CN110473960B - Piezoelectric material, preparation method and application thereof - Google Patents

Piezoelectric material, preparation method and application thereof Download PDF

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CN110473960B
CN110473960B CN201910789686.XA CN201910789686A CN110473960B CN 110473960 B CN110473960 B CN 110473960B CN 201910789686 A CN201910789686 A CN 201910789686A CN 110473960 B CN110473960 B CN 110473960B
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piezoelectric
raw material
rare earth
lead
earth element
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CN110473960A (en
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顾陇
刘金妹
焦婧一
秦勇
王政
王远
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Xidian University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10N30/00—Piezoelectric or electrostrictive devices
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    • H10N30/01—Manufacture or treatment
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    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/852—Composite materials, e.g. having 1-3 or 2-2 type connectivity
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
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Abstract

The invention discloses a piezoelectric material, a preparation method and application thereof, wherein the preparation method comprises the steps of weighing raw materials of each component according to the molar ratio in a chemical formula of rare earth element doped lead magnesium niobate-lead titanate; under a dry inert atmosphere, adding the weighed raw materials of each component into 2-methoxy ethanol, and distilling and refluxing to form a complex precursor; adding a 2-methoxyethanol solution of polyvinylpyrrolidone to the complex precursor to form a homogeneous precursor solution; adding the precursor solution into a liquid storage device of electrostatic spinning equipment for spinning; and annealing the collected spinning to form the rare earth element doped lead magnesium niobate-lead titanate micro-nanofiber. The RE-PMN-PT polycrystalline micro-nanofiber has excellent piezoelectric performance.

Description

Piezoelectric material, preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrostatic spinning, and particularly relates to a piezoelectric material, a preparation method of the piezoelectric material and application of the piezoelectric material.
Background
In order to meet the increasing demand for distributed power sources for multifunctional electronic devices such as portable electronic devices, implantable devices, and wireless sensor networks, energy harvesting techniques capable of efficiently converting environmental energy have been actively developed in recent years. Piezoelectric nanogenerators (PENG), a promising energy harvesting technology, convert small and irregular mechanical energy (such as vibration, walking, wind, heartbeat, and respiratory movement) into usable electrical energy, has attracted great attention because PENG has high energy conversion efficiency.
At the center of the art, considerable effort has been made by researchers to increase the output voltage and current of PENG from 8mV to 250V, and from 0.4nA to 134 μ A, respectively, in order to improve its output performance to meet the power requirements of electronic devices. It should be noted that the output voltage has increased rapidly to hundreds of volts, which is high enough for most electronic devices in our daily lives, but the output current is still insufficient, which has been a bottleneck in the development of PENG, which severely limits the application of PENG as a promising micro power source in collecting mechanical energy of the surroundings.
Considering that the output current of a normal PENG device under a certain driving condition mainly depends on the current density, and the current density is closely related to the piezoelectric coefficient of the piezoelectric material, the selection of the piezoelectric material with a higher piezoelectric coefficient is an important factor for realizing the high output current density of the PENG device, and in order to improve the output current of the piezoelectric nano generator, the appropriate piezoelectric material with the higher piezoelectric coefficient can be selected. The rare earth element doped lead magnesium niobate-lead titanate (PMN-PT) material has a piezoelectric coefficient much higher than that of the conventional piezoelectric material, for example, the Sm doped lead magnesium niobate-lead titanate polycrystalline structure has a piezoelectric coefficient of about 1500pC/N, and the single crystal has a piezoelectric coefficient of about 4100pC/N, whereas in the conventional piezoelectric material, the PZT has a piezoelectric coefficient of about 500-600 pC/N, and the PMN-PT has a piezoelectric coefficient of about 620pC/N.
However, the rare earth element doped lead magnesium niobate-lead titanate in the prior art is generally prepared by a molten salt method, an oxide mixing method (CMO method) and a secondary synthesis method, and the method is generally a block material, is not suitable for preparing a flexible piezoelectric nano generator for collecting low-frequency weak mechanical energy in the environment, and has the problems of high sintering temperature, easy generation of impure phase and uncontrollable appearance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a piezoelectric material, a preparation method and application of the piezoelectric material, and aims to solve the technical problems that in the prior art, the rare earth element doped lead magnesium niobate-lead titanate is high in sintering temperature, easy to generate impurity phases, uncontrollable in appearance and not suitable for preparing a flexible piezoelectric nano generator for collecting low-frequency weak mechanical energy in the environment.
To achieve the above and other related objects, the present invention provides a method for manufacturing a piezoelectric material, the method comprising:
weighing raw materials of each component according to the molar ratio in the chemical formula of the rare earth element doped lead magnesium niobate-lead titanate;
under a dry inert atmosphere, adding the weighed raw materials of each component into 2-methoxyethanol, and distilling and refluxing to form a complex precursor;
adding a 2-methoxyethanol solution of polyvinylpyrrolidone to the complex precursor to form a homogeneous precursor solution;
adding the precursor solution into a liquid storage device of electrostatic spinning equipment for spinning;
and annealing the collected spinning to form the rare earth element doped lead magnesium niobate-lead titanate micro-nanofiber.
In one embodiment, the rare earth element doped lead magnesium niobate-lead titanate has a chemical formula of
RE-Pb(Nb 2/3 Mg 1/3 )O 3 -xPbTiO 3
Wherein x is between 0.2 and 0.55, RE is a rare earth element, and the doping amount of the rare earth element is between 0 and 10mol percent.
In one embodiment, the rare earth element comprises one or a combination of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In one embodiment, when the lead raw material is weighed, 3 to 7mol% of the lead raw material is additionally weighed.
In one embodiment, the annealing temperature of the annealing treatment is 700-1000 ℃, and the holding time is 2-5 h.
In one embodiment, the spinning process includes the following steps: the spinning voltage is between 15kV and 24kV, the advancing speed is between 0.05 mL/min and 0.15mL/min, and the distance between the spinning nozzle and the receiver is between 10 cm and 20 cm.
In one embodiment, the step of distilling and refluxing the weighed raw materials of each component in 2-methoxyethanol under a dry inert atmosphere to form a complex precursor comprises:
adding weighed niobium raw material and magnesium raw material into 2-methoxyethanol under a dry inert atmosphere, rectifying and refluxing for a first set time, and adding a first set amount of water into the mixture to hydrolyze the niobium raw material and the magnesium raw material to form a first mixed solution;
adding a lead raw material, a titanium raw material and a rare earth element raw material into 2-methoxy ethanol in a dry inert atmosphere, and heating and distilling to form a second mixed solution;
adding the second mixed solution to the first mixed solution, distilling and refluxing for a second set time to form the complex precursor.
In order to achieve the above objects and other related objects, the present invention further provides a piezoelectric material prepared by the preparation method described in any one of the above objects, wherein the piezoelectric material is a rare earth element doped lead magnesium niobate-lead titanate micro nanofiber.
In one embodiment, the diameter of the rare earth element doped lead magnesium niobate-lead titanate micro-nanofiber is 70-400 nm.
In one embodiment, the rare earth doping elements in the rare earth doped lead magnesio-niobate-lead titanate micro-nanofibers include combinations of one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In one embodiment, the rare earth element doped lead magnesium niobate-lead titanate micro-nano fibers comprise samarium doped lead magnesium niobate-lead titanate micro-nano fibers, and the electromechanical coupling coefficient d33 of the nano fibers is between 100 and 142pm/V.
The piezoelectric material can be used for preparing a piezoelectric generator.
The RE-PMN-PT micro-nano fiber has excellent piezoelectric performance;
according to the invention, the RE-PMN-PT micro-nano fiber is prepared by adopting an electrostatic spinning method, the sol-gel method realizes uniform mixing of molecular weight, the preparation temperature is effectively reduced, and the micro-nano fiber has good mechanical property and can be used for collecting low-frequency weak mechanical energy;
the Sm-PMN-PT micro-nanofiber disclosed by the invention can be used for preparing a laminated piezoelectric nano-generator with high output current density, the influence of dipole moment on the change of driving charge in each laminated piezoelectric unit is maximized, the quantity of parallel power generation units (the piezoelectric units and membrane electrode layers on the upper side and the lower side of the piezoelectric units) is increased by reasonably utilizing space, the output current density of a power generation device is improved, and the maximum output current density is 290 mu A/cm 2 。
Drawings
Fig. 1 is a schematic structural diagram of a power generation device according to the present invention.
Fig. 2 is a schematic view showing the mechanism of the piezoelectric unit of the power generation device of the present invention.
Fig. 3 is a schematic structural view of a membrane electrode layer and an adhesive layer of the power generation device of the present invention.
Fig. 4 is a schematic structural view of a piezoelectric composite film of the power generation device of the present invention.
FIG. 5 is a schematic flow diagram of a method of manufacturing a power plant according to the present invention.
Fig. 6 is a sub-flowchart of step S11 in fig. 5.
Fig. 7 is a sub-flowchart of step S12 in fig. 5.
FIGS. 8a-d are graphs showing the output data of the power plants P1-P6 of the present invention.
FIGS. 9a, b show graphs of rectified output current and output voltage data for power plant P7 of the present invention.
FIGS. 10a and b are a schematic diagram and a charging graph, respectively, showing the structure of charging a capacitor by a power generating device.
FIG. 11 shows a flow chart of a method for preparing Sm-PMN-PT micro-nano fibers by electrospinning.
FIG. 12 shows SEM images of the Sm-PMN-PT micro-nanofibers after annealing.
FIG. 13 shows TEM image of Sm-PMN-PT micro-nanofibers after annealing.
Fig. 14 is a high magnification HRTEM of fig. 13.
Figure 15 shows XRD spectra of undoped and Sm doped PMN-PT micro-nanofibers.
Fig. 16 is an enlarged view of a portion of the area indicated by the dashed line box in fig. 15.
FIG. 17 shows XRD spectra of Sm-PMN-PT micro-nanofibers at different annealing temperatures.
FIG. 18 is a graph showing the output voltage and output current of the piezoelectric composite film as a function of the Sm-PMN-PT piezoelectric powder content.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1-18. It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and the components related to the present invention are only shown in the drawings rather than drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of the components in actual implementation may be changed freely, and the layout of the components may be more complicated.
As shown in fig. 1 to 4, an embodiment of the present invention discloses a laminated piezoelectric nano generator (PENG) as a power generation device 100, where the power generation device 100 includes a plurality of membrane electrode layers 4 sequentially arranged at intervals along a thickness direction of the power generation device 100; and several piezoelectric units 2, one said piezoelectric unit 2 is located between two said membrane electrode layers 4 adjacent to each other, one said piezoelectric unit 2 includes a piezoelectric complex film 21 at least; wherein, in the thickness direction of the power generation device 100, the membrane electrode layers 4 of odd number layers are communicated with each other to constitute a first electrode 1, and the membrane electrode layers 4 of even number layers are communicated with each other to constitute a second electrode 3. The power generation device 100 of the present invention can effectively increase the output current density of the power generation device 100 by maximizing the influence of the dipole moment on the variation of the driving charge in each of the piezoelectric units 2 and by increasing the number of the parallel power generation units (the piezoelectric units 2 and the membrane electrode layers 4 on the upper and lower sides of the piezoelectric units 2) by reasonably utilizing the space. A flow chart of the production of the power generation device 100 is illustrated.
The structure and the flow of the manufacturing method of the power generation device 100 of the present invention will be described with reference to fig. 2 to 5.
As shown in fig. 5, the method for manufacturing the power generation device 100 of the present invention includes the steps of: s11, preparing a piezoelectric composite film 21; step S12, sequentially and alternately stacking the membrane electrode layer 4 and the piezoelectric unit 2 to form a stacked structure, where the membrane electrode layer 4 is disposed on both sides of the stacked structure, and the piezoelectric unit 2 at least includes one piezoelectric composite membrane 21; step S13, communicating the odd-numbered film electrode layers 4 with each other along the thickness direction of the stacked structure to form a first electrode 1, and communicating the even-numbered film electrode layers 4 with each other to form a second electrode 3.
In step S11, as shown in fig. 6, the step of preparing the piezoelectric composite film 21 includes step S111 of preparing a polyvinylidene fluoride solution; step S112, adding piezoelectric powder into the polyvinylidene fluoride solution to form a uniform mixed solution; step S113 of spin-coating the mixed solution on a substrate, and heating and curing the mixed solution to form a piezoelectric composite film 21 on the substrate; step S114, peeling the piezoelectric composite film 21 from the substrate (as shown in fig. 5).
In step S111, polyvinylidene fluoride (PVDF) is dissolved in a solvent, DMF and acetone are adopted as the solvent of the PVDF solution, and the configuration of the PVDF solution is as follows: adding (2-5 g) PVDF into (4-10.5 g) DMF (dimethyl formamide) and (6-16 g) acetone solution, sealing and stirring to completely dissolve the PVDF to form PVDF solution, wherein the usage amount of the PVDF, the DMF and the acetone can be adjusted according to the requirement as long as the prepared PVDF solution can form uniform mixed solution after being added into piezoelectric powder. By way of example, 3.75g of PVDF may be added to 8.5g of DMF and 12.75 g of acetone, sealed and stirred to form a PVDF solution.
In other embodiments, the solvent of the PVDF solution may be, for example, one or a combination of N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), and N, N-Dimethylformamide (DMF), and/or acetone.
In step S112, considering that the output current of the normal PENG device under a certain driving condition mainly depends on the current density, and the current density is closely related to the piezoelectric coefficient of the piezoelectric material, selecting the piezoelectric material with a higher piezoelectric coefficient is an important factor for achieving a high output current density of the PENG device, and in order to increase the current density of the power generation apparatus 100, it is necessary to select a suitable piezoelectric material with a higher piezoelectric coefficient.
In step S112, the piezoelectric material of the power generation device 100 in this embodiment may be, for example, samarium-doped lead magnesium niobate-lead titanate (Sm-PMN-PT) micro-nanofibers with a high bulk piezoelectric coefficient, and the samarium-doped lead magnesium niobate-lead titanate (Sm-PMN-PT) micro-nanofibers may be synthesized by an electrospinning method as shown in fig. 11, where the diameter of the samarium-doped lead magnesium niobate-lead titanate (Sm-PMN-PT) micro-nanofibers is between 70 and 400 nanometers, and the synthesis is described in detail in the relevant portions below. Because the samarium-doped lead magnesium niobate-lead titanate micro-nanofiber prepared by the electrostatic spinning method is long in length, the samarium-doped lead magnesium niobate-lead titanate micro-nanofiber prepared by the electrostatic spinning method needs to be ground into piezoelectric powder (namely, piezoelectric micro-nanowire) with the length of 3-15 micrometers, and then the piezoelectric powder is added into the PVDF solution obtained in the step S111, and the piezoelectric powder and the PVDF solution are stirred to form a uniform mixed solution, wherein the mass ratio of the piezoelectric powder to the PVDF in the mixed solution is 0-5 (excluding 0).
In one embodiment, the mass ratio of the piezoelectric powder to the PVDF in the mixed solution is between 0 and 2 (excluding 0).
For example, the mass ratio of the piezoelectric powder to the PVDF in the mixed solution may be, for example, 1 2 ) The peak values of the maximum current and voltage of these 5 PENGs are shown in fig. 18, and it can be seen that the output current and voltage both increase with the increase of the weight percentage of the piezoelectric powder filler, and the maximum output current and voltage are about 18 and 7V.
In other embodiments, the piezoelectric composite film may be formed using a piezoelectric powder and a high polymer material capable of forming a film, such as polydimethylsiloxane, nylon, or polymethyl methacrylate.
It should be noted that, in some embodiments, the piezoelectric material of the power generation apparatus 100 may also be, for example, a rare earth-doped lead magnesium niobate-lead titanate material other than samarium (Sm), and the rare earth-doped elements in the rare earth-doped lead magnesium niobate-lead titanate micro-nanofibers may include, for example, a combination of one or more of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), and yttrium (Y) other than samarium (Sm).
In some embodiments, the piezoelectric powder may also be piezoelectric powder of other materials (micro-nano sphere, micro-nano rod, micro-nano wire, etc.), which is not limited to this embodiment.
In step S113, the spin-coating speed may be, for example, 1000 to 3000r/min (revolutions per minute), the spin-coating speed may be selected according to the required thickness of the piezoelectric composite film 21, and the piezoelectric composite film 21 of polyvinylidene fluoride and piezoelectric powder is formed in a state of the samarium-doped lead magnesium niobate-lead titanate micro-nanofiber in PVDF due to evaporation or volatilization of a solvent (DMF and acetone) in a mixed solution during the heating and curing process, where the samarium-doped lead magnesium niobate-lead titanate micro-nanofiber is converted from loose packing to tight packing due to shrinkage of the piezoelectric composite film 21, as shown in fig. 4, a structural schematic diagram of the piezoelectric composite film 21 is shown, as shown in fig. 4, the piezoelectric composite film 21 is composed of a polyvinylidene fluoride substrate 211 and a nano powder 212 filled in the polyvinylidene fluoride substrate 211, and the nano powder 212 may be, for example, a powder formed by grinding Sm-PMN-PT micro-nanofiber prepared later.
The thickness of the piezoelectric composite film 21 may be controlled according to the spin coating rate and the solid-to-liquid ratio in the mixed solution formed in step S112, and in this embodiment, the thickness of the prepared piezoelectric composite film 21 is between 2 μm and 40 μm.
In step S113, the substrate may be, for example, a silicon wafer, a glass wafer, a ceramic wafer, or the like, which is easy to peel off the piezoelectric composite film 21.
The piezoelectric composite film 21 prepared by the invention has the advantages of simple manufacturing process and low cost, and is suitable for large-scale production.
In step S12, the step of alternately stacking the membrane electrode layer 4 and the piezoelectric unit 2 in sequence to form a stacked structure, where the two sides of the stacked structure are the membrane electrode layer 4, includes step S121 of spin-coating diluted Polydimethylsiloxane (PDMS) on the membrane electrode layer 4, and performing pre-curing to form a first PDMS layer (adhesive layer 5); step S122, attaching a piezoelectric unit 2 to the first PDMS layer; step S123, spin-coating diluted PDMS on the piezoelectric unit 2, and performing pre-curing to form a second PDMS layer (adhesive layer 5); step S124, attaching a membrane electrode layer 4 to the second PDMS layer; and step S125, repeating the steps S121-S124 until the stacked structure is formed.
In this embodiment, the adhesive layer 5 may also be other suitable adhesive layers, and is not limited to the PDMS exemplified in the present invention, as long as the adhesive layer can be bonded while ensuring that the adhesive layer is as thin as possible.
In steps S121 and S123, the rotation speed is 1000 to 3000r/min when the diluted PDMS is spin-coated, the spin-coating time is 10 to 30S, and the diluted PDMS is pre-cured by curing at 90 to 120 ℃ for 50 to 70S after the spin-coating, wherein when the PDMS is diluted, the ratio (volume ratio) of the PDMS to the diluent is 1:5 to 15, and the diluent may be any diluent used for diluting the PDMS, such as cyclohexane, n-hexane, or acetone. In other embodiments, the adhesive layer 5 may be made of other suitable materials.
For example, when diluted PDMS is spin-coated, the rotation speed is between 2000, the spin-coating time is 15s, and the PDMS is pre-cured after the spin-coating is finished and cured at 110 ℃ for 60 s.
In this embodiment, the piezoelectric unit 2 includes at least one piezoelectric composite film 21 obtained in step S11, and when the piezoelectric unit 2 includes a plurality of piezoelectric composite films 21, the piezoelectric composite films 21 are adhered to each other by using pre-cured PDMS. Fig. 2 shows a piezoelectric unit 2 including three piezoelectric composite films 21, and the adhesive layer 5 between two piezoelectric composite films 21 is not shown in fig. 2. The number of the piezoelectric composite films 21 in the piezoelectric unit 2 and the thickness of the piezoelectric composite films 21 are reasonably selected mainly according to the requirement on the output voltage, the larger the required output voltage is, the thicker the thickness of the piezoelectric unit 2 is, and the larger the number of the required piezoelectric composite films is under the condition that the thicknesses of the piezoelectric composite films are the same, and vice versa.
In step S12, the diluted PDMS is used for spin coating to control the thickness of the spin coating layer, so that the thickness of the PDMS coating layer (the adhesive layer 5) is thinner; the precuring is adopted to ensure that the PDMS layer keeps better viscosity, so that the two layers of materials on the two sides of the PDMS layer can be bonded better.
In the present embodiment, the film electrode layer 4 is, for example, an aluminum foil having a thickness of, for example, 10 to 20 μm, and, for example, 15 μm. In other embodiments, the film electrode layer 4 may be a metal film such as gold foil, silver foil, copper foil, or tin foil, or other flexible conductive film.
In an embodiment, the method for manufacturing the power generation device 100 further includes providing a substrate (not shown), and forming the stacked structure on the substrate.
For convenience of manufacturing, the stacked structure may be formed on a substrate, for example, a Polyethylene terephthalate (PET) sheet or other substrate material, and the substrate is connected to the bottom layer film electrode layer 4 of the stacked structure through a PDMS bonding layer 5.
In step S13, as shown in fig. 1, the left ends of the 1 st, 3 rd and 5 th (odd number) film electrode layers 4 are connected together from top to bottom to form a first electrode 1, and the left ends of the 2 st, 4 th and 6 th (even number) film electrode layers 4 are connected together in sections to form a second electrode 3, and the first electrode 1 and the second electrode 3 are not connected, so that the first electrode 1 and the second electrode 3 constitute a three-dimensional fork layer electrode.
The power generation device 100 shown in fig. 1 is finally prepared through the steps of S11 to S13, and in fig. 1, only the power generation device 100 including 5 layers of the piezoelectric units 2 and 6 layers of the film electrode layer 4 is shown.
Next, a study of the performance of the power generation device 100 of the present invention will be explained.
In order to ensure the same experimental conditions, in the present invention, all the power generation apparatuses 100 were subjected to polarization treatment before electrical performance test, and the parameters of the polarization treatment were: the polarization electric field is 5kV/mm, the polarization temperature is 110 ℃, and the polarization time is 30min. It should be noted that, the parameters of the polarization treatment can be reasonably adjusted according to the needs; the power generation apparatus 100 was periodically driven by a linear motor (LinMot E1100), the output voltage and the output current of the power generation apparatus 100 were measured using low-noise preamplifiers SR570 and SR560, and data was collected using PCI-6259 (National Instruments).
In order to study the influence of the number of piezoelectric units 2 in the power generation apparatus 100 on the output, 6 power generation apparatuses 100 were prepared, and labeled as device P1, device P2, device P3, device P4, device P5, and device P6, respectively. In the 6 power generation apparatuses 100, each of the power generation apparatuses 100 is composed of 12 piezoelectric composite films 21 (in each piezoelectric composite film 21, the mass fraction of the samarium-doped lead magnesium niobate-lead titanate micro-nano fiber (piezoelectric powder) is 50%, and the thickness of the samarium-doped lead magnesium niobate-lead titanate micro-nano fiber is about 30 micrometers), but the number of the included piezoelectric units 2 is 1,2,3,4,6 and 12, that is, each piezoelectric unit 2 in the device P1 includes 12 piezoelectric composite films 21, each piezoelectric unit 2 in the device P2 includes 6 piezoelectric composite films 21, each piezoelectric unit 2 in the device P3 includes 4 piezoelectric composite films 21, each piezoelectric unit 2 in the device P4 includes 3 piezoelectric composite films 21, each piezoelectric unit 2 in the device P5 includes 2 piezoelectric composite films 21, and each piezoelectric unit 2 in the device P6 includes 1 piezoelectric composite film 21; the output current and the output voltage of the 6 power generation devices 100 are shown in fig. 8a and 8b, respectively, the average peak value of the output current and the average peak value of the output voltage of the 6 power generation devices 100 are shown in fig. 8c, and the output charge density of the 6 power generation devices 100 is shown in fig. 8 d. As shown in fig. 8a, as the number of the piezoelectric units 2 is reduced from 12 (device P6) to 6 (device P5), there is almost no difference between the output currents, which is about 150 μ a, and as the number of the piezoelectric units 2 is reduced from 6 (device P5) to 1 (device P1), the output current is reduced from 150 μ a to 25 μ a; however, as the number of piezoelectric elements 2 decreases from 12 to 1 as shown in fig. 8b, the output voltage increases from 6V to 84V. In addition, as shown in fig. 8c, it can be seen that the output voltage (indicated by solid squares) of the power generation device 100 decreases non-linearly as the number of the piezoelectric units 2 increases; as shown in fig. 8c and 8d, when the number of the piezoelectric units 2 of the power generation apparatus 100 is increased from 1 to 6, the output current (indicated by solid triangles) and the output charge density are increased approximately linearly, but when the number of the piezoelectric units 2 in the power generation apparatus 100 is increased from 6 to 12, the average peak values of the output current and the output charge density are both slightly decreased because more piezoelectric units 2 mean more membrane electrode layers 4 (aluminum foil) and PDMS adhesion layers, and a high ratio of the soft Al membrane electrode layers 4 and/or PDMS adhesion layers in the power generation apparatus 100 generates a stronger buffer effect, resulting in less strain transferred to the piezoelectric units 2, thereby causing the current and charge density of the power generation apparatus 100 to start to decrease.
In order to investigate the maximum output performance of the power plant 100, a power plant 100 comprising 24 piezoelectric elements 2, denoted P7, was prepared, the active area of the device P7 being about 1.2cm 2 . In the device P7, each piezoelectric unit 2 includes 3 piezoelectric composite films 21, and the reason why 3 piezoelectric composite films 21 are selected is that the output voltage of 3 piezoelectric composite films 21 is greater than 20V, which is enough for most applications, and of course, the number of piezoelectric composite films 21 included in each piezoelectric unit 2 can be reasonably selected according to the requirement of the maximum output voltage. FIGS. 9a and 9b show the rectified output current and output voltage of device P7. As can be seen from FIGS. 9a and 9b, under a stress of 0.1MPa, the maximum output current of device P7 reaches 320 μ A, and the output current density reaches 290 μ A/cm 2 The output voltage reached 28V.
In order to demonstrate that the power generation device 100 of the present invention can meet the application of high power, the device P7 is directly connected to the commercial LED array composed of 100 commercial red LEDs, and 100 commercial red LEDs can be instantly lighted by using the device P7, wherein 10 commercial red LEDs are connected in series to form one group, and ten groups are connected in parallel.
In order to demonstrate that a power generation device 100 has a high output performance, the output charge will be a more powerful data than the current density, and fig. 10a is a schematic diagram showing the charging of a capacitor C with the power generation device 100. As shown in FIG. 10a, the output terminal of the power generation device 100 (device P7) is connected to the input terminal of a capacitor C with a capacity of 1 μ F via a rectifying circuit 5 (after using a rectifying bridge composed of four rectifying diodes D1-D4) for charging the capacitor C and the capacitor C is connected to the output terminal of the rectifying circuitA voltmeter 4 is connected in parallel between the two electrode plates of the capacitor C for detecting the voltage between the two electrode plates of the capacitor C, during the charging process, the variation curve of the voltage between the two electrode plates of the capacitor C (the charging curve of the capacitor) is shown in fig. 10b, as can be seen from fig. 10b, when the device P7 works, the voltage at the two ends of the capacitor C can be increased from 0 to 8V within 21 cycles, the average charging rate is 405 nC/cycle, and the surface charge density of the device P7 is 1690 μ C/m 2 。
It should be noted that, by maximizing the influence of dipole moment on the variation of the driving charge in each layer of the piezoelectric unit 2, the number of the parallel power generation units (the piezoelectric unit 2 and the membrane electrode layers 4 on the upper and lower sides of the piezoelectric unit 2) is increased by reasonably utilizing the space, so as to increase the output current density of the power generation device 100; the maximum output current density of the power generation apparatus 100 of the present invention is 290. Mu.A/cm 2 (ii) a The power generation device 100 of the invention has higher output power, and can instantly light 100 commercial red LEDs; the power generation device 100 of the invention has ultrahigh surface charge density, and the maximum surface charge density is 1690 mu C/m 2 。
Next, as shown in fig. 11, an embodiment of the present invention introduces a method for preparing samarium-doped lead magnesium niobate-lead titanate (Sm-PMN-PT) micro-nanofibers by electrospinning, where the preparation method includes, in step S21, weighing raw materials of each component according to a molar ratio in a chemical formula of the rare earth element-doped lead magnesium niobate-lead titanate; s22, adding the weighed raw materials of the components into 2-methoxy ethanol in a dry inert atmosphere, and distilling and refluxing to form a complex precursor; step S23, adding a 2-methoxy ethanol solution of polyvinylpyrrolidone (PVP) into the complex precursor to form a uniform precursor solution; s24, adding the precursor solution into a liquid storage device of electrostatic spinning equipment for spinning; and S25, annealing the collected spinning to form the rare earth element doped lead magnesium niobate-lead titanate micro-nano fiber.
In step S21, the rare earth element-doped lead magnesium niobate-lead titanate has a chemical formula of
RE-Pb(Nb 2/3 Mg 1/3 )O 3 -xPbTiO 3
Wherein x is between 0.2 and 0.55, and RE is a rare earth element.
The rare earth element Sm will be explained as an example.
In step S21, in order to compensate for the loss of lead during the subsequent rapid annealing, in the process of weighing the lead raw material, additionally weighing 3 to 7mol% of the lead raw material to be added to the complex precursor of step S22; as an example, 5mol% of lead raw material is additionally weighed to be added to the complex precursor of step S22.
In step S21, 0 to 10mol% of Sm is weighed, that is, in the samarium-doped lead magnesium niobate-lead titanate micro-nanofiber formed in step S25, the doping amount of Sm is 0 to 10mol%. By way of example, the doping amount of Sm is 2.5mol%, and the doping amount of Sm of the samarium-doped lead magnesium niobate-lead titanate micro-nanofibers in the piezoelectric composite film 21 used in the preparation of the power generation device 100 is 2.5mol%.
In step S21, the lead raw material may be, for example, one or a combination of several of lead acetate trihydrate, lead carbonate, lead nitrate and basic lead carbonate; the niobium raw material can adopt one or a combination of several of niobium ethoxide, niobium n-propoxide, niobium n-butoxide, niobium nitrate, niobium acetate and niobium carbonate; the magnesium raw material can be selected from one or a combination of several of magnesium ethoxide, magnesium n-propoxide, magnesium n-butoxide, magnesium nitrate, magnesium acetate and magnesium carbonate; the samarium raw material can be one or a combination of more of samarium nitrate hexahydrate, samarium acetate, samarium carbonate and samarium acetate; the titanium raw material can be one or a combination of more of titanium isopropoxide, tetrabutyl titanate, titanium nitrate, titanium acetate and titanium carbonate. In this embodiment, the lead raw material may adopt lead acetate trihydrate, the magnesium raw material may adopt magnesium ethoxide, the niobium raw material may adopt niobium ethoxide, the samarium raw material may adopt samarium nitrate hexahydrate, and the titanium raw material may adopt titanium isopropoxide.
The step S22 comprises the steps of adding weighed niobium raw material, magnesium raw material and acetylacetone complexing agent into 2-methoxyethanol under a dry inert atmosphere, distilling and refluxing for a first set time, and then adding a first dose of water into the mixture to hydrolyze the niobium raw material and the magnesium raw material to form a first mixed solution; adding a lead raw material, a titanium raw material and a samarium raw material into 2-methoxy ethanol in a dry inert atmosphere, heating to dissolve, and removing water in the mixed solution to form a second mixed solution; adding the second mixed solution to the first mixed solution, distilling and refluxing for a second set time to form the complex precursor.
In step S22, an oil bath is adopted for the whole distillation and reflux, and stirring is carried out, wherein the temperature of the oil bath is between 110 and 120 ℃; the dry inert atmosphere is maintained to prevent hydrolysis of the easily hydrolyzed raw material (e.g., magnesium ethoxide niobium), and may be, for example, a nitrogen atmosphere or other rare gas atmosphere in a dry inert atmosphere.
In step S22, the first set time is greater than or equal to 3 hours, that is, after the weighed niobium raw material and magnesium raw material are added into 2-methoxyethanol, the distillation and refluxing time is at least 3 hours, so as to mix them uniformly, and impurities (including crystal water) are removed; the first dosage is determined according to the amount of the niobium raw material (magnesium ethoxide); the second set time is 10-14h, that is, after the second mixed solution is continuously added into the first mixed solution, distillation and reflux are needed for 10-14h to form the complex precursor, and during the distillation and reflux, various raw materials can be fully mixed, and part of 2-methoxy ethanol can be distilled off.
In step S23, a 2-methoxyethanol solution of the prepared PVP is added to the complex precursor obtained in step S22 under vigorous stirring, wherein the molecular weight of the PVP is 1300,000 in this embodiment, and the amount of the PVP added can be controlled according to the viscosity of the precursor solution.
As an example, 0.001mol of magnesium ethoxide is weighed, and raw materials of other components are weighed based on the amount of the magnesium ethoxide; adding weighed niobium raw material, magnesium raw material and 2-3 g acetylacetone complexing agent into 8-12 g 2-methoxyethanol, distilling for at least 3h, and adding 0.25-0.35 g water into the mixture to hydrolyze the niobium raw material and the magnesium raw material to form a first mixed solution; adding a lead raw material, a titanium raw material and a samarium raw material into 3-5 g of 2-methoxy ethanol in a dry inert atmosphere, heating to dissolve, and removing water in the mixed solution to form a second mixed solution; adding the second mixed solution into the first mixed solution, distilling and refluxing for 12-14 h until 3.5-4.5 mL of solution remains in the container, thereby forming the complex precursor; under the condition of vigorous stirring, 1.5-2.5 g of PVP 2-methoxy ethanol solution is added into the complex precursor, and the stirring is continued until a uniform precursor solution is formed, wherein the PVP 2-methoxy ethanol solution is prepared according to the mass ratio of the PVP to the 2-methoxy ethanol of 1:3.
In step S24, when performing electrostatic spinning, the precursor solution is added into an injector (liquid reservoir) of an electrostatic spinning device, the advancing speed is controlled to be 0.05-0.15 mL/min by an injection pump, the high voltage between a spinning nozzle and a receiver is controlled to be 15 kV-24 kV voltage, that is, the spinning voltage is controlled to be 15 kV-24 kV, the distance between the spinning nozzle and the receiver is controlled to be 10-20 cm, so as to obtain an undetermined Tylor cone, and the electrostatic spinning is performed and collected. By way of example, the advancing speed is, for example, 0.01mL/min, the spinning voltage is 18kV and the distance between the spinning nozzle and the receiver is 15mm.
In step S25, the collected spun yarn is annealed to form a desired crystal structure, wherein the annealing conditions include: the temperature rise speed is 2-4 ℃/min, the annealing temperature is 700-1000 ℃, and the heat preservation time is 2-5 h.
Next, we characterized the annealed sample, wherein fig. 12 is a Scanning Electron Microscope (SEM) image of the annealed sample, from which it can be seen that the diameter of the micro-nanofibers in the annealed sample is distributed between 75nm and 330nm, the surface of the micro-nanofibers is relatively rough due to the removal of organic components and the growth of the crystal grains during the annealing process, and fig. 13 is a Transmission Electron Microscope (TEM) image of the annealed sample showing the micro-fibersThe nanofibers are compact and continuous in structure; fig. 14 is a high magnification, high Resolution Transmission Electron Microscope (HRTEM) of fig. 13, from which it can be seen that the lattice spacing at the marked locations in fig. 14 is 0.27nm, which corresponds to the (110) crystal plane, and the regular arrangement of atoms indicates that the synthesized Sm-PMN-PT micro-nanofibers have good crystallinity; fig. 15 shows XRD patterns of Sm doped (doping concentration 2.5mol%, upper curve in fig. 15) and undoped PMN-PT micro-nanofibers (corresponding to lower curve in fig. 15), indicating that they are polycrystalline perovskite structures. The pseudo-cubic-tetragonal (pseudo-tetragonal) Morphotropic Phase Boundary (MPB) of PMN-xPT was shifted from 0.35 to 0.28 of PT content by adding 2.5mol% of Sm instead of a partial position of a site (Pb). In general, the diffraction peak of Sm-PMN-PT at about 45 ° (dashed box position in fig. 15) will be divided into two diffraction peaks, but in the present invention, since the micro-nanofiber is composed of small particles, the diffraction peak will be obviously broadened to cover the peak division, as shown in 16; in addition, sm is added 3+ Has an ionic radius (95.8 pm) of less than Pb 2+ Compared to undoped PMN-PT (see fig. 16), the diffraction pattern of Sm-PMN-PT is slightly shifted to a high angle, which is strong evidence that Sm is indeed doped in the lattice of PMN-PT.
As shown in fig. 17, during the preparation process, all raw materials are mixed at the molecular level, and atomic nucleation and diffusion barrier are low, so that pure-phase Sm-PMN-PT micro-nanofibers can be synthesized at a lower temperature (e.g. 700 ℃), which is much lower than the sintering temperature in the solid state.
And measuring the electromechanical coupling coefficient (d 33) of the single Sm-PMN-PT micro-nanofiber by using a piezoelectric response force microscope (PFM), wherein the value of d33 is between 100 and 142pm/V. Thanks to the excellent piezoelectric property of the Sm-PMN-PT micro-nanofiber, the Sm-PMN-PT micro-nanofiber/PVDF piezoelectric composite film 21 (the detailed preparation process is shown above) is suitable for manufacturing the piezoelectric nano-generator PENG.
The Sm-PMN-PT micro-nanofiber is prepared by adopting an electrostatic spinning method, the sol-gel method realizes uniform mixing of molecular weight, the preparation temperature is effectively reduced, and the micro-nanofiber has good mechanical property and can be used for collecting low-frequency weak mechanical energy.
It should be noted that, although the embodiment only introduces the electrospinning method for preparing Sm-PMN-PT micro-nanofibers, the method is also applicable to the electrospinning method for preparing other similar rare earth element doped PMN-PT micro-nanofibers.
In the description herein, numerous specific details are provided, such as examples of components and/or methods, to provide a thorough understanding of embodiments of the invention. One skilled in the relevant art will recognize, however, that an embodiment of the invention can be practiced without one or more of the specific details, or with other apparatus, systems, assemblies, methods, components, materials, parts, and/or the like. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of embodiments of the invention.
Reference throughout this specification to "one embodiment", "an embodiment", or "a specific embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment, and not necessarily all embodiments, of the present invention. Thus, respective appearances of the phrases "in one embodiment", "in an embodiment", or "in a specific embodiment" in various places throughout this specification are not necessarily referring to the same embodiment. Furthermore, the particular features, structures, or characteristics of any specific embodiment of the present invention may be combined in any suitable manner with one or more other embodiments. It is to be understood that other variations and modifications of the embodiments of the invention described and illustrated herein are possible in light of the teachings herein and are to be considered as part of the spirit and scope of the present invention.
It will also be appreciated that one or more of the elements shown in the figures can also be implemented in a more separated or integrated manner, or even removed for inoperability in some circumstances or provided for usefulness in accordance with a particular application.
Additionally, any labeled arrows in the drawings/figures should be considered only as exemplary, and not limiting, unless otherwise specifically noted. Further, as used herein, the term "or" is generally intended to mean "and/or" unless otherwise indicated. Combinations of components or steps will also be considered as being noted where terminology is foreseen as rendering the ability to separate or combine is unclear.
As used in the description herein and throughout the claims that follow, "a", "an", and "the" include plural references unless otherwise indicated. Also, as used in the description herein and throughout the claims that follow, unless otherwise indicated, the meaning of "in …" includes "in …" and "on … (on)".
The above description of illustrated embodiments of the invention, including what is described in the abstract of the specification, is not intended to be exhaustive or to limit the invention to the precise forms disclosed herein. While specific embodiments of, and examples for, the invention are described herein for illustrative purposes only, various equivalent modifications are possible within the spirit and scope of the present invention, as those skilled in the relevant art will recognize and appreciate. As indicated, these modifications may be made to the present invention in light of the foregoing description of illustrated embodiments of the present invention and are to be included within the spirit and scope of the present invention.
The systems and methods have been described herein in general terms as the details aid in understanding the invention. Furthermore, various specific details have been given to provide a general understanding of the embodiments of the invention. One skilled in the relevant art will recognize, however, that an embodiment of the invention can be practiced without one or more of the specific details, or with other apparatus, systems, assemblies, methods, components, materials, parts, and/or the like. In other instances, well-known structures, materials, and/or operations are not specifically shown or described in detail to avoid obscuring aspects of embodiments of the invention.
Thus, although the present invention has been described herein with reference to particular embodiments thereof, a latitude of modification, various changes and substitutions are intended in the foregoing disclosures, and it will be appreciated that in some instances some features of the invention will be employed without a corresponding use of other features without departing from the scope and spirit of the invention as set forth. Accordingly, many modifications may be made to adapt a particular situation or material to the essential scope and spirit of the present invention. It is intended that the invention not be limited to the particular terms used in following claims and/or to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include any and all embodiments and equivalents falling within the scope of the appended claims. Accordingly, the scope of the invention is to be determined solely by the appended claims.

Claims (9)

1. A method of preparing a piezoelectric material, comprising:
weighing raw materials of each component according to the molar ratio in the chemical formula of the rare earth element doped lead magnesium niobate-lead titanate;
under a dry inert atmosphere, adding the weighed raw materials of each component into 2-methoxyethanol, and distilling and refluxing to form a complex precursor;
adding a 2-methoxyethanol solution of polyvinylpyrrolidone to the complex precursor to form a homogeneous precursor solution;
adding the precursor solution into a liquid storage device of electrostatic spinning equipment for spinning;
and annealing the collected spinning to form the rare earth element doped lead magnesium niobate-lead titanate micro-nanofiber, wherein the annealing temperature of the annealing treatment is 700-1000 ℃, and the heat preservation time is 2-5 h.
2. The method for producing a piezoelectric material according to claim 1, wherein the rare earth element-doped lead magnesium niobate-lead titanate has a chemical formula of RE-Pb (Nb) 2/3 Mg 1/3 )O 3 -xPbTiO 3
Wherein x is between 0.2 and 0.55, RE is a rare earth element, and the doping amount of the rare earth element is between 0 and 10mol percent.
3. The method according to claim 2, wherein the rare earth element comprises one or a combination of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
4. The method for preparing a piezoelectric material according to claim 1, wherein 3 to 7mol% of the lead raw material is additionally weighed while the lead raw material is weighed.
5. The method for preparing a piezoelectric material according to claim 1, wherein the spinning is carried out with process parameters including: the spinning voltage is between 15kV and 24kV, the advancing speed is between 0.05 mL/min and 0.15mL/min, and the distance between the spinning nozzle and the receiver is between 10 cm and 20 cm.
6. The method for preparing a piezoelectric material according to any one of claims 1 to 5, wherein the step of distilling and refluxing the weighed raw materials of the components in 2-methoxyethanol under a dry inert atmosphere to form a complex precursor comprises:
adding weighed niobium raw material and magnesium raw material into 2-methoxyethanol under a dry inert atmosphere, rectifying and refluxing for a first set time, and adding a first set amount of water into the mixture to hydrolyze the niobium raw material and the magnesium raw material to form a first mixed solution;
adding a lead raw material, a titanium raw material and a samarium raw material into 2-methoxy ethanol in a dry inert atmosphere, and heating and distilling to form a second mixed solution;
adding the second mixed solution to the first mixed solution, distilling and refluxing for a second set time to form the complex precursor.
7. The piezoelectric material prepared by the preparation method according to any one of claims 1 to 6, wherein the piezoelectric material is a rare earth element doped lead magnesium niobate-lead titanate micro-nanofiber.
8. The piezoelectric material prepared by the preparation method according to claim 7, wherein the diameter of the rare earth element doped lead magnesium niobate-lead titanate micro-nanofiber is 70-400 nm.
9. A piezoelectric generator, wherein the piezoelectric material according to claim 7 or 8 is used for the piezoelectric generator.
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