CN116218105A - Porous PVDF composite material, nano generator thereof and piezoelectric catalysis application - Google Patents
Porous PVDF composite material, nano generator thereof and piezoelectric catalysis application Download PDFInfo
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N2/00—Electric machines in general using piezoelectric effect, electrostriction or magnetostriction
- H02N2/18—Electric machines in general using piezoelectric effect, electrostriction or magnetostriction producing electrical output from mechanical input, e.g. generators
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- C—CHEMISTRY; METALLURGY
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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Abstract
Porous PVDF composite material, nano generator and piezoelectric catalysis application thereof, wherein the composite material is barium calcium zirconate titanate ceramic Ba 0.85 Ca 0.15 Zr 0.1 Ti 0.9 O 3 (BCZT) as inorganic filler, polyethylene glycol (PEG 4000) as plasticizer and pore-forming agent, polyvinylidene fluoride (PVDF) as organic matrixThe piezoelectric performance of the flexible composite material is obviously improved, the piezoelectric output of the nano generator prepared by taking the flexible composite material as a matrix can reach 30V, the piezoelectric catalytic degradation rate of rhodamine B (RhB) can reach 92%, and the reaction constant can reach 0.01555min ‑1 Preparing BCZT ceramic powder by a sol-gel sintering method, and preparing a porous BCZT/PVDF composite membrane by a solution blending-phase separation method. The content of the composite filler is less (lower than 12wt percent), so that the flexibility of the organic polymer material is maintained, and the economic cost is saved. Meanwhile, the BCZT is an environment-friendly ferroelectric material, and can effectively relieve the problem of environmental pollution caused by scrapping lead-containing piezoelectric ceramic electronic devices such as lead zirconate titanate (PZT).
Description
Technical Field
The invention belongs to the technical field of piezoelectric material preparation, and particularly relates to a porous PVDF composite material, a nano generator thereof and piezoelectric catalysis application.
Background
With the rapid development of miniaturization, portability and intellectualization of electronic devices, new electronic devices are in need of high-performance, lightweight and sustainable self-powered energy materials. Most of the energy consumed at present is pollution materials such as fossil energy, so that the pollution materials are not renewable, and the environment is seriously influenced, and the development and the utilization of renewable energy are relatively deficient, so that the development of novel renewable energy materials is a great challenge for sustainable development. The flexible polymer-based piezoelectric material has good biocompatibility, is considered as a first-choice material of self-powered energy sources in novel intelligent electronic equipment, and has great potential in applications such as wearable equipment, artificial limbs, medical care monitoring equipment and the like.
Piezoelectric materials have the ability to convert various mechanical energies in nature into electrical energies, and the unique property makes them already used in various fields such as sensors, nano-generators, piezoelectric catalysis, biomedicine and the like. With the rapid development of the internet of things technology and microelectronic technology nowadays, products such as wearable electronic equipment, electronic skin and the like are layered in recent years, and the development of flexible electronic devices is valued in various countries. The fabrication of new electronic devices is more miniaturized and integrated, which requires better performance of existing piezoelectric materials, for example, it is required that piezoelectric materials must have good flexibility, and its volume is small, its texture is light, etc. While traditional piezoelectric materials such as PZT (piezoelectric ceramics) obviously do not have the requirements of environmental protection and performance, PVDF materials are the most outstanding high-molecular piezoelectric polymers at present, have good piezoelectric performance, and have the advantages of good flexibility, light weight, strong anti-interference capability and the like, so that the PVDF materials are widely focused and researched by researchers. In addition, the periodic ultrasonic wave or vibration applied to the piezoelectric material can play a role in catalytic degradation, and the PVDF piezoelectric film type catalyst has better repeated usability, is simple and efficient to process and can be recycled. Therefore, developing the PVDF material device with high-voltage electrical property has great significance for developing flexible intelligent equipment and environment-friendly material in the future.
The stress induced polarization intensity and the residual polarization intensity of the PVDF-based copolymer can be improved through structural optimization of the PVDF-based copolymer and organic-inorganic material compounding, so that the flexible piezoelectric material with high-voltage output performance is obtained, and the PVDF-based copolymer has great development potential in various piezoelectric fields. The problem that piezoelectric coefficient of piezoelectric polymer is low compared with that of piezoelectric ceramic such as traditional PZT can be solved by adding inorganic piezoelectric material to PVDF and its copolymer, and piezoelectric performance is greatly improved. Calcium barium zirconate titanate (BCZT)/polyvinylidene fluoride (PVDF) is a composite system that combines high dielectric constant and flexibility. In general, in order to maintain a high dielectric constant, most researches have been conducted from the viewpoint of increasing the mass ratio of the inorganic ferroelectric material, so that although the desired dielectric constant can be maintained, the reduction of the relative PVDF content greatly affects the flexibility of the capacitor.
In order to ensure high-voltage electrical performance and improve flexibility, in recent years, research is mostly carried out on a composite system from filling materials and a preparation process as an entry point. PVDF is the preferred material to enhance the flexibility of the material, but is still more useful in inorganic materials and has some limitations in application.
Disclosure of Invention
The invention aims to provide a preparation method of a porous PVDF composite material, a nano-generator and piezoelectric catalysis application thereof, wherein the porous flexible membrane is formed by compounding inorganic filler, the filler is BCZT piezoelectric ceramic powder, and the pore-forming agent is PEG4000, so that the flexibility can be improved while the piezoelectric performance is ensured, the compatibility of the filler and a matrix is improved, and the piezoelectric performance is improved, so that the porous flexible membrane is further applied to the nano-generator and piezoelectric catalysis.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a porous BCZT/PVDF flexible composite comprising: the BCZT filler is an inorganic filler of the porous composite membrane, the PEG4000 is a plasticizer and a pore-forming agent of the porous composite membrane, and the PVDF polymer material is a main matrix; the main matrix is filled with PEG4000 for pore-forming and compounding, and then is compounded with BCZT inorganic filler; the filling amount of PEG4000 is 2wt.% and the filling amount of BCZT inorganic filler is 2-12wt.% in terms of the percentage mass fraction of filling.
Optionally, the BCZT inorganic filler is present in an amount of 2, 4, 6, 8, 10 or 12wt.%.
Optionally, the thickness of the porous BCZT/PVDF flexible composite material is 15-100um.
The porous BCZT/PVDF flexible composite material is any porous BCZT/PVDF composite material of the invention; the preparation method comprises the following steps:
step one, preparing BCZT powder by a sol-gel-sintering method: according to Ba 0.85 Ca 0.15 Zr 0.1 Ti 0.9 O 3 Mixing barium acetate, calcium acetate and water in the stoichiometric ratio in the BCZT filler to obtain a solution A; at the same time, proper amount of acetic acid and ethanol are added into Ba 0.85 Ca 0.15 Zr 0.1 Ti 0.9 O 3 Butyl titanate, zirconium n-butoxide and acetylacetone which are in stoichiometric proportion in the BCZT filler are mixed to obtain a solution B; mixing the solution A and the solution B to prepare BCZT gel, drying, sintering at high temperature, and grinding to obtain BCZT piezoelectric ceramic powder;
step two, preparing a porous PVDF film by a phase separation method: dissolving PEG4000 and PVDF in an organic solvent according to a fixed mass fraction ratio to obtain a PVDF casting film solution, casting the casting film solution on a glass sheet, carrying out coagulation bath drying treatment, and then quenching and stripping to obtain a porous PVDF film;
preparing a porous BCZT/PVDF flexible composite film by adopting a solution blending method and a phase separation method: firstly, dissolving BCZT inorganic filler in an organic solvent, compounding PVDF casting film solution, drying in a coagulating bath, quenching and stripping to obtain the porous BCZT/PVDF flexible composite film material.
Optionally, the third step specifically includes:
3.1, dissolving PEG4000 and PVDF powder in an organic solvent to obtain a PVDF casting film solution;
3.2, adding the BCZT piezoelectric ceramic powder prepared in the step one into the PVDF casting film solution, and uniformly stirring to obtain a porous BCZT/PVDF composite material; optionally, in 3.1, the organic solvent is N, N-dimethylformamide, the dissolution temperature is room temperature, and the dissolution time is 6-7.5 h.
Optionally, the stirring temperature in 3.2 is room temperature, and the stirring time is 6h.
The porous BCZT/PVDF flexible composite material is formed by compounding any porous BCZT/PVDF material
The method specifically comprises the following steps: and (5) dissolving the BCZT, PVDF, PEG4000 material in an organic solvent, and then carrying out tape casting or coating to form a film to prepare the porous BCZT/PVDF flexible film.
Optionally, the method specifically comprises the following steps:
step one, preparing BCZT powder by a sol-gel-sintering method: mixing barium acetate, calcium acetate and water according to the formula amount to obtain a solution A; mixing the acetic acid, ethanol, butyl titanate, zirconium n-butoxide and acetylacetone according to the formula amount to obtain a solution B; mixing the solution A and the solution B to prepare BCZT gel, drying, sintering at high temperature, and grinding to obtain BCZT piezoelectric ceramic powder;
step two, preparing a porous PVDF film by a phase separation method: dissolving PEG4000 and PVDF in an organic solvent according to a fixed mass fraction ratio to obtain a PVDF casting film solution, casting the casting film solution on a glass sheet, carrying out coagulation bath drying treatment, and then quenching and stripping to obtain a porous PVDF film;
preparing a porous BCZT/PVDF flexible composite film by adopting a solution blending method and a phase separation method: firstly, dissolving BCZT inorganic filler in an organic solvent, compounding PVDF casting film solution, drying in a coagulating bath, quenching and stripping to obtain the porous BCZT/PVDF flexible composite film material.
The invention discloses a flexible nano generator, which is prepared by coating an electrode on the surface of a porous BCZT/PVDF flexible film.
The invention discloses a thin film type piezoelectric catalyst, which is prepared by sputtering gold on the surface of a porous BCZT/PVDF flexible film.
The invention has the beneficial effects that:
the method prepares barium calcium zirconate titanate Ba 0.85 Ca 0.15 Zr 0.1 Ti 0.9 O (BCZT) is used as an inorganic filler, polyethylene glycol (PEG 4000) is used as a plasticizer and a pore-forming agent, polyvinylidene fluoride (PVDF) is used as a BCZT/PVDF composite material of an organic matrix, the piezoelectric performance of the flexible composite material is obviously improved, the optimized piezoelectric output of the material can reach 30V, the piezoelectric catalytic degradation rate of rhodamine B (RhB) can reach 92%, and the reaction constant can reach 0.01555min -1 Further, based on the porous BCZT/PVDF composite material, only a filling amount lower than 12wt.% is needed, and the porous BCZT/PVDF composite material is combined with PVDF to prepare the flexible nano-generator and the thin-film piezoelectric catalyst with excellent performance. While maintaining the flexibility of the material, economic costs are saved. Meanwhile, the BCZT is an environment-friendly ferroelectric material, and can effectively relieve the problem of environmental pollution caused by scrapping of lead-containing piezoelectric ceramic electronic devices.
Drawings
FIG. 1 is an X-ray diffraction pattern of the porous BCZT/PVDF flexible composite film prepared in examples 2-7;
FIG. 2 scanning electron micrographs of porous BCZT/PVDF flexible composite films prepared in examples 2-7
FIG. 3 shows piezoelectric output performance graphs of porous BCZT/PVDF flexible composite membranes prepared in examples 2-7;
FIG. 4 shows the piezoelectric catalytic performance of porous BCZT/PVDF flexible composite membranes prepared in examples 2-7;
Detailed Description
The present invention will be described in further detail with reference to examples.
The porous BCZT/PVDF flexible membrane is formed by compounding inorganic filler and pore-forming agent material, and is specifically a Barium Calcium Zirconate Titanate (BCZT)/polyvinylidene fluoride (PVDF) composite material of polyethylene glycol 4000 (PEG 4000). In the study of flexible piezoelectric materials, inorganic filler is a source of high piezoelectric coefficient, BCZT is a high dielectric lead-free material, and Zr is used for preparing the piezoelectric ceramic material 4+ And Ca 2+ Introduction of BaTiO 3 Zr in the crystal lattice 4+ Substituted for part of Ti 4+ ，Ca 2+ Substituted for part of Ba 2+ The dielectric peak at the Curie point is widened and extended to the vicinity of room temperature, thereby making the dielectric constant thereof higher than BaTiO 3 The temperature coefficient of capacitance is higher, and the requirement of an electronic device can be better met. However, as the demand of electronic devices for flexibility is increasing, polymer organic molecular materials and inorganic materials are industrially selected for compounding, but the piezoelectric performance of the polymer materials is lower, and the application of the materials is limited in terms of performance. Therefore, in order to improve the flexibility while improving the piezoelectric coefficient, the invention combines the BCZT with good ferroelectricity with the porous PVDF by a sol-gel sintering method, a phase separation method and a solution blending casting method, improves the compatibility of the filler and a matrix, and improves the piezoelectric performance so as to be further applied to flexible composite electronic devices.
The porous BCZT/PVDF composite material of the invention comprises: the BCZT filler is an inorganic filler of the porous composite membrane, the PEG4000 is a plasticizer and a pore-forming agent of the porous composite membrane, and the PVDF polymer material is a main matrix; the main matrix is filled with PEG4000 for pore-forming and compounding, and then is compounded with BCZT inorganic filler; the filling amount of PEG4000 is 2wt.% and the filling amount of BCZT inorganic filler is 2-12wt.% in terms of the percentage mass fraction of filling. Specifically, the filling amount of the BCZT inorganic filler is 2, 4, 6, 8, 10 or 12wt.%, and the thickness of the porous BCZT/PVDF flexible composite material is 15-100um.
Barium calcium zirconate titanate Ba 0.85 Ca 0.15 Zr 0.1 Ti 0.9 O 3 (BCZT) is used as an inorganic filler, polyethylene glycol (PEG 4000) is used as a plasticizer and a pore-forming agent, polyvinylidene fluoride (PVDF) is used as a BCZT/PVDF composite material of an organic matrix, the piezoelectric performance of the flexible composite material is obviously improved, the piezoelectric output of a nano generator prepared from the flexible composite material can reach 30V, the piezoelectric catalytic degradation rate of rhodamine B (RhB) can reach 92%, and the reaction constant can reach 0.01555min -1 Further, based on the BCZT/PVDF porous composite material, only a filling amount lower than 12wt.% is needed, and the flexible nano-generator and the thin film type piezoelectric catalyst with excellent performance are prepared by combining with PVDF and the additional electrode. While maintaining the flexibility of the material, economic costs are saved. Meanwhile, the BCZT is an environment-friendly ferroelectric material, and can effectively relieve the problem of environmental pollution caused by scrapping of lead-containing piezoelectric ceramic electronic devices.
The preparation method of the porous BCZT/PVDF flexible film comprises the following steps:
step one, preparing BCZT powder by a sol-gel-sintering method: mixing barium acetate, calcium acetate and water according to the formula amount to obtain a solution A; mixing the acetic acid, ethanol, butyl titanate, zirconium n-butoxide and acetylacetone according to the formula amount to obtain a solution B; mixing the solution A and the solution B to prepare BCZT gel, drying, sintering at high temperature, and grinding to obtain BCZT piezoelectric ceramic powder;
step two, preparing a porous PVDF film by a phase separation method: dissolving PEG4000 and PVDF in an organic solvent according to a fixed mass fraction ratio to obtain a PVDF casting film solution, casting the casting film solution on a glass sheet, carrying out coagulation bath drying treatment, and then quenching and stripping to obtain a porous PVDF film;
preparing a porous BCZT/PVDF flexible composite film by adopting a solution blending method and a phase separation method: firstly, dissolving BCZT inorganic filler in an organic solvent, compounding PVDF casting film solution, drying in a coagulating bath, quenching and stripping to obtain the porous BCZT/PVDF flexible composite film material.
In the first step, in the prepared porous BCZT/PVDF composite material, positive and negative charge separation is controlled under stress, so that the charge density is enhanced, and the piezoelectric performance is improved.
The porous BCZT/PVDF flexible membrane can be prepared by dissolving a BCZT/PVDF material in an organic solvent, and then carrying out tape casting or coating to form a membrane; specifically, dissolving PEG4000 and PVDF powder in an organic solvent to obtain a PVDF casting film solution; and (3) adding the BCZT piezoelectric ceramic powder prepared in the step (A) into the PVDF casting film solution, and uniformly stirring to obtain the porous BCZT/PVDF composite material.
The preparation method of the flexible nano generator comprises the following steps: the surface of the porous BCZT/PVDF flexible film is coated with an electrode to prepare the flexible nano generator, the electrode material is one or a mixture of a plurality of conductive silver, gold powder, copper foil or aluminum foil, and the combination mode of the electrode material is one of a vacuum plating method, a magnetron sputtering method, a spraying method or a dry pressing method.
The preparation method of the thin film type piezoelectric catalyst comprises the following steps: and sputtering gold on the surface of the porous BCZT/PVDF flexible film to prepare the thin film type piezoelectric catalyst.
The following describes the technical scheme of the present invention in detail with reference to specific examples, and it should be understood that materials used in the following experiments are all commercially available unless otherwise specified; all methods used, unless otherwise specified, are those commonly used in the art.
Example 1:
the method for preparing the inorganic filler BCZT piezoelectric ceramic powder comprises the following steps:
6.5g of Ba (CH) 3 COO) 2 And 0.79g of Ca (CH 3 COO) 2 Dissolved in 15ml deionized water, added to a mixed solution of 5ml acetic acid and 33ml ethanol to dissolve 9.19g Ti (OC) 4 H 9 ) 4 And 1.44g of C 16 H 36 O 4 Zr, adding 20 drops of acetylacetone, fully stirring to obtain uniform BCZT gel, drying and grinding the gel, and then sintering the gel in a muffle furnace at high temperature, and drying and grinding to obtain BCZT powder.
Example 2:
the BCZT powder in example 1 was added to 6ml of N-Dimethylformamide (DMF) at a filling mass fraction ratio of 2wt.%, and after sufficient ultrasonic stirring, BCZT was uniformly dispersed in DMF. Then, 0.45g of PVDF and 0.012553 g of PEG4000 are added into the mixed solution, and the casting solution is obtained after sufficient ultrasonic stirring. Casting the porous BCZT/PVDF flexible composite film on a glass sheet, drying, quenching, stripping, and carrying out vacuum ion sputtering on the upper surface and the lower surface of the porous BCZT/PVDF flexible composite film to obtain the porous BCZT/PVDF-2.
XRD of the BCZT/PVDF-2 composite membrane is shown in figure 1, SEM is shown in figure 2, the filler is uniformly dispersed in PVDF, the matrix and the filler have good interface compatibility, the output performance of the nano generator prepared by the flexible composite membrane can reach 2V, as shown in figure 3, the catalytic efficiency of the prepared piezoelectric catalyst can reach 24%, and the reaction constant can reach 0.00167min -1 . In the following experiments, the addition amount and concentration of the substances are referred to in example 2 unless specified by the specific amounts.
Example 3:
the BCZT powder in example 1 was added to N-Dimethylformamide (DMF) at a packing mass fraction ratio of 4wt.%, and after sufficient ultrasonic agitation, BCZT was uniformly dispersed in DMF. And then PVDF and PEG4000 are added into the mixed solution, and the casting solution is obtained after sufficient ultrasonic stirring. Casting the porous BCZT/PVDF flexible composite film on a glass sheet, drying, quenching, stripping, and carrying out vacuum ion sputtering on the upper surface and the lower surface of the porous BCZT/PVDF flexible composite film to obtain the porous BCZT/PVDF-4.
XRD of the BCZT/PVDF-4 composite membrane is shown in figure 1, SEM is shown in figure 2, the filler is uniformly dispersed in PVDF, the matrix and the filler have good interface compatibility, the output performance of the nano generator prepared by the flexible composite membrane can reach 2V, as shown in figure 3, the catalytic efficiency of the prepared piezoelectric catalyst can reach 30%, and the reaction constant can reach 0.00222min -1 As shown in fig. 4.
Example 4:
the BCZT powder in example 1 was added to N-Dimethylformamide (DMF) at a filling mass fraction ratio of 6wt.%, and after sufficient ultrasonic agitation, BCZT was uniformly dispersed in DMF. And then PVDF and PEG4000 are added into the mixed solution, and the casting solution is obtained after sufficient ultrasonic stirring. Casting the porous BCZT/PVDF flexible composite film on a glass sheet, drying, quenching, stripping, and carrying out vacuum ion sputtering on the upper surface and the lower surface of the porous BCZT/PVDF flexible composite film to obtain the porous BCZT/PVDF-6.
XRD of the BCZT/PVDF-6 composite membrane is shown in figure 1, SEM is shown in figure 2, the filler is uniformly dispersed in PVDF, the matrix and the filler have good interface compatibility, the output performance of the nano generator prepared by the flexible composite membrane can reach 6V, as shown in figure 3, the catalytic efficiency of the prepared piezoelectric catalyst can reach 33%, and the reaction constant can reach 0.00253min -1 As shown in fig. 4.
Example 5:
the BCZT powder in example 1 was added to N-Dimethylformamide (DMF) at a filling mass fraction ratio of 8wt.%, and after sufficient ultrasonic agitation, BCZT was uniformly dispersed in DMF. And then PVDF and PEG4000 are added into the mixed solution, and the casting solution is obtained after sufficient ultrasonic stirring. Casting the porous BCZT/PVDF flexible composite film on a glass sheet, drying, quenching, stripping, and carrying out vacuum ion sputtering on the upper surface and the lower surface of the porous BCZT/PVDF flexible composite film to obtain the porous BCZT/PVDF-8.
XRD of the BCZT/PVDF-6 composite membrane is shown in figure 1, SEM is shown in figure 2, the filler is uniformly dispersed in PVDF, the matrix and the filler have good interface compatibility, the output performance of the nano generator prepared by the flexible composite membrane can reach 15V, as shown in figure 3, the catalytic efficiency of the prepared piezoelectric catalyst can reach 56%, and the reaction constant can reach 0.00496min -1 As shown in fig. 4.
Example 6:
the BCZT powder in example 1 was added to N-Dimethylformamide (DMF) at a packing mass fraction ratio of 10wt.%, and after sufficient ultrasonic agitation, BCZT was uniformly dispersed in DMF. And then PVDF and PEG4000 are added into the mixed solution, and the casting solution is obtained after sufficient ultrasonic stirring. Casting the porous BCZT/PVDF flexible composite film on a glass sheet, drying, quenching, stripping, and carrying out vacuum ion sputtering on the upper surface and the lower surface of the porous BCZT/PVDF flexible composite film to obtain the porous BCZT/PVDF-10.
XRD of the BCZT/PVDF-6 composite membrane is shown in figure 1, SEM is shown in figure 2, the filler is uniformly dispersed in PVDF, the matrix and the filler have good interface compatibility, the output performance of the nano generator prepared by the flexible composite membrane can reach 30V, as shown in figure 3, the catalytic efficiency of the prepared piezoelectric catalyst can reach 92%, and the reaction constant can reach 0.01555min -1 As shown in fig. 4.
Example 7:
the BCZT powder in example 1 was added to N-Dimethylformamide (DMF) at a packing mass fraction ratio of 12wt.%, and after sufficient ultrasonic agitation, BCZT was uniformly dispersed in DMF. And then PVDF and PEG4000 are added into the mixed solution, and the casting solution is obtained after sufficient ultrasonic stirring. Casting the porous BCZT/PVDF flexible composite film on a glass sheet, drying, quenching, stripping, and carrying out vacuum ion sputtering on the upper surface and the lower surface of the porous BCZT/PVDF flexible composite film to obtain the porous BCZT/PVDF-12.
XRD of the BCZT/PVDF-12 composite membrane is shown in figure 1, SEM is shown in figure 2, the filler is uniformly dispersed in PVDF, the matrix and the filler have good interface compatibility, the output performance of the nano generator prepared by the flexible composite membrane can reach 15V, as shown in figure 3, the catalytic efficiency of the prepared piezoelectric catalyst can reach 55%, and the reaction constant can reach 0.00479min -1 As shown in fig. 4.
The preferred embodiments have been discussed in detail above in connection with the drawings and are not intended to limit the invention. The above-described specific technical features may be combined in any suitable form under the condition of no contradiction, and the present invention will not be described in detail. Any person skilled in the art adopts simple modification or amendment means such as arbitrary combination or equivalent replacement of technical schemes without departing from the scope of the technical schemes, and does not affect the essence of the technical schemes, and the technical schemes still belong to the protection scope of the technical schemes represented by the embodiments of the invention.
Claims (10)
1. A porous BCZT/PVDF flexible composite, comprising:
barium calcium zirconate titanate ceramic Ba 0.85 Ca 0.15 Zr 0.1 Ti 0.9 O 3 The BCZT filler is an inorganic filler of the porous composite membrane, the PEG4000 is a plasticizer and a pore-forming agent of the porous composite membrane, and the PVDF polymer material is a main matrix;
the main matrix is filled with PEG4000 for pore-forming and compounding, and then is compounded with BCZT inorganic filler;
the filling amount of PEG4000 is 2wt.% and the filling amount of BCZT inorganic filler is 2-12wt.% in terms of the percentage mass fraction of filling.
2. The porous BCZT/PVDF flexible composite according to claim 1, wherein the loading of BCZT inorganic filler is 2, 4, 6, 8, 10 or 12wt.%; the thickness of the flexible composite material is 15-100um.
3. The preparation method of the porous BCZT/PVDF composite material is characterized in that the porous BCZT/PVDF flexible composite material is any one of the porous BCZT/PVDF composite materials in claims 1-3, and the preparation method comprises the following steps:
step one, preparing BCZT powder by a sol-gel-sintering method: according to Ba 0.85 Ca 0.15 Zr 0.1 Ti 0.9 O 3 Mixing barium acetate, calcium acetate and water in the stoichiometric ratio in the BCZT filler to obtain a solution A; at the same time, proper amount of acetic acid and ethanol are added into Ba 0.85 Ca 0.15 Zr 0.1 Ti 0.9 O 3 Butyl titanate, zirconium n-butoxide and acetylacetone which are in stoichiometric proportion in the BCZT filler are mixed to obtain a solution B; mixing the solution A and the solution B to prepare BCZT gel, drying, sintering at high temperature, and grinding to obtain BCZT piezoelectric ceramic powder;
step two, preparing a porous PVDF film by a phase separation method: dissolving PEG4000 and PVDF in an organic solvent according to a fixed mass fraction ratio to obtain a PVDF casting film solution, casting the casting film solution on a glass sheet, carrying out coagulation bath drying treatment, and then quenching and stripping to obtain a porous PVDF film;
preparing a porous BCZT/PVDF flexible composite film by adopting a solution blending method and a phase separation method: firstly, dissolving BCZT inorganic filler in an organic solvent, compounding PVDF casting film solution, drying in a coagulating bath, quenching and stripping to obtain the porous BCZT/PVDF flexible composite film material.
4. The method for preparing the porous BCZT/PVDF flexible composite film material according to claim 3, wherein the third step comprises:
1) Dissolving PEG4000 and PVDF powder in an organic solvent to obtain a PVDF casting film solution;
2) And adding the BCZT piezoelectric ceramic powder prepared in the step one into the PVDF casting film solution, and uniformly stirring to obtain the porous BCZT/PVDF composite material.
5. The method for preparing porous BCZT/PVDF composite according to claim 3, wherein the organic solvent in step 1) is N, N-dimethylformamide, the dissolution temperature is room temperature, and the dissolution time is 6 to 7.5 hours.
6. The method for preparing porous BCZT/PVDF composite according to claim 3, wherein the stirring temperature in step 4) 2) is room temperature and the stirring time is 6h.
7. The porous BCZT/PVDF flexible composite material is characterized in that the porous BCZT/PVDF flexible composite film is formed by compounding the porous BCZT/PVDF material according to any one of claims 1-2;
the method specifically comprises the following steps: and (5) dissolving the BCZT, PVDF, PEG4000 material in an organic solvent, and then carrying out tape casting or coating to form a film to prepare the porous BCZT/PVDF flexible film.
8. The porous BCZT/PVDF flexible composite according to claim 7, characterized in that it comprises in particular:
step one, preparing BCZT powder by a sol-gel-sintering method: mixing barium acetate, calcium acetate and water according to the formula amount to obtain a solution A; mixing the acetic acid, ethanol, butyl titanate, zirconium n-butoxide and acetylacetone according to the formula amount to obtain a solution B; mixing the solution A and the solution B to prepare BCZT gel, drying, sintering at high temperature, and grinding to obtain BCZT piezoelectric ceramic powder;
step two, preparing a porous PVDF film by a phase separation method: dissolving PEG4000 and PVDF in an organic solvent according to a fixed mass fraction ratio to obtain a PVDF casting film solution, casting the casting film solution on a glass sheet, carrying out coagulation bath drying treatment, and then quenching and stripping to obtain a porous PVDF film;
preparing a porous BCZT/PVDF flexible composite film by adopting a solution blending method and a phase separation method: firstly, dissolving BCZT inorganic filler in an organic solvent, compounding PVDF casting film solution, drying in a coagulating bath, quenching and stripping to obtain the porous BCZT/PVDF flexible composite film material.
9. A nano-generator, which is characterized in that an electrode is coated on the surface of the porous BCZT/PVDF flexible film according to claim 7 or 8, and the flexible nano-generator is prepared.
10. A thin film piezoelectric catalyst, characterized in that gold is sputtered on the surface of the porous BCZT/PVDF flexible film according to claim 7 or 8, so as to prepare the thin film piezoelectric catalyst.
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