, N-dimethylformamide solution of the PVDF, and then mixing the PbZrO3Dispersing nano-fiber powder into the N, N-dimethylformamide solution of PVDF to obtain a mixed colloid, performing ultrasonic treatment on the mixed colloid, and stirring to obtain 5 wt% of PbZrO30.05g/m L mass concentration of PVDF in N, N-dimethylformamide solution of PVDF, and 5 wt% of PbZrO3-95% by weight of PVDF stabilizing colloid, the 5% by weight of PbZrO3-concentration of 95 wt% PVDF of 1.6 mol/L, wherein PVDF has a weight average molecular weight of 825000.
(3) Coating 5 wt% of PbZrO on ITO conductive glass bottom electrode by adopting spin coating process3-95% by weight of PVDF stabilizing colloid, to obtain 5% by weight of PbZrO3-95 wt% PVDF wet gel film. The spin speed was 2500r/min and the spin time was 40 s.
(4) The 5 wt% of PbZrO3And (3) preserving the heat of the-95 wt% PVDF wet gel film at the temperature of 75 ℃ for 35min, then preserving the heat at the temperature of 195 ℃ for 65min, and then putting the PVDF wet gel film into ice water for rapid cooling to obtain the composite ferroelectric thick film.
Example c
Example c presents a composite ferroelectric thick film having a thickness of 10 μm comprising PbZrO having a chemical formula of 10 wt%3-90% by weight of PVDF.
The method of making a composite ferroelectric thick film of embodiment c, comprising the steps of:
(1) adding lead acetate into acetic acid to obtain an acetic acid solution with the lead acetate concentration of 0.85 mol/L, stirring for 17min at the temperature of 110 ℃ until the lead acetate is dissolved and boiled, after the solution is cooled to room temperature, adding zirconium n-propoxide into the solution according to the molar ratio of the lead acetate to the zirconium n-propoxide of 1:1, stirring for 35min by using a constant-temperature magnetic stirrer to obtain stable colloid, adding lactic acid and ethylene glycol into the solution, and stirring for 35min by using a constant-temperature magnetic stirrer to obtain stable PbZrO3And (3) colloid. Then the PbZrO is subjected to3Adding polyvinylpyrrolidone into the colloid, and then using an electrostatic spinning machine to spin the PbZrO3The mixture of the colloid and the polyvinylpyrrolidone is subjected to electrostatic spinning to obtain PbZrO3And (3) nano fibers. Wherein the molar ratio of lead acetate, zirconium n-propoxide, lactic acid and ethylene glycol is 1: 1: 1:1, PbZrO3The mass ratio of the colloid to the polyvinylpyrrolidone is 2: 3. Then the PbZrO is mixed3The temperature of the nano-fiber is increased from room temperature to 750 ℃ at the temperature increasing rate of 10 ℃/min, the temperature is kept at 750 ℃ for 60min, then the temperature is reduced to room temperature at the temperature decreasing rate of 10 ℃/min, and the PbZrO after heat treatment is ground3Nano-fiber to obtain PbZrO3A nanofiber powder; wherein the weight average molecular weight of polyvinylpyrrolidone is 1500000.
(2) According to PVDF and said PbZrO3The mass ratio of the nanofiber powder is 90: 10 are proportioned and then mixedDissolving the PVDF in an N, N-dimethylformamide solution, performing ultrasonic treatment to obtain the N, N-dimethylformamide solution of the PVDF, and then dissolving the PbZrO in the N, N-dimethylformamide solution3Dispersing nano-fiber powder into the N, N-dimethylformamide solution of PVDF to obtain a mixed colloid, performing ultrasonic treatment on the mixed colloid, and stirring to obtain 10 wt% of PbZrO3The mass concentration of PVDF in the N, N-dimethylformamide solution of PVDF is 0.1g/m L, and the 10 wt% of PbZrO is3-90% by weight of PVDF stabilizing colloid, the 10% by weight of PbZrO3-90% by weight PVDF at a concentration of 1.4 mol/L, where the PVDF has a weight average molecular weight of 835000.
(3) Coating 10 wt% of PbZrO on ITO conductive glass bottom electrode by adopting spin coating process 390% by weight of PVDF stabilizing colloid, to obtain 10% by weight of PbZrO3-90 wt% PVDF wet gel film. The spin speed was 2700r/min and 35 s.
(4) The 10 wt% of PbZrO3And (3) preserving the heat of the PVDF wet gel film with the concentration of 90 wt% at the temperature of 80 ℃ for 32min, then preserving the heat at the temperature of 200 ℃ for 60min, and then putting the PVDF wet gel film into ice water for rapid cooling to obtain the composite ferroelectric thick film.
Example d
Example d presents a thick composite ferroelectric film having a thickness of 11 μm comprising PbZrO of formula 15 wt%3-85% by weight of PVDF.
The method of making a composite ferroelectric thick film of embodiment d, comprising the steps of:
(1) adding lead acetate into acetic acid to obtain an acetic acid solution with lead acetate concentration of 0.87 mol/L, stirring at 114 ℃ for 19min until the lead acetate is dissolved and boiled, cooling the solution to room temperature, adding zirconium n-propoxide into the solution according to the molar ratio of 1:1 of the lead acetate to the zirconium n-propoxide, stirring for 32min by using a constant-temperature magnetic stirrer to obtain stable colloid, adding lactic acid and ethylene glycol into the solution, and stirring for 33min by using a constant-temperature magnetic stirrer to obtain stable PbZrO3And (3) colloid. Then the PbZrO is subjected to3Adding polyvinylpyrrolidone into the colloid, and spinning with electrostatic spinning machinePbZrO3The mixture of the colloid and the polyvinylpyrrolidone is subjected to electrostatic spinning to obtain PbZrO3And (3) nano fibers. Wherein the molar ratio of lead acetate, zirconium n-propoxide, lactic acid and ethylene glycol is 1: 1: 1:1, PbZrO3The mass ratio of the colloid to the polyvinylpyrrolidone is 2: 3. Then the PbZrO is mixed3The temperature of the nano-fiber is increased from room temperature to 740 ℃ at the temperature increasing rate of 10 ℃/min, the temperature is kept at the temperature of 740 ℃ for 56min, then the temperature is reduced to room temperature at the temperature decreasing rate of 10 ℃/min, and the heat-treated PbZrO is ground3Nano-fiber to obtain PbZrO3A nanofiber powder; wherein, the weight average molecular weight of the polyvinylpyrrolidone is 1300000.
(2) According to PVDF and said PbZrO3The mass ratio of the nanofiber powder is 85: 15, dissolving the PVDF in an N, N-dimethylformamide solution, performing ultrasonic treatment to obtain the N, N-dimethylformamide solution of the PVDF, and then mixing the PbZrO3Dispersing nano-fiber powder into the N, N-dimethylformamide solution of PVDF to obtain a mixed colloid, performing ultrasonic treatment on the mixed colloid, and stirring to obtain 15 wt% of PbZrO3The mass concentration of PVDF in the PVDF N, N-dimethylformamide solution is 0.12g/m L, and the 15 wt% PbZrO is3-85% by weight of PVDF stabilizing colloid, the 15% by weight of PbZrO3-85% by weight PVDF at a concentration of 1.3 mol/L, wherein the weight average molecular weight of PVDF is 845000.
(3) Coating 15 wt% of PbZrO on ITO conductive glass bottom electrode by adopting spin coating process385% by weight of PVDF stabilizing colloid, to obtain 15% by weight of PbZrO3-85 wt% PVDF wet gel film. The spin speed was 2900r/min and the spin time was 33 s.
(4) The 15 wt% of PbZrO3And (3) preserving the heat of the PVDF wet gel film with the concentration of 85 wt% at the temperature of 79 ℃ for 32min, then preserving the heat at the temperature of 196 ℃ for 57min, and then putting the PVDF wet gel film into ice water for rapid cooling to obtain the composite ferroelectric thick film.
Example e
Example e presents a thick composite ferroelectric film having a thickness of 12.5 μmThe composite ferroelectric thick film comprises 20 wt% PbZrO3-80% by weight of PVDF material.
The method of making a composite ferroelectric thick film of embodiment e, comprising the steps of:
(1) adding lead acetate into acetic acid to obtain an acetic acid solution with lead acetate concentration of 0.9 mol/L, stirring at 105 ℃ for 20min until the lead acetate is dissolved and boiled, cooling the solution to room temperature, adding zirconium n-propoxide into the solution according to the molar ratio of the lead acetate to the zirconium n-propoxide of 1:1, stirring for 30min by using a constant-temperature magnetic stirrer to obtain stable colloid, adding lactic acid and ethylene glycol into the solution, and stirring for 40min by using a constant-temperature magnetic stirrer to obtain stable PbZrO3And (3) colloid. Then the PbZrO is subjected to3Adding polyvinylpyrrolidone into the colloid, and then using an electrostatic spinning machine to spin the PbZrO3The mixture of the colloid and the polyvinylpyrrolidone is subjected to electrostatic spinning to obtain PbZrO3And (3) nano fibers. Wherein the molar ratio of lead acetate, zirconium n-propoxide, lactic acid and ethylene glycol is 1: 1: 1:1, PbZrO3The mass ratio of the colloid to the polyvinylpyrrolidone is 2: 3. Then the PbZrO is mixed3The temperature of the nano-fiber is increased from room temperature to 730 ℃ at the temperature increase rate of 10 ℃/min, the heat is preserved for 55min at the temperature of 780 ℃, then the temperature is reduced to the room temperature at the temperature reduction rate of 10 ℃/min, and the PbZrO after heat treatment is ground3Nano-fiber to obtain PbZrO3A nanofiber powder; wherein the weight average molecular weight of the polyvinylpyrrolidone is 1100000.
(2) According to PVDF and said PbZrO3The mass ratio of the nanofiber powder is 80: 20, dissolving the PVDF in an N, N-dimethylformamide solution, performing ultrasonic treatment to obtain the N, N-dimethylformamide solution of the PVDF, and then mixing the PbZrO3Dispersing nano-fiber powder into the N, N-dimethylformamide solution of PVDF to obtain a mixed colloid, performing ultrasonic treatment on the mixed colloid, and stirring to obtain 20 wt% of PbZrO3The mass concentration of the PVDF in the N, N-dimethylformamide solution of the PVDF is 0.15g/m L, and the mass concentration of the 20 wt% PbZrO is3-80% by weight of PVDF stabilizing colloid, said 20% by weight of PbZrO3-concentration of 80 wt% PVDF 1.2 mol/L, wherein the weight average molecular weight of PVDF is 825000.
(3) Coating 20 wt% of PbZrO on ITO conductive glass bottom electrode by adopting spin coating process3-80% by weight of PVDF stabilizing colloid, to obtain 20% by weight of PbZrO3-80 wt% PVDF wet gel film. The spin speed was 3000r/min and the spin time was 30 s.
(4) The 20 wt% of PbZrO3And (3) preserving the heat of the PVDF wet gel film with the concentration of 80 wt% at the temperature of 85 ℃ for 30min, then preserving the heat at the temperature of 205 ℃ for 55min, and then putting the PVDF wet gel film into ice water for rapid cooling to obtain the composite ferroelectric thick film.
(5) Repeating the step (3) and the step (5) in this order until 20 wt% of PbZrO380 wt% PVDF ferroelectric thick film to about 12.5 μm, i.e. 20 wt% PbZrO3-80 wt% PVDF ferroelectric thick film.
Comparative example a
Comparative example a shows a thick PVDF ferroelectric film of 10 μm thickness.
The method of making the PVDF ferroelectric thick film of comparative example a, comprising the steps of:
(1) and dissolving the PVDF in an N, N-dimethylformamide solution and carrying out ultrasonic treatment to obtain an N, N-dimethylformamide colloidal solution of the PVDF, wherein the mass concentration of the PVDF is 0.1g/m L, and the weight average molecular weight of the PVDF is 825000.
(2) And (3) coating PVDF stable colloid on the ITO conductive glass bottom electrode by adopting a spin coating process to obtain the PVDF wet gel film. The spin speed was 2900r/min and the spin time was 33 s.
(3) And (2) preserving the temperature of the PVDF wet gel film at 80 ℃ for 32min, then preserving the temperature at 196 ℃ for 57min, then slowly pushing the PVDF wet gel film into a tubular resistance furnace, treating the PVDF wet gel film for 60min at 200 ℃, slowly taking out the PVDF wet gel film, and immediately placing the PVDF wet gel film into ice water for cooling to obtain the PVDF ferroelectric thick film.
(4) And (4) sequentially repeating the step (2) and the step (3) until the PVDF ferroelectric thick film reaches about 10 mu m, thus obtaining the PVDF ferroelectric thick film.
In the order of example b to example eThe surfaces of the prepared composite ferroelectric thick film and the PVDF ferroelectric thick film prepared in the comparative example a are sprayed with an electrode material Au by ion sputtering, the XRD patterns of the Au are measured, and the five ferroelectric thick films are analyzed. Referring to FIG. 1, which is an XRD pattern of five-component ferroelectric thick films prepared according to the processes of comparative example a, examples b, c, d, and e, it can be seen that the composite ferroelectric thick films of b, c, d, and e all show peaks corresponding to perovskite phase structures, indicating PbZrO, compared to comparative example a3The addition of the nanofiber powder successfully introduces a perovskite structure into the pure PVDF ferroelectric thick film. Referring to FIG. 2, a P-E plot of five component ferroelectric thick films prepared according to the process of comparative example a, examples b, c, d, E at 3000kV/cm field strength. From this figure, it can be seen that the ferroelectric hysteresis loops of the respective compositions exhibit typical ferroelectric characteristics, and the thick composite ferroelectric films of examples b, c, d and e have extremely large saturation polarization values, which indicates that appropriate amounts of PbZrO were added3The nano-fiber powder can positively influence the energy storage behavior of the PVDF ferroelectric thick film, and is beneficial to improving the energy storage density and the energy storage efficiency. Referring to fig. 3, which is a graph of energy storage density and energy storage efficiency of a five-component ferroelectric thick film prepared by the process of comparative example a, examples b, c, d and e from 600kV/cm to 3000kV/cm field strength, under a certain electric field strength, a variable broken line corresponds to the energy storage density on the left side coordinate axis and the energy storage efficiency on the right side coordinate axis. By comparison, it can be seen that the appropriate content of PbZrO was added3The nano-fiber powder can increase the energy storage density of the PVDF ferroelectric thick film, and in example e, the composite ferroelectric thick film has the maximum energy storage density and larger energy storage efficiency, and in examples b, c and d, larger energy storage density is obtained, which can show that a proper amount of PbZrO is added3The nano-fiber powder can positively influence the energy storage behavior of the PVDF ferroelectric thick film, and can be beneficial to improving the energy storage density and the energy storage efficiency.
The composite ferroelectric thick film provided by the invention is prepared by adding PbZrO during preparation3The nanofiber can improve the saturation polarization value, so that the energy storage density is correspondingly improved. X wt% PbZrO under the action of external electric field3-(100-x) the wt% PVDF ferroelectric thick film enables a large polarization difference to be obtained, thereby facilitating an increase in energy storage density and an improvement in energy storage efficiency.
Therefore, the method for manufacturing the composite ferroelectric thick film can successfully prepare the composite ferroelectric thick film with high energy storage density, high energy storage efficiency and strong stability.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (5)
1. A composite ferroelectric thick film comprising x wt% PbZrO based on the chemical formula3- (100-x) materials of wt% PVDF; wherein, 0<x is less than or equal to 20; the composite ferroelectric thick film is prepared by adopting the preparation method which comprises the following steps:
s101: obtaining PbZrO by adopting electrostatic spinning process3Nano-fiber, and then subjecting the PbZrO to a first heat treatment process3The nano-fiber is heat treated and then the heat treated PbZrO is ground3Nano-fiber to obtain PbZrO3A nanofiber powder;
s102: dissolving the PVDF in an N, N-dimethylformamide solution, carrying out ultrasonic treatment to obtain the N, N-dimethylformamide solution of the PVDF, and then carrying out the PbZrO3Dispersing nano-fiber powder into the N, N-dimethylformamide solution of PVDF to obtain a mixed colloid, performing ultrasonic treatment on the mixed colloid, and stirring to obtain x wt% of PbZrO3- (100-x) wt% of PVDF stable colloid, wherein x is more than 0 and less than or equal to 20, the mass concentration of PVDF in the N, N-dimethylformamide solution of PVDF is 0.05g/m L-0.15 g/m L, and x wt% of PbZrO is3- (100-x) wt% PVDF stabilizing colloid, said x wt% PbZrO3The concentration of (100-x) wt% PVDF is 1.2 mol/L-1.6 mol/L, wherein the weight average molecular weight of the PVDF is 800000-850000;
s103: coating the x wt% PbZrO on the ITO conductive glass bottom electrode by adopting a spin coating process3- (100-x) wt% PVDF stabilizing colloid, to obtain x wt% PbZrO3- (100-x) wt% PVDF wet gel film;
s104: applying a second heat treatment process to the x wt% PbZrO3-(100-x)
Carrying out heat treatment on the wt% PVDF wet gel film to obtain a composite ferroelectric thick film;
the thickness of the composite ferroelectric thick film is 10-15 μm; the composite ferroelectric thick film is colloid;
in the step S101, the PbZrO3The preparation process of the nanofiber specifically comprises the following steps:
mixing and stirring lead acetate and acetic acid, adding zirconium n-propoxide after the lead acetate is completely dissolved, and adding lactic acid and ethylene glycol after stirring to obtain PbZrO3Colloid, then adding to said PbZrO3Adding polyvinylpyrrolidone into the colloid, and then using an electrostatic spinning machine to spin the PbZrO3The mixture of the colloid and the polyvinylpyrrolidone is subjected to electrostatic spinning to obtain PbZrO3A nanofiber; wherein the molar ratio of lead acetate, zirconium n-propoxide, lactic acid and ethylene glycol is 1: 1: 1:1, PbZrO3The mass ratio of the colloid to the polyvinylpyrrolidone is 2: 3; wherein the weight average molecular weight of the polyvinylpyrrolidone is: 1000000-1500000。
2. The method of preparing a composite ferroelectric thick film according to claim 1, wherein the first thermal treatment process is specifically performed by: the PbZrO is mixed3The temperature of the nano-fiber is increased from the room temperature to 730-780 ℃, the temperature is kept at 730-780 ℃ for 55-65 min, and then the temperature is reduced to the room temperature.
3. The method of preparing a composite ferroelectric thick film according to claim 2, wherein the temperature-raising rate at the time of the temperature-raising operation is: 10 ℃/min; the cooling rate when the cooling operation is performed is: 10 ℃/min.
4. The method of preparing a composite ferroelectric thick film according to claim 1, wherein the second thermal treatment process is specifically performed by:
mixing the x wt% of PbZrO3The PVDF wet gel film with the weight percent of (100-x) is insulated for 30min to 35min at the temperature of 75 ℃ to 85 ℃, then is insulated for 55min to 65min at the temperature of 195 ℃ to 205 ℃, and then is put into ice water for rapid cooling, wherein x is more than 0 and less than or equal to 20.
5. The method of preparing a composite ferroelectric thick film according to any one of claims 1-4, further comprising, after said step S104, the steps of: and repeating the step S103 and the step S104 in sequence to obtain a composite ferroelectric thick film with a preset thickness.
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