CN111755593A - Piezoelectric composite material, piezoelectric composite film, preparation method of piezoelectric composite film and piezoelectric device - Google Patents

Piezoelectric composite material, piezoelectric composite film, preparation method of piezoelectric composite film and piezoelectric device Download PDF

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CN111755593A
CN111755593A CN202010547060.0A CN202010547060A CN111755593A CN 111755593 A CN111755593 A CN 111755593A CN 202010547060 A CN202010547060 A CN 202010547060A CN 111755593 A CN111755593 A CN 111755593A
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piezoelectric
organic polymer
polymer matrix
piezoelectric composite
ferroelectric material
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李宋楚
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OFilm Microelectronics Technology Co Ltd
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OFilm Microelectronics Technology Co Ltd
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    • H—ELECTRICITY
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    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/04—Treatments to modify a piezoelectric or electrostrictive property, e.g. polarisation characteristics, vibration characteristics or mode tuning
    • H10N30/045—Treatments to modify a piezoelectric or electrostrictive property, e.g. polarisation characteristics, vibration characteristics or mode tuning by polarising
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/09—Forming piezoelectric or electrostrictive materials
    • H10N30/098—Forming organic materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract

The invention relates to a piezoelectric composite material, a piezoelectric composite film, a preparation method and application thereof and a piezoelectric device. The piezoelectric composite material comprises an organic polymer matrix and a molecular ferroelectric material, wherein the molecular ferroelectric material is distributed in the organic polymer matrix and is selected from TMCM-MnCl3、TMCM‑CdCl3And (TMFM)x(TMCM)1–xCdCl3Wherein x is more than or equal to 0 and less than or equal to 1; the mass content of the molecular ferroelectric material in the total amount of the organic polymer matrix and the molecular ferroelectric material is 5-70%. The piezoelectric composite material compounds the molecular ferroelectric material of a specific kind with the organic polymer matrix and controls the molecular ferroelectric material in a specific content, thereby overcoming the problem of uneven film formation of the molecular ferroelectric material and endowing the piezoelectric composite material withBetter piezoelectric performance; meanwhile, the high flexibility of the organic polymer matrix endows the piezoelectric composite material with excellent flexibility, and the piezoelectric composite material has high piezoelectric performance and flexibility.

Description

Piezoelectric composite material, piezoelectric composite film, preparation method of piezoelectric composite film and piezoelectric device
Technical Field
The invention relates to the technical field of piezoelectric materials, in particular to a piezoelectric composite material, a piezoelectric composite film, a preparation method of the piezoelectric composite film and a piezoelectric device.
Background
With the development of current VR, artificial skin, wrappable sensors and other tactile feedback devices, the requirements for piezoelectric materials are increasing day by day. In particular, piezoelectric materials having both good piezoelectric performance and flexibility have become a hot point of research in the industry.
The current piezoelectric materials mainly include: inorganic piezoelectric ceramic materials, piezoelectric polymers, piezoelectric composite materials and molecular ferroelectric materials with perovskite structures. Among them, the inorganic piezoelectric ceramic material has a high D33 (piezoelectric constant, which is a constant for measuring piezoelectric properties) and excellent piezoelectric properties, but has the disadvantages of hardness and brittleness, no flexibility, difficulty in film formation, and the like, and is generally used for preparing rigid piezoelectric devices. Piezoelectric polymers have good ductility and flexibility but lack voltage performance, D33 is very low, and D33 is only 1/10, or even lower, of inorganic piezoelectric ceramic materials. The piezoelectric composite material is generally compounded by an inorganic piezoelectric ceramic material and a piezoelectric polymer or an organic polymer matrix, and the idea is that the compounded material is expected to have both the high piezoelectric performance of the inorganic piezoelectric material and the flexibility of the piezoelectric polymer or the organic polymer matrix, but according to research, the piezoelectric performance of the compound material after polarization in actual production is very low and even lower than that of the piezoelectric polymer. The molecular ferroelectric material with the perovskite structure is an organic salt with the perovskite structure, and has the advantages of brittle property and poor flexibility, thereby greatly limiting the application of the molecular ferroelectric material.
Disclosure of Invention
Accordingly, there is a need for a piezoelectric composite material, a piezoelectric composite film, a method for manufacturing the same, applications thereof, and a piezoelectric device, which can improve flexibility on the basis of higher piezoelectric performance.
In one aspect of the invention, a piezoelectric composite material is provided, which comprises an organic polymer matrix and a molecular ferroelectric material, wherein the molecular ferroelectric material is distributed in the organic polymer matrix, and is selected from TMCM-MnCl3、TMCM-CdCl3And (TMFM)x(TMCM)1–xCdCl3Wherein x is more than or equal to 0 and less than or equal to 1; in the total amount of the organic polymer matrix and the molecular ferroelectric material, the mass content of the molecular ferroelectric material is 5-70%.
The piezoelectric composite material compounds a molecular ferroelectric material of a specific kind with an organic polymer matrix and controls the specific content of the molecular ferroelectric material, the molecular ferroelectric material is embedded in the flexible organic polymer matrix, the molecular ferroelectric material can adhere to the framework fiber of the organic polymer matrix for nucleation during crystallization precipitation, and the framework fiber of the organic polymer matrix in the film layer is uniformly distributed, so that the molecular ferroelectric material is uniformly distributed during crystallization precipitation, the problem of non-uniform film formation of the molecular ferroelectric material is solved, and the piezoelectric composite material is endowed with better piezoelectric performance; meanwhile, the high flexibility of the organic polymer matrix endows the piezoelectric composite material with excellent flexibility, and overcomes the defect that the pure molecular ferroelectric material is brittle and fragile. Therefore, the piezoelectric composite material has high piezoelectric performance and flexibility.
In some embodiments, the total amount of the organic polymer matrix and the molecular ferroelectric material is 20% to 50% by mass of the molecular ferroelectric material. Within this range, the piezoelectric composite material has more excellent piezoelectric performance and flexibility.
In some embodiments, the total amount of the organic polymer matrix and the molecular ferroelectric material is 30 to 50% by mass of the molecular ferroelectric material. Within this range, the piezoelectric composite material has more excellent piezoelectric performance and flexibility.
In some of these embodiments, the organic polymer matrix is selected from at least one of polyvinylidene fluoride-trifluoroethylene copolymer, polyvinylidene fluoride, polymethyl methacrylate, and polydimethylsiloxane. It is understood that the material selection of the organic polymer matrix is not limited thereto.
In some of these embodiments, the molecular ferroelectric material is (TMFM)x(TMCM)1–xCdCl3Wherein x is more than or equal to 0 and less than or equal to 1; the organic polymer matrix is polyvinylidene fluoride-trifluoroethylene copolymer. Compared with TMCM-MnCl3And TMCM-CdCl3，(TMFM)x(TMCM)1–xCdCl3Has better piezoelectric performance, and is compounded by adopting the specific material, so that the piezoelectric composite material is preparedHas better piezoelectric performance and flexibility.
In a further aspect of the present invention, there is provided a method for preparing a piezoelectric composite material of any one of the above, comprising the steps of:
the organic polymer matrix and the molecular ferroelectric material are uniformly mixed.
According to the preparation method of the piezoelectric composite material, the piezoelectric composite material is prepared by taking the organic polymer matrix and the molecular ferroelectric material with specific types and specific contents as raw materials, the molecular ferroelectric material is embedded in the flexible organic polymer matrix, the molecular ferroelectric material can adhere to the skeleton fiber of the organic polymer matrix for nucleation during crystallization, and the skeleton fiber of the organic polymer matrix in the film layer is uniformly distributed, so that the molecular ferroelectric material is uniformly distributed during crystallization, the problem of non-uniform film formation of the molecular ferroelectric material is solved, and the piezoelectric composite material is endowed with better piezoelectric performance; meanwhile, the high flexibility of the organic polymer matrix endows the piezoelectric composite material with excellent flexibility, and overcomes the defect that the pure molecular ferroelectric material is brittle and fragile. Therefore, the piezoelectric composite material has high piezoelectric performance and flexibility.
In some embodiments, the step of uniformly mixing the organic polymer matrix and the molecular ferroelectric material further comprises the step of adding an organic solvent to mix to prepare a slurry. It is understood that the piezoelectric composite material prepared by the above preparation method may be in the form of a slurry.
In some embodiments, the method for preparing the piezoelectric composite material further comprises the step of drying and shaping the slurry. The piezoelectric composite material thus obtained is a dried molded material.
In some of these embodiments, the step of preparing the slurry comprises the steps of:
mixing the organic polymer matrix with the organic solvent to obtain an organic polymer matrix solution;
adding the molecular ferroelectric material into the organic polymer matrix solution and uniformly mixing. Therefore, the organic polymer matrix and the molecular ferroelectric material are mixed more fully, and the uniformity of the piezoelectric composite material is improved.
In some embodiments, the organic polymer matrix solution contains 5% to 30% by mass of the organic polymer matrix. Therefore, the organic polymer matrix and the molecular ferroelectric material are mixed more fully, and the uniformity of the piezoelectric composite material is improved.
In still another aspect of the present invention, there is provided a piezoelectric composite film, which is obtained by poling a piezoelectric composite material as described in any one of the above.
In a further aspect of the present invention, there is provided a use of the piezoelectric composite material described in any one of the above or the piezoelectric composite thin film described above for manufacturing an electronic device.
The piezoelectric composite material or the piezoelectric composite film has high piezoelectric performance and flexibility, and can be widely applied to touch feedback devices such as VR, artificial skin and wrappable sensors and other electronic devices.
In still another aspect of the present invention, there is provided a piezoelectric device comprising the above piezoelectric composite film.
The piezoelectric device applies the piezoelectric composite film, and can meet the requirements on piezoelectric performance and bending performance at the same time.
In some embodiments, the piezoelectric device further includes a first electrode and a second electrode, and the first electrode and the second electrode are electrically connected to two sides of the piezoelectric composite film, respectively. The piezoelectric device may be a piezoelectric thin film sensor.
In still another aspect of the present invention, there is provided a method for manufacturing a piezoelectric device, including the steps of:
mixing an organic polymer matrix, a molecular ferroelectric material and an organic solvent to obtain slurry; wherein the molecular ferroelectric material is selected from TMCM-MnCl3、TMCM-CdCl3And (TMFM)x(TMCM)1–xCdCl3Wherein x is more than or equal to 0 and less than or equal to 1; in the total amount of the organic polymer matrix and the molecular ferroelectric material, the mass content of the molecular ferroelectric material is 5-70%;
preparing a film on a substrate by adopting the slurry, drying, and removing the substrate to obtain an unpolarized piezoelectric composite film;
and electrically connecting a first electrode and a second electrode to two sides of the unpolarized piezoelectric composite film respectively, and polarizing to obtain the piezoelectric device.
The preparation method of the piezoelectric device is characterized in that a slurry method is adopted to prepare the membrane, an unpolarized piezoelectric composite film is formed on a substrate, and then the membrane is combined with two electrodes and polarized, so that the piezoelectric device with high piezoelectric performance and flexibility can be prepared.
Drawings
Fig. 1 is a schematic structural view showing a flow state of a doctor blade method employed in a method for manufacturing a piezoelectric device according to an embodiment;
FIG. 2 is a cross-sectional view of the schematic structure shown in FIG. 1;
FIG. 3 is a comparative graph of tensile stress strain performance for example 3;
FIG. 4 is a comparative graph of tensile stress strain performance of comparative example 1;
fig. 5 is a graph comparing piezoelectric properties of each example and comparative example 1.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Through a great deal of research, researchers of the invention find that although the molecular ferroelectric material with the perovskite structure has higher piezoelectric performance, the D33 value of some molecular ferroelectric materials can reach 3 times (more than 1500 pC/N) of that of lead zirconate titanate (PZT ceramic material), the practical application of the molecular ferroelectric material still faces great difficulty. 1) Difficulty in film formation: the film preparation generally adopts a water-based solvent volatilization method, but crystal grains are easy to appear during precipitation, so that the film layer is not uniform; 2) the film layer is easy to be brittle: the film layer of the molecular ferroelectric material can be prepared by vacuum evaporation coating, and the molecular ferroelectric material with the perovskite structure belongs to organic salt, is brittle and extremely fragile, has no flexibility, and can be broken and layered even peeled off after being slightly deformed. These have all greatly limited the application of molecular ferroelectric materials of perovskite structure.
Based on this, an embodiment of the present invention provides a piezoelectric composite material, which includes an organic polymer matrix and a molecular ferroelectric material, wherein the molecular ferroelectric material is distributed in the organic polymer matrix.
The molecular ferroelectric material is selected from TMCM-MnCl3(trimethyl chloromethyl ammonium manganese chlorate), TMCM-CdCl3(trimethyl chloromethyl ammonium cadmium salt) and (TMFM)x(TMCM)1–xCdCl3(TMFM, trimethyl fluoromethyl ammonium; TMCM, trimethyl chloromethyl ammonium), wherein x is more than or equal to 0 and less than or equal to 1.
The mass content of the molecular ferroelectric material in the total amount of the organic polymer matrix and the molecular ferroelectric material is 5-70%.
The piezoelectric composite material compounds a molecular ferroelectric material of a specific kind with an organic polymer matrix and controls the specific content of the molecular ferroelectric material, the molecular ferroelectric material is embedded in the flexible organic polymer matrix, the molecular ferroelectric material can adhere to the framework fiber of the organic polymer matrix for nucleation during crystallization precipitation, and the framework fiber of the organic polymer matrix in the film layer is uniformly distributed, so that the molecular ferroelectric material is uniformly distributed during crystallization precipitation, the problem of non-uniform film formation of the molecular ferroelectric material is solved, and the piezoelectric composite material is endowed with better piezoelectric performance; meanwhile, the high flexibility of the organic polymer matrix endows the piezoelectric composite material with excellent flexibility, and overcomes the defect that the pure molecular ferroelectric material is brittle and fragile. Therefore, the piezoelectric composite material has high piezoelectric performance and flexibility.
Researches find that the piezoelectric property cannot be well improved when the mass content of the molecular ferroelectric material is too low, and the mass content of the molecular ferroelectric material is too high, such as more than 70%, large-particle crystals of the material can absorb water and are easy to embrittle in the subsequent drying process, so that the polarization degree and the piezoelectric property are reduced.
In some of these embodiments, the molecular ferroelectric material is present in an amount of 20% to 50% by mass of the total amount of molecular ferroelectric material and organic polymer matrix. Within this range, the piezoelectric composite material has more excellent piezoelectric performance and flexibility.
Further, in the total amount of the molecular ferroelectric material and the organic polymer matrix, the mass content of the molecular ferroelectric material is 30-50%. Within this range, the piezoelectric composite material has more excellent piezoelectric performance and flexibility.
In some of these embodiments, the organic polymer matrix is selected from at least one of a piezoelectric polymer and an organic polymer that does not have piezoelectric properties. It is understood that both the piezoelectric polymer and the organic polymer having no piezoelectric property function in the piezoelectric composite material function as an organic polymer matrix. The piezoelectric polymer includes, but is not limited to, polyvinylidene fluoride-trifluoroethylene copolymer (PVDF-Trfe) and polyvinylidene fluoride (PVDF), and the organic polymer having no piezoelectric property includes, but is not limited to, polymethyl methacrylate (PMMA) and Polydimethylsiloxane (PDMS).
In some of these embodiments, the organic polymer matrix is selected from at least one of polyvinylidene fluoride-trifluoroethylene copolymer, polyvinylidene fluoride, polymethyl methacrylate, and polydimethylsiloxane.
Further, when the piezoelectric polymer is selected from organic polymers having no piezoelectric property, the molecular ferroelectric material is preferably (TMFM)x(TMCM)1–xCdCl3。
In some of these embodiments, the molecular ferroelectric material is (TMFM)x(TMCM)1–xCdCl3Wherein x is more than or equal to 0 and less than or equal to 1; the organic polymer matrix is polyvinylidene fluoride-trifluoroethylene copolymer. Compared with TMCM-MnCl3And TMCM-CdCl3，(TMFM)x(TMCM)1–xCdCl3The piezoelectric composite material has better piezoelectric performance, and the specific material is adopted for compounding, so that the piezoelectric composite material has better piezoelectric performance and flexibility. Further preferably, where 0.2 ≦ x ≦ 0.5, in one example, x ≦ 0.26.
An embodiment of the present invention further provides a method for preparing any one of the above piezoelectric composite materials, including the steps of: the organic polymer matrix and the molecular ferroelectric material are uniformly mixed. Wherein the molecular ferroelectric material is selected from TMCM-MnCl3、TMCM-CdCl3And (TMFM)x(TMCM)1–xCdCl3Wherein x is more than or equal to 0 and less than or equal to 1; the mass content of the molecular ferroelectric material in the total amount of the organic polymer matrix and the molecular ferroelectric material is 5-70%.
According to the preparation method of the piezoelectric composite material, the piezoelectric composite material is prepared by taking the organic polymer matrix and the molecular ferroelectric material with specific types and specific contents as raw materials, the molecular ferroelectric material is embedded in the flexible organic polymer matrix, the molecular ferroelectric material can adhere to the skeleton fiber of the organic polymer matrix for nucleation during crystallization, and the skeleton fiber of the organic polymer matrix in the film layer is uniformly distributed, so that the molecular ferroelectric material is uniformly distributed during crystallization, the problem of non-uniform film formation of the molecular ferroelectric material is solved, and the piezoelectric composite material is endowed with better piezoelectric performance; meanwhile, the high flexibility of the organic polymer matrix endows the piezoelectric composite material with excellent flexibility, and overcomes the defect that the pure molecular ferroelectric material is brittle and fragile. Therefore, the piezoelectric composite material has high piezoelectric performance and flexibility.
It is understood that in some examples, the organic polymer matrix and the molecular ferroelectric material may be directly mixed to homogeneity using a solid phase method. For example, when the organic polymer matrix is PDMS, PDMS with molecular weight of 4000-20000 is a viscous liquid at normal temperature, and the PDMS can be directly mixed with the molecular ferroelectric material without adding an organic solvent, and preferably a curing agent is further added therein to facilitate subsequent curing.
In some embodiments, the step of uniformly mixing the organic polymer matrix and the molecular ferroelectric material further comprises the step of adding an organic solvent to mix to prepare a slurry. It is understood that the piezoelectric composite material prepared by the above preparation method may be in the form of a slurry.
Further, the preparation method of the piezoelectric composite material also comprises the step of drying and forming the slurry. The piezoelectric composite material thus obtained is a dried molded material.
In some embodiments, the step of preparing the slurry by the step of mixing the organic polymer matrix, the molecular ferroelectric material and the organic solvent as described above includes the following steps S12 to S14.
Step S12: mixing an organic polymer matrix with an organic solvent to obtain an organic polymer matrix solution;
further, the solid content of the organic polymer matrix solution (i.e., the mass content of the organic polymer matrix) is 5 wt% to 30 wt% so that the organic polymer matrix can be sufficiently mixed with the organic polymer matrix. Further, the organic solvent is selected from Dimethylformamide (DMF) or Methyl Ethyl Ketone (MEK). In one example, the solid content of the organic polymer matrix solution (i.e., the mass content of the organic polymer matrix) is 15 wt%.
Step S14: adding a molecular ferroelectric material into the organic polymer matrix solution, and uniformly mixing to obtain slurry. The adding amount of the molecular ferroelectric material is as follows: the mass content of the composite material in the total amount of the molecular ferroelectric material and the organic polymer matrix is controlled to be 5-70%.
Therefore, the organic polymer matrix and the molecular ferroelectric material are mixed more fully, and the uniformity of the piezoelectric composite material is improved. Further, the mixing step in step S14 employs ball milling.
The invention further provides a piezoelectric composite film, which is prepared by polarizing the piezoelectric composite material.
The piezoelectric composite film comprises an organic polymer matrix and a molecular ferroelectric material. The molecular ferroelectric material is selected from TMCM-MnCl3、TMCM-CdCl3And (TMFM)x(TMCM)1–xCdCl3Wherein x is more than or equal to 0 and less than or equal to 1. The mass content of the molecular ferroelectric material in the total amount of the organic polymer matrix and the molecular ferroelectric material is 5-70%.
The piezoelectric composite film is prepared by polarizing any one of the piezoelectric composite materials, and the prepared piezoelectric composite film has high piezoelectric performance and flexibility.
In some embodiments, the piezoelectric composite material of any one of the above embodiments can be formed into a film by a slurry method, and specifically, the slurry can be formed into a film by a blade method and a spin coating method.
An embodiment of the present invention further provides an application of the piezoelectric composite material or the piezoelectric composite thin film in preparing an electronic device.
The piezoelectric composite material or the piezoelectric composite film has high piezoelectric performance and flexibility, and can be widely applied to touch feedback devices such as VR, artificial skin and wrappable sensors and other electronic devices.
It is understood that the electronic devices include, but are not limited to, transducers, sensors, drivers, frequency discriminators, piezoelectric oscillators, transformers, filters, and the like.
The embodiment of the invention also provides a piezoelectric device which comprises the piezoelectric composite film.
The piezoelectric device applies the piezoelectric composite film, and can meet the requirements on piezoelectric performance and bending performance at the same time.
In some embodiments, the piezoelectric device further includes a first electrode and a second electrode, and the first electrode and the second electrode are electrically connected to two sides of the piezoelectric composite film, respectively. The piezoelectric device may be a piezoelectric thin film sensor. Further, the first electrode, the piezoelectric composite film, and the second electrode are sequentially stacked.
In some of these embodiments, the first electrode and the second electrode may each be independently selected from electrodes of copper foil, silver foil, aluminum foil, and the like.
An embodiment of the present invention further provides a method for manufacturing a piezoelectric device, including the following steps S10 to S30.
Step S10: mixing the organic polymer matrix, the molecular ferroelectric material and an organic solvent to obtain slurry.
Wherein the molecular ferroelectric material is selected from TMCM-MnCl3、TMCM-CdCl3And (TMFM)x(TMCM)1–xCdCl3Wherein x is more than or equal to 0 and less than or equal to 1. The mass content of the molecular ferroelectric material in the total amount of the organic polymer matrix and the molecular ferroelectric material is 5-70%.
In some embodiments, step S10 includes steps S12-S14 described above. Details are not repeated.
Step S20: and (3) adopting the slurry to prepare a film on the substrate, drying and removing the substrate to obtain the unpolarized piezoelectric composite film.
In step S20, a film is formed by a slurry method. Further, the slurry can be formed into a film by a doctor blade method and a spin coating method.
Referring to fig. 1 and 2, in some examples, the step of forming the slurry into a film by using a doctor blade method includes the following steps: the method comprises the steps of cleaning a substrate 201 made of glass and the like, limiting a groove-shaped area to be coated by scraping by using an adhesive tape 202, pouring slurry into the groove-shaped area, and scraping the slurry to be uniformly distributed in the groove-shaped area. It is understood that the total thickness of the tape 202 can be selected based on the thickness of the slurry to be applied, and that the total thickness of the tape 202 can be adjusted by applying multiple layers of tape in a stacked manner.
In some examples, the slurry is formed into a film by using a spin coating method, which comprises the following steps: the substrate is arranged on a rotary platform of a spin coating instrument, the slurry is dripped on the substrate in the process that the rotary platform drives the substrate to rotate, and the substrate is uniformly distributed by utilizing the rotation speed of the substrate.
In some of these embodiments, the conditions of drying are: drying for 1-15 h at 30-150 ℃ to obtain a flat and uniform film.
Step S30: and electrically connecting the first electrode and the second electrode to two sides of the unpolarized piezoelectric composite film respectively, and polarizing to obtain the piezoelectric device.
The preparation method of the piezoelectric device is characterized in that a slurry method is adopted to prepare the membrane, an unpolarized piezoelectric composite film is formed on a substrate, and then the membrane is combined with two electrodes and polarized, so that the piezoelectric device with high piezoelectric performance and flexibility can be prepared.
In some of these embodiments, the first electrode and the second electrode may each be independently selected from electrodes of copper foil, silver foil, aluminum foil, and the like.
In some embodiments, the polarization condition is that the DC voltage is 300-1000V, the thermal polarization temperature is 70-110 ℃, and the polarization time is 2-5 h.
Specifically, the step of polarizing comprises the steps of:
putting the piezoelectric composite film attached with the lead, the first electrode and the second electrode into dimethyl silicone oil, and heating the piezoelectric composite film to 90-110 ℃ in an oil bath; then, applying 300V-1000V direct current voltage to two ends of the piezoelectric composite film, keeping for 4h, and then closing heating and naturally cooling; and maintaining the voltage in the process of cooling to 70 ℃ until the temperature is reduced to below 70 ℃, removing the loaded voltage, and finishing the film polarization.
Further, the step of applying 300V-1000V direct current voltage to the two ends of the piezoelectric composite film is divided into multiple times of pressurization, the pressurization is stopped when the monitoring current exceeds 20 muA, the pressurization is continued when the current is lower than 10 muA, and the process is circulated until the target voltage is reached.
The following are specific examples.
Used Therein (TMFM)x(TMCM)1–xCdCl3X of the powder was 0.26.
Example 1
1) Preparing a DMF solution of PVDF-Trfe (content of 15 wt%) as a precursor of an organic polymer matrix; adding into the solution(TMFM)x(TMCM)1–xCdCl3Powder, control (TMFM)x(TMCM)1–xCdCl3Powder of PVDF-Trfe He (TMFM)x(TMCM)1–xCdCl3The mass content of the total powder (not calculating DMF) is 20%, transferring the sample into a beaker, and stirring by using a magnetic stirrer to prepare slurry;
2) and (3) film preparation by a blade coating method: cleaning the surface of glass with the thickness of 500 mu m, and attaching a plurality of layers of high-temperature adhesive tapes with the thickness of 50 mu m according to the shape and the thickness of a required film to form a groove-shaped area; pouring the slurry at the front end of the groove, using another piece of clean glass to strickn off from front to back, and baking at 70 ℃ for 4h to obtain a flat and uniform film;
3) the film was carefully peeled off from the glass, and copper foil electrodes were applied to both the upper and lower surfaces of the film, followed by polarization, to obtain a piezoelectric device. Wherein the polarization step is: putting the piezoelectric composite film attached with the lead, the first electrode and the second electrode into the dimeticone, and heating the film to 100 ℃ in an oil bath; then, adding 500V direct current voltage (pressurizing for multiple times, stopping boosting when the monitored current exceeds 20 muA, continuing boosting when the current is lower than 10 muA, and repeating the steps until the target voltage is reached), keeping for 4h, and then closing heating and naturally cooling; and (3) continuing the process of cooling to 70 ℃ for 1h, and maintaining the voltage in the process of cooling to 70 ℃ until the temperature is reduced to below 70 ℃, removing the loaded voltage, and finishing the film polarization.
Example 2
1) Preparing a DMF solution of PVDF-Trfe (content of 15 wt%) as a precursor of an organic polymer matrix; adding (TMFM) to the solutionx(TMCM)1–xCdCl3Powder, control (TMFM)x(TMCM)1–xCdCl3Powder of PVDF-Trfe He (TMFM)x(TMCM)1–xCdCl3Transferring the sample into a beaker, and stirring by using a magnetic stirrer to prepare slurry, wherein the mass content of the total amount of the powder (DMF is not calculated) is 40%;
2) and (3) film preparation by a blade coating method: cleaning the surface of glass with the thickness of 500 mu m, and attaching a plurality of layers of high-temperature adhesive tapes with the thickness of 50 mu m according to the shape and the thickness of a required film to form a groove-shaped area; pouring the slurry at the front end of the groove, using another piece of clean glass to strickn off from front to back, and baking at 70 ℃ for 4h to obtain a flat and uniform film;
3) the film was carefully peeled from the glass, and copper foil electrodes were applied to both the upper and lower surfaces of the film, followed by polarization (polarization conditions were the same as in example 1), thereby obtaining a piezoelectric device.
Example 3
1) Preparing a DMF solution of PVDF-Trfe (content of 15 wt%) as a precursor of an organic polymer matrix; adding (TMFM) to the solutionx(TMCM)1–xCdCl3Powder, control (TMFM)x(TMCM)1–xCdCl3Powder of PVDF-Trfe He (TMFM)x(TMCM)1–xCdCl3The mass content of the total powder (not calculating DMF) is 50%, transferring the sample into a beaker, and stirring by using a magnetic stirrer to prepare slurry;
2) and (3) film preparation by a blade coating method: cleaning the surface of glass with the thickness of 500 mu m, and attaching a plurality of layers of high-temperature adhesive tapes with the thickness of 50 mu m according to the shape and the thickness of a required film to form a groove-shaped area; pouring the slurry at the front end of the groove, using another piece of clean glass to strickn off from front to back, and baking at 70 ℃ for 4h to obtain a flat and uniform film;
3) the film was carefully peeled from the glass, and copper foil electrodes were applied to both the upper and lower surfaces of the film, followed by polarization (polarization conditions were the same as in example 1), thereby obtaining a piezoelectric device.
Example 4
1) Preparing a DMF solution of PVDF-Trfe (content of 15 wt%) as a precursor of an organic polymer matrix; adding (TMFM) to the solutionx(TMCM)1–xCdCl3Powder, control (TMFM)x(TMCM)1–xCdCl3Powder of PVDF-Trfe He (TMFM)x(TMCM)1–xCdCl3The mass content of the total powder (not calculating DMF) is 70%, transferring the sample into a beaker, and stirring by using a magnetic stirrer to prepare slurry;
2) and (3) film preparation by a blade coating method: cleaning the surface of glass with the thickness of 500 mu m, and attaching a plurality of layers of high-temperature adhesive tapes with the thickness of 50 mu m according to the shape and the thickness of a required film to form a groove-shaped area; pouring the slurry at the front end of the groove, using another piece of clean glass to strickn off from front to back, and baking at 70 ℃ for 4h to obtain a flat and uniform film;
3) the film was carefully peeled from the glass, and copper foil electrodes were applied to both the upper and lower surfaces of the film, followed by polarization (polarization conditions were the same as in example 1), thereby obtaining a piezoelectric device.
Example 5
1) Preparing a DMF solution of PVDF-Trfe (content of 15 wt%) as a precursor of an organic polymer matrix; adding (TMFM) to the solutionx(TMCM)1–xCdCl3Powder, control (TMFM)x(TMCM)1–xCdCl3Powder of PVDF-Trfe He (TMFM)x(TMCM)1–xCdCl3Transferring the sample into a beaker, and stirring by using a magnetic stirrer to prepare slurry, wherein the mass content of the total amount of the powder (DMF is not calculated) is 5%;
2) and (3) film preparation by a blade coating method: cleaning the surface of glass with the thickness of 500 mu m, and attaching a plurality of layers of high-temperature adhesive tapes with the thickness of 50 mu m according to the shape and the thickness of a required film to form a groove-shaped area; pouring the slurry at the front end of the groove, using another piece of clean glass to strickn off from front to back, and baking at 70 ℃ for 4h to obtain a flat and uniform film;
3) the film was carefully peeled from the glass, and copper foil electrodes were applied to both the upper and lower surfaces of the film, followed by polarization (polarization conditions were the same as in example 1), thereby obtaining a piezoelectric device.
Example 6
1) 25g of PDMS and 25g of a molecular ferroelectric material (TMFM)x(TMCM)1–xCdCl3Mixing the powder, performing ball milling for 1h, uniformly dispersing, adding 2.5g of Dow Corning 184 curing agent, continuing ball milling for 1h, standing, and discharging bubbles for 1h to obtain slurry to be coated;
2) and (3) film preparation by a blade coating method: cleaning the surface of glass with the thickness of 500 mu m, and attaching a plurality of layers of high-temperature adhesive tapes with the thickness of 50 mu m according to the shape and the thickness of a required film to form a groove-shaped area; pouring the slurry at the front end of the groove, using another piece of clean glass to strickn off from front to back, and baking at 50 ℃ for 4h to obtain a flat and uniform film;
3) the film was carefully peeled from the glass, and copper foil electrodes were applied to both the upper and lower surfaces of the film, followed by polarization (polarization conditions were the same as in example 1), thereby obtaining a piezoelectric device.
Example 7
Example 7 is essentially the same as example 3, except that: adopts the molecular ferroelectric material TMCM-MnCl with equal mass3Powder substitute for (TMFM) in example 3x(TMCM)1–xCdCl3(ii) a Other steps are similar, and the piezoelectric device is obtained.
Comparative example 1
Comparative example 1 is essentially the same as example 1 except that comparative example 1 omits the addition of (TMFM) to example 1x(TMCM)1–xCdCl3And (3) powder step, wherein the obtained piezoelectric composite film is an undoped pure PVDF-Trfe film.
The piezoelectric composite films prepared in the examples 1 to 7 are molecular ferroelectric doped composite films, and the preparation parameters of the examples 1 to 7 and the comparative example 1 are shown in the following table 1. Wherein, taking example 1 as an example, the content of the organic polymer matrix refers to the mass content of PVDF-Trfe in DMF solution of PVDF-Trfe, and the content of the molecular ferroelectric material refers To (TMFM)x(TMCM)1–xCdCl3Of PVDF-Trfe and (TMFM)x(TMCM)1–xCdCl3Mass content in total powder (not counting DMF); other examples and comparative examples were analogized in turn.
TABLE 1
Figure BDA0002541078800000131
Figure BDA0002541078800000141
The piezoelectric composite film obtained in example 3 and the pure PVDF-Trfe film obtained in comparative example 1 were subjected to tensile stress strain properties, and the results are shown in fig. 3 and 4, respectively. It can be seen that the piezoelectric composite film prepared in example 3 still maintains good tensile strain properties.
Cutting the piezoelectric device samples prepared in the embodiments 1 to 7 and the comparative example 1 into square pieces of 10mm × 10mm, placing the square pieces on a test platform of a triaxial full-braking load tester (Beijing Waohua comet measurement and control technology, Inc.), carrying out vacuum adsorption, and connecting an extraction electrode into an oscilloscope; the triaxial load tester impacts the surface of the film at a pressure of 6g and a speed of 100mm/min, so that the trigger voltage can be obtained on an oscilloscope, and the trigger voltage and the feedback voltage are obtained after the trigger voltage is lifted up for 1s, and the results are shown in fig. 5. From fig. 5, it can be seen that, compared with a pure PVDF-Trfe film, piezoelectric properties such as trigger voltage and feedback voltage of the piezoelectric composite film of the present invention are significantly improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (13)

1. A piezoelectric composite material is characterized by comprising an organic polymer matrix and a molecular ferroelectric material, wherein the molecular ferroelectric material is distributed in the organic polymer matrix and is selected from TMCM-MnCl3、TMCM-CdCl3And (TMFM)x(TMCM)1–xCdCl3Wherein x is more than or equal to 0 and less than or equal to 1; in the total amount of the organic polymer matrix and the molecular ferroelectric material, the mass content of the molecular ferroelectric material is 5-70%.
2. The piezoelectric composite of claim 1, wherein the molecular ferroelectric material is present in an amount of 20% to 50% by mass of the total amount of the organic polymer matrix and the molecular ferroelectric material.
3. The piezoelectric composite of claim 2, wherein the molecular ferroelectric material is present in an amount of 30% to 50% by mass of the total amount of the organic polymer matrix and the molecular ferroelectric material.
4. A piezoelectric composite material according to any one of claims 1 to 3, wherein the organic polymer matrix is at least one selected from the group consisting of polyvinylidene fluoride-trifluoroethylene copolymer, polyvinylidene fluoride, polymethyl methacrylate, and polydimethylsiloxane.
5. A piezoelectric composite material according to any one of claims 1 to 3, wherein the molecular ferroelectric material is (TMFM)x(TMCM)1–xCdCl3Wherein x is more than or equal to 0 and less than or equal to 1; the organic polymer matrix is polyvinylidene fluoride-trifluoroethylene copolymer.
6. A method of preparing a piezoelectric composite material as claimed in any one of claims 1 to 5, comprising the steps of:
and uniformly mixing the organic polymer matrix and the molecular ferroelectric material.
7. The method of preparing a piezoelectric composite material according to claim 6, wherein the step of uniformly mixing the organic polymer matrix and the molecular ferroelectric material further comprises a step of adding an organic solvent to mix to prepare a slurry.
8. The method of manufacturing a piezoelectric composite material according to claim 7, further comprising a step of drying and molding the slurry.
9. A method of preparing a piezoelectric composite material as claimed in claim 7 or 8,
the step of preparing the slurry comprises the following steps:
mixing the organic polymer matrix with the organic solvent to obtain an organic polymer matrix solution;
adding the molecular ferroelectric material into the organic polymer matrix solution and uniformly mixing.
10. The method for producing a piezoelectric composite material according to claim 9, wherein the organic polymer matrix solution contains 5 to 30% by mass of the organic polymer matrix.
11. A piezoelectric composite film, characterized by being obtained by polarizing the piezoelectric composite material according to any one of claims 1 to 5.
12. Use of a piezoelectric composite material as claimed in any one of claims 1 to 5, or a piezoelectric composite thin film as claimed in claim 11, in the manufacture of an electronic device.
13. A piezoelectric device comprising the piezoelectric composite film according to claim 11.
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