CN110746185B - Titanium oxide nanowire array/lead lanthanum zirconate antiferroelectric composite film material and preparation method thereof - Google Patents
Titanium oxide nanowire array/lead lanthanum zirconate antiferroelectric composite film material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film material and a preparation method thereof, wherein the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film material comprises the following components in parts by weight: the titanium oxide nanowire array and the lead lanthanum zirconate film are formed on the surface of the substrate, and the lead lanthanum zirconate film is used for covering and filling the titanium oxide nanowire array; the chemical composition of the lead lanthanum zirconate film is Pb x1‑3/ 2La x ZrO3Wherein x is more than or equal to 0 and less than or equal to 0.12; the titanium oxide nanowire array is composed of a plurality of titanium oxide nanowires growing along the vertical direction of the substrate.
Description
Technical Field
The invention relates to an anti-ferroelectric film material, in particular to a titanium oxide nanowire array/lanthanum lead zirconate anti-ferroelectric composite film material and a preparation method thereof.
Background
In recent years, with the rapid development of pulse power technology, energy storage materials and devices have become hot spots for research in the field of pulse power technology. In order to meet the demands for integrated, lightweight, miniaturized, and highly reliable electronic devices, it is urgently required to develop a high power density capacitor, i.e., a dielectric energy storage material having high energy storage density, energy storage efficiency, and high reliability.
Compared with linear dielectric and ferroelectric materials, the antiferroelectric material has characteristic antiferroelectric-ferroelectric phase transition behavior, and has very high theoretical energy storage density due to the sudden increase of polarization strength and dielectric constant at a phase transition electric field, thereby becoming an important energy storage dielectric material of a pulse capacitor. The energy storage principle is that under the action of an electric field, a stable antiferroelectric phase in an antiferroelectric material is converted into a ferroelectric phase, which is a process of storing electric energy; when the electric field strength is removed, the ferroelectric phase returns to the antiferroelectric phase, which is the process of releasing electric energy. The anti-ferroelectric film prepared according to the principle has the advantages of small volume, high energy storage density, high power density and the like, and plays an increasingly important role in modern high and new technologies.
Lead zirconate (PbZrO)3) The base material is typical antiferroelectric with a perovskite structure, is an antiferroelectric compound which is discovered at the earliest time, lead zirconate is an orthogonal antiferroelectric phase at the Curie temperature (230 ℃) and the antiferroelectric property is derived from the combination of two soft modes, namely Pb atomic displacement sigma mode and oxygen octahedron distortion R mode, and the PbZrO is explained3Has strong antiferroelectricity in a plane vertical to the c-axis direction. The important characteristic of antiferroelectricity is that the antiferroelectricity has double electric hysteresis loops. However, the results of the present study show that the breakdown strength of the pure lead zirconate antiferroelectric film is low, and the energy storage density is small, although different ions (such as La) can pass through the film3+、Sr2+、Ti4+、Sn4+) The substitution at the A site or the B site is carried out to improve the energy storage characteristic, but the energy storage density does not always break through 50J/cm at present3And the temperature stability of the energy storage performance of the lead zirconate-based antiferroelectric film is poor in a working temperature range of-55-125 ℃, for example, the energy storage efficiency is reduced by 18.6% in a range of 25-105 ℃, and the requirement of practical application cannot be met. Therefore, how to proceedThe primary task of increasing the energy storage density of the lead zirconate-based antiferroelectric film and the temperature stability of a wide temperature zone is to realize the wide application of the lead zirconate-based antiferroelectric film in electronic devices such as capacitors or transducers.
Disclosure of Invention
The invention aims to provide a titanium oxide nanowire array/lead lanthanum zirconate antiferroelectric composite film material to solve the problems of low breakdown strength, low energy storage density and poor temperature stability of the conventional antiferroelectric material. The titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film material comprises a titanium oxide nanowire array formed on the surface of a substrate and a lanthanum lead zirconate film for covering and filling the titanium oxide nanowire array;
the chemical composition of the lead lanthanum zirconate film is Pb1-3x/2LaxZrO3Wherein x is more than or equal to 0 and less than or equal to 0.12;
the titanium oxide nanowire array is composed of a plurality of titanium oxide nanowires growing along the vertical direction of the substrate.
In the present invention, the titanium oxide nanowire array is composed of titanium oxide nanowires grown in a vertical direction of the substrate. Adopting lead lanthanum zirconate film (Pb)1-3x/2LaxZrO3And x is more than or equal to 0 and less than or equal to 0.12) is used for covering and filling the titanium oxide nanowire array so as to form the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film material. In addition, the invention utilizes the highly oriented titanium oxide nanowire array as the substrate, and then the anti-ferroelectric film is compounded on the substrate, because the rutile phase titanium dioxide has a stable structure and a dielectric constant which is not dispersed along with the frequency and the temperature, the titanium oxide nanowire with low dielectric constant and high breakdown strength in the composite structure can bear a higher electric field, the breakdown strength can be effectively improved, and meanwhile, the interface polarization is introduced into the composite structure, so that the dielectric constant is improved, and excellent energy storage characteristics and wide temperature stability are obtained.
Preferably, the length of the titanium oxide nanowire in the titanium oxide nanowire array is 50-500 nm, and the diameter of the titanium oxide nanowire array is 10-80 nm. Preferably, the length of the titanium oxide nanowire in the titanium oxide nanowire array is 50-250 nm, and the diameter of the titanium oxide nanowire array is 10-50 nm.
Preferably, the thickness of the titanium oxide nanowire array/lead lanthanum zirconate antiferroelectric composite film material is 200-600 nm.
Preferably, the substrate is FTO conductive glass.
The second purpose of the invention is to provide a preparation method of the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film, so that the antiferroelectric composite film material with excellent dielectric and energy storage properties can be prepared by an economic and simple method. The preparation method of the titanium oxide nanowire array/lead lanthanum zirconate antiferroelectric composite film material comprises the following steps:
(1) growing a titanium oxide nanowire array on the surface of the substrate;
(2) spin-coating lanthanum lead zirconate precursor liquid on the titanium oxide nanowire array, and then carrying out annealing treatment;
(3) and (3) repeating the step (2) for 3-10 times, coating a lead oxide precursor solution on the surface in a spin coating manner, and then performing annealing treatment (to compensate lead volatilization) to obtain the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film material.
Preferably, a hydrothermal method is adopted to grow the titanium oxide nanowire array on the surface of the substrate, and the hydrothermal method comprises the following steps:
(1) mixing titanate and acid liquor to obtain a precursor solution; controlling the concentration of Ti in the precursor solution to be 0.01-0.05 mol/L;
(2) putting the substrate into the precursor solution, and carrying out hydrothermal reaction for 3-6 hours at the temperature of 140-160 ℃; and then cleaning and drying to grow and form the titanium oxide nanowire array on the surface of the substrate.
Preferably, the preparation method of the lead lanthanum zirconate precursor liquid comprises the following steps: mixing lead acetate, lanthanum acetate, zirconate, a complexing agent and a solvent, refluxing in a water bath at the temperature of 60-80 ℃ for 0.5-2 hours, standing and aging for 24-48 hours to obtain the complex, so that metal cations and the complexing agent are fully crosslinked to form a stable network structure, and agglomeration or precipitation is avoided; preferably, the molar concentration of the lead lanthanum zirconate precursor liquid is 0.2-0.4 mol/L.
Also, preferably, the zirconate is at least one selected from the group consisting of tetra-n-propyl zirconate and tetrabutyl zirconate; the complexing agent is selected from at least one of acetylacetone, lactic acid, ethylene glycol and isopropanol; the solvent is at least one of acetic acid and ethylene glycol monomethyl ether.
Preferably, the volume of the complexing agent is 1/10-1/2 of the total volume of the lead lanthanum zirconate precursor liquid.
Preferably, the method for preparing the lead oxide precursor liquid comprises the following steps: mixing lead acetate and a solvent, refluxing in a water bath at 60-80 ℃ for 0.5-2 hours, standing and aging for 24-48 hours to obtain the metal complex, so that metal cations and a complexing agent are fully crosslinked to form a stable network structure, and agglomeration or precipitation is avoided.
Further, preferably, the solvent is at least one of acetic acid and ethylene glycol monomethyl ether; more preferably, the concentration of the lead oxide precursor solution is 0.1 to 0.3 mol/L.
Preferably, the annealing temperature is 600-800 ℃ for 3-60 minutes.
Further, preferably, the annealing treatment includes: the heat preservation is carried out for 2-10 minutes at the temperature of 150-250 ℃, then the pyrolysis is carried out for 3-30 minutes at the temperature of 300-450 ℃, and finally the annealing is carried out for 3-60 minutes at the temperature of 600-800 ℃.
The titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film prepared by the invention has the advantages that the diameter, the thickness and the distribution density of the titanium oxide nanowire array are accurate and controllable, the obtained titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film has excellent energy storage density, temperature stability and dielectric property, the comprehensive performance of the composite film material is effectively improved, and the highest energy storage density and the breakdown strength of the composite film can reach 50.6J/cm3And 2230kV/cm, the change rates of the energy storage density and the energy storage efficiency are respectively less than 5 percent and 7 percent within a wide temperature range of-120-130 ℃, and the excellent temperature stability is shown.
The preparation process of the titanium oxide nanowire array/lead lanthanum zirconate antiferroelectric composite film material is simple and feasible, the method is economic and effective, the production cost is low, the obtained antiferroelectric composite film material can be used for manufacturing pulse high-power energy storage capacitors, super capacitors, micro-electromechanical devices and related fields thereof, the excellent wide-temperature stability meets the requirements of application from low temperature to higher temperature, and the preparation method has important significance for industrialization and practicability and wide application prospect.
Drawings
FIG. 1 is a scanning electron microscope image of the surface of the titanium oxide nanowire array prepared in example 1, from which TiO can be seen2The nanowire is 50-100 nm in length and 10-30 nm in diameter;
FIG. 2 is a scanning electron microscope image of the surface of the titanium oxide nanowire array prepared in example 2, from which TiO can be seen2The nanowire is 200-250 nm in length and 30-50 nm in diameter;
FIG. 3 is a scanning electron microscope image of the surface of the titanium oxide nanowire array prepared in example 3, from which TiO can be seen2The nanowire is 400-450 nm in length and 50-70 nm in diameter;
FIG. 4 is a cross-sectional scanning electron microscope image of the titanium oxide nanowire array prepared in example 3, in which it can be seen that the titanium oxide nanowires are uniformly distributed on the surface of the substrate;
FIG. 5 is a scanning electron microscope image of a cross section of the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film prepared in example 1, wherein the composite film is 480nm thick;
fig. 6 is a transmission electron microscope image of the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film prepared in example 1, and it can be known from the image that two-phase composite interfaces of titanium oxide nanowires and lanthanum lead zirconate in the titanium oxide nanowire array are clear, the spacing between crystal planes of titanium oxide is 0.324nm, and the spacing between crystal planes of lanthanum lead zirconate is 0.295 nm;
FIG. 7 is an X-ray diffraction pattern of the Titania nanowire array/lanthanum lead zirconate antiferroelectric composite film prepared in examples 1-3, wherein it can be seen that the Titania nanowire array corresponds to the rutile phase and the lead lanthanum zirconate corresponds to the perovskite pseudo-cubic phase;
FIG. 8 is a dielectric property diagram of the Titania nanowire array/lanthanum lead zirconate antiferroelectric composite film prepared in examples 1-3 and the lanthanum lead zirconate antiferroelectric film prepared in comparative example 1, wherein it can be seen that the relative dielectric constant of the Titania nanowire array/lanthanum lead zirconate antiferroelectric composite film material can be 400-800;
FIG. 9 is a Weber distribution diagram of breakdown strengths of the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film prepared in examples 1-3 and the lanthanum lead zirconate antiferroelectric film prepared in comparative example 1, wherein it can be known that the breakdown strength of the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film material can be 1000-2300 kV/cm;
fig. 10 is a graph showing the trend of dielectric constant changes under bias fields of the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film prepared in examples 1-3 and the lanthanum lead zirconate antiferroelectric composite film prepared in comparative example 1, and it can be known that the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film material both shows "double butterfly curve" antiferroelectric characteristics;
fig. 11 is hysteresis curves of the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film prepared in examples 1-3 and the lanthanum lead zirconate antiferroelectric film prepared in comparative example 1, and it can be known that the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film material both exhibit "double hysteresis curves" antiferroelectric characteristics;
FIG. 12 is a graph showing the relationship between the energy storage performance and the electric field of the Titania nanowire array/lanthanum lead zirconate antiferroelectric composite film prepared in examples 1-3 and the lanthanum lead zirconate antiferroelectric composite film prepared in comparative example 1, and it can be seen that the energy storage density of the Titania nanowire array/lanthanum lead zirconate antiferroelectric composite film can be 15-50.6J/cm3；
FIG. 13 is a hysteresis loop diagram of the Titania nanowire array/lanthanum lead zirconate antiferroelectric composite film prepared in example 1 at-120 ℃ and 130 ℃, which shows that the polarization intensity changes from 88 to 92 μ C/cm at-120 ℃ to 130 ℃2；
Fig. 14 is a graph showing the change of the energy storage performance and the temperature of the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film prepared in example 1 in the temperature range of-120 ℃ to 130 ℃, and it can be seen that the change rates of the energy storage density and the energy storage efficiency are respectively less than 5% and 7% in the temperature range of-120 ℃ to 130 ℃, and the excellent temperature stability is shown.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the present disclosure, the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite thin film material includes: the titanium oxide nanowire array comprises a plurality of titanium oxide nanowires growing along the vertical direction of a substrate, and a lead lanthanum zirconate film used for filling and covering the titanium oxide nanowire array. Wherein, the titanium oxide nano array is composed of a plurality of titanium oxide nano wires growing along the vertical direction of the substrate. The chemical composition of the lead lanthanum zirconate film can be Pb1-3x/2LaxZrO3Wherein x is more than or equal to 0 and less than or equal to 0.12. The titanium oxide nanowire has a length of 50-500 nm and a diameter of 10-80 nm. Preferably, the length of the titanium oxide nanowire in the titanium oxide nanowire array is 50-250 nm, and the diameter of the titanium oxide nanowire array is 10-50 nm.
In an alternative embodiment, the substrate may be FTO conductive glass.
In an optional embodiment, the thickness of the composite film material may be 200 to 600 nm.
In one embodiment of the invention, the titanium oxide nanowire array is firstly grown on the surface of the substrate, then the lanthanum lead zirconate precursor solution is coated on the titanium oxide nanowire array in a spin coating manner, and then annealing treatment is carried out, so that the composite film material is obtained. The preparation method of the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film material is exemplarily described below.
Growing the titanium oxide nanowire array on the surface of the substrate by a hydrothermal method. Specifically, a titanate (e.g., tetrabutyl titanate, isopropyl titanate, etc.) and an acid solution (e.g., hydrochloric acid, sulfuric acid, etc.) are mixed to obtain a precursor solution. Putting the substrate into the precursor solution, and carrying out hydrothermal reaction for 3-6 hours at the temperature of 140-160 ℃. And after the hydrothermal reaction, taking out the substrate on which the titanium oxide nanowire array grows, cleaning and drying the substrate, thereby growing the titanium oxide nanowire array on the surface of the substrate. In the precursor solution, the concentration of Ti can be controlled to be 0.01-0.05 mol/L;
and spin-coating a lanthanum lead zirconate precursor liquid on the titanium oxide nanowire array, then annealing, and repeating the steps for 3-10 times to obtain the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film material. Mixing lead acetate, lanthanum acetate, zirconate, a complexing agent and a solvent, refluxing in a water bath at the temperature of 60-80 ℃ for 0.5-2 hours, and standing and aging for 24-48 hours to obtain the lead lanthanum zirconate precursor liquid. Among them, the zirconate may be at least one of tetra-n-propyl zirconate, tetrabutyl zirconate, and the like. The complexing agent may be at least one of acetylacetone, lactic acid, ethylene glycol, isopropyl alcohol, and the like. The volume of the complexing agent can be 1/8-1/2 of the total volume of the precursor liquid. The solvent may be at least one of acetic acid, ethylene glycol methyl ether, and the like. Preferably, the molar concentration of the lead lanthanum zirconate precursor liquid can be 0.2-0.4 mol/L. The annealing treatment is rapid sectional heat treatment; the rapid staging heat treatment comprises: the heat preservation is carried out for 2-10 minutes at the temperature of 150-250 ℃, then the pyrolysis is carried out for 3-30 minutes at the temperature of 300-450 ℃, and finally the annealing is carried out for 3-60 minutes at the temperature of 600-800 ℃. Preferably, the rotation speed of the spin coating covering can be 2000-4000 rpm, and the time is 15-35 seconds.
Preferably, the surface is spin coated with a precursor solution of lead oxide and an annealing treatment is performed in order to compensate for lead volatilization. The precursor in the lead oxide precursor liquid is lead acetate, and the concentration of the lead acetate can be 0.1-0.3 mol/L. The annealing treatment is rapid sectional heat treatment. The rapid stage heat treatment comprises: the heat preservation is carried out for 2-10 minutes at the temperature of 150-250 ℃, then the pyrolysis is carried out for 3-30 minutes at the temperature of 300-450 ℃, and finally the annealing is carried out for 3-60 minutes at the temperature of 600-800 ℃. Preferably, the rotation speed of the spin coating covering can be 2000-4000 rpm, and the time is 15-35 seconds.
In the present disclosure, the dielectric properties (dielectric constant, etc.) of the films were tested using a precision LCR analyzer E4990A. The relative dielectric constant of the titanium oxide nanowire array/lead lanthanum zirconate antiferroelectric composite film material can be 400-800. The electrical properties (polarization strength, breakdown strength, energy storage density and the like) are tested by adopting a TF Analyzer 2000 hysteresis loop tester. The maximum polarization strength of the titanium oxide nanowire array/lead lanthanum zirconate antiferroelectric composite film material can be measured to be 30-111.3 mu C/cm2The breakdown strength can be 1000-2300 kVcm, energy storage density of 15J/cm3～50.6J/cm3。
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below. The reagents used in the following examples and comparative examples are either analytically or chemically pure and are either commercially available or prepared by methods well known to those of ordinary skill in the art.
Example 1
The preparation method of the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film specifically comprises the following steps:
(1) firstly, 30mL of concentrated hydrochloric acid and 30mL of deionized water are measured, mixed and stirred for 4-8 minutes, then tetrabutyl titanate is added, stirred for 5-10 minutes to obtain a clear and transparent mixed solution, and the concentration of tetrabutyl titanate in the mixed solution is controlled to be 0.02 mol/L. The mixed solution was poured into a 100mL reaction vessel, and then 2 pieces of FTO conductive glass (1 cm. times.1.5 cm) were placed in the reaction vessel with the front side facing upward, and reacted at 150 ℃ for 4 hours. After the reaction is finished, taking out the FTO conductive glass, cleaning the FTO conductive glass by absolute ethyl alcohol, and then drying the FTO conductive glass in a drying oven for 5 to 10 minutes, wherein TiO grows on the FTO conductive glass2And (4) nanowire arrays. Referring to FIG. 1, TiO in the obtained titanium oxide nanowire array2The nanowire is 50-100 nm in length and 10-30 nm in diameter;
(2) appropriate amounts of lead acetate, lanthanum acetate and tetra-n-propyl zirconate are weighed so that the molar ratio of Pb to La to Zr is 0.88 to 0.08 to 1. Dissolving weighed lead acetate and lanthanum acetate in a proper amount of acetic acid, refluxing in a water bath at 80 ℃, stirring and preserving heat for 30 minutes to obtain a clear and transparent solution. After cooling to room temperature, adding a proper amount of acetylacetone to ensure that the volume ratio of the acetylacetone to the total solution is 3:10, refluxing in a water bath at 80 ℃, and preserving the temperature for 30 minutes. After the mixed solution is cooled to room temperature, tetra-n-propyl zirconate is added, and then the mixture is refluxed in a water bath at the temperature of 80 ℃ and is kept for 60 minutes. After the water bath is finished, the concentration of the lead lanthanum zirconate precursor liquid is adjusted to be 0.3 mol/L. And standing and aging the mixed solution for 24 hours to obtain the lead lanthanum zirconate precursor solution. And weighing a proper amount of lead acetate, dissolving the lead acetate in a proper amount of acetic acid, refluxing in a water bath at the temperature of 80 ℃, and preserving the heat for 1 hour to obtain a clear and transparent solution. After the water bath is finished, the concentration of the lead oxide precursor liquid is adjusted to be 0.15 mol/L. Standing and aging the mixed solution for 24 hours to obtain lead oxide precursor liquid;
(3) and soaking the FTO with the grown nanowire array in a lead lanthanum zirconate precursor liquid for 5 minutes, then carrying out spin coating at the rotating speed of 1000r/min for 5s, and then at the rotating speed of 2000r/min for 15 s. Putting the glass into a rapid annealing furnace for annealing treatment. The annealing is divided into three stages, the first stage is kept at 200 ℃ for 3 minutes, the second stage is pyrolyzed at 350 ℃ for 3 minutes, and the third stage is annealed at 600 ℃ for 5 minutes;
(4) and (4) repeating the step (3) for 6 times, coating the surface with a lead oxide precursor solution in a spin coating manner, and carrying out annealing treatment. The annealing is divided into three stages, the first stage is kept at 200 ℃ for 3 minutes, the second stage is pyrolyzed at 350 ℃ for 3 minutes, and the third stage is annealed at 700 ℃ for 15 minutes, so that the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film material is obtained, and is marked as S-1.
And depositing a circular gold electrode with the diameter of 100 microns on the upper surface of the film by adopting a direct current sputtering method, and then testing the electrical property of the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film. The dielectric constant and the breakdown strength of the prepared composite film are improved, as shown in figures 8-10. The composite film prepared in this example obtained the highest energy storage density of 50.6J/cm3The energy storage efficiency is 61 percent, and the change rates of the energy storage density and the energy storage efficiency are respectively less than 5 percent and 7 percent in a wide temperature range of-120 ℃ and 130 ℃, thereby showing excellent temperature stability.
Example 2
Compared with the example 1, the difference is that in the step (1), the concentration of tetrabutyl titanate in the solution is controlled to be 0.03mol/L, and the prepared titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film material is marked as S-2. The dielectric properties and breakdown strength are shown in fig. 8 and 9, and the energy storage properties are shown in fig. 12.
Example 3
Compared with the example 1, the difference is that in the step (1), the concentration of tetrabutyl titanate in the solution is controlled to be 0.04mol/L, and the prepared titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film material is marked as S-3. The dielectric properties and breakdown strength are shown in fig. 8 and 9, and the energy storage properties are shown in fig. 12.
Comparative example 1
The difference compared to example 1 is that no titanium oxide nanowire array was grown directly on the FTO substrate, labeled S-0. The dielectric property (figure 8), the breakdown strength (figure 9) and the energy storage property (figure 12) of the composite film are shown, and the performance of the composite film prepared by the comparative example is obviously inferior to that of the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film prepared by the invention on the basis of relevant experimental data.
Comparative example 2
Compared with the example 1, the difference is that the titanium oxide nanowire array is not arranged, and the titanium oxide nanowire array is directly spun and annealed on the strontium titanate/lanthanum nickelate conventional substrate. The dielectric property, the breakdown strength and the energy storage property (table 1) of the composite film are shown in the relevant experimental data, and the performance of the film prepared by the comparative example is obviously inferior to that of the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film prepared by the invention.
Table 1 shows the composition and performance parameters of the titanium oxide nanowire array/lead lanthanum zirconate antiferroelectric composite film material prepared in the present invention:
the maximum energy storage density refers to the corresponding energy storage density when the electric field of the obtained composite film material is breakdown strength at 25 ℃; the change rate of the energy storage density and the change rate of the energy storage efficiency refer to the change condition of the obtained composite film material in the temperature range shown in the table.
Claims (15)
1. A titanium oxide nanowire array/lead lanthanum zirconate antiferroelectric composite film material is characterized by comprising the following components in percentage by weight: the titanium oxide nanowire array and the lead lanthanum zirconate film are formed on the surface of the substrate, and the lead lanthanum zirconate film is used for covering and filling the titanium oxide nanowire array;
the chemical composition of the lead lanthanum zirconate film is Pb x1-3/2La x ZrO3Wherein x is more than or equal to 0 and less than or equal to 0.12;
the titanium oxide nanowire array consists of a plurality of titanium oxide nanowires growing along the vertical direction of the substrate;
growing a titanium oxide nanowire array on the surface of a substrate by adopting a hydrothermal method, wherein the hydrothermal method comprises the following steps:
(1) mixing titanate and acid liquor to obtain precursor liquid; controlling the concentration of Ti in the precursor solution to be 0.01-0.03 mol/L;
(2) putting the substrate into the precursor liquid, and carrying out hydrothermal reaction for 3-6 hours at the temperature of 140-160 ℃; and then cleaning and drying to grow and form the titanium oxide nanowire array on the surface of the substrate.
2. The titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film material as claimed in claim 1, wherein the length of the titanium oxide nanowires in the titanium oxide nanowire array is 50-500 nm, and the diameter of the titanium oxide nanowires is 10-80 nm.
3. The titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film material according to claim 2, wherein the length of the titanium oxide nanowires in the titanium oxide nanowire array is 50-250 nm, and the diameter of the titanium oxide nanowires is 10-50 nm.
4. The titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film material as claimed in claim 1, wherein the thickness of the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film material is 200-600 nm.
5. The titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite thin film material of any one of claims 1-4, wherein the substrate is FTO conductive glass.
6. A method for preparing the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite thin film material as claimed in any one of claims 1 to 5, which comprises the following steps:
(1) growing a titanium oxide nanowire array on the surface of a substrate by adopting a hydrothermal method, wherein the hydrothermal method comprises the following steps: mixing titanate and acid liquor to obtain precursor liquid; controlling the concentration of Ti in the precursor solution to be 0.01-0.03 mol/L; putting the substrate into the precursor liquid, and carrying out hydrothermal reaction for 3-6 hours at the temperature of 140-160 ℃; then cleaning and drying the substrate to grow and form a titanium oxide nanowire array on the surface of the substrate;
(2) spin-coating lanthanum lead zirconate precursor liquid on the titanium oxide nanowire array, and then carrying out annealing treatment;
(3) and (3) repeating the step (2) for 3-10 times, coating the surface with a lead oxide precursor solution in a spin coating manner, and then performing annealing treatment to obtain the titanium oxide nanowire array/lanthanum lead zirconate antiferroelectric composite film material.
7. The method according to claim 6, wherein the method for preparing the lead lanthanum zirconate precursor liquid comprises: mixing lead acetate, lanthanum acetate, zirconate, a complexing agent and a solvent, refluxing in a water bath at the temperature of 60-80 ℃ for 0.5-2 hours, and standing and aging for 24-48 hours to obtain the lead acetate-lanthanum zirconate titanate.
8. The preparation method according to claim 7, wherein the molar concentration of the lead lanthanum zirconate precursor solution is 0.2 to 0.4 mol/L.
9. The production method according to claim 7 or 8, characterized in that the zirconate is selected from at least one of tetra-n-propyl zirconate and tetrabutyl zirconate; the solvent is at least one of acetic acid and ethylene glycol monomethyl ether; the complexing agent is selected from at least one of acetylacetone, lactic acid, ethylene glycol and isopropanol; preferably, the volume of the complexing agent is 1/10-1/2 of the total volume of the lead lanthanum zirconate precursor liquid.
10. The preparation method according to claim 9, wherein the volume of the complexing agent is 1/10-1/2 of the total volume of the lead lanthanum zirconate precursor liquid.
11. The method according to claim 6, wherein the method for preparing the lead oxide precursor liquid comprises: mixing lead acetate and a solvent, refluxing in a water bath at the temperature of 60-80 ℃ for 0.5-2 hours, and standing and aging for 24-48 hours to obtain the lead acetate.
12. The production method according to claim 11, wherein the solvent is at least one of acetic acid and ethylene glycol methyl ether.
13. The method according to claim 12, wherein the concentration of the lead oxide precursor liquid is 0.1 to 0.3 mol/L.
14. The method according to claim 6, wherein the annealing is performed at 600 to 800 ℃ for 3 to 60 minutes.
15. The method of manufacturing according to claim 14, wherein the annealing treatment includes: the heat preservation is carried out for 2-10 minutes at the temperature of 150-250 ℃, then the pyrolysis is carried out for 3-30 minutes at the temperature of 300-450 ℃, and finally the annealing is carried out for 3-60 minutes at the temperature of 600-800 ℃.
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