CN114541042A - Composite piezoelectric nanofiber membrane and preparation method thereof, flexible sensor and preparation method thereof - Google Patents
Composite piezoelectric nanofiber membrane and preparation method thereof, flexible sensor and preparation method thereof Download PDFInfo
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- CN114541042A CN114541042A CN202210152237.6A CN202210152237A CN114541042A CN 114541042 A CN114541042 A CN 114541042A CN 202210152237 A CN202210152237 A CN 202210152237A CN 114541042 A CN114541042 A CN 114541042A
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- nanofiber membrane
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- polyvinylidene fluoride
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- piezoelectric nanofiber
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- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 23
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- 238000000034 method Methods 0.000 claims abstract description 12
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- 238000010438 heat treatment Methods 0.000 claims description 10
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 10
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
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Classifications
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- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/43—Acrylonitrile series
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/4318—Fluorine series
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
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- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/16—Measuring force or stress, in general using properties of piezoelectric devices
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L9/00—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means
- G01L9/08—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means by making use of piezoelectric devices, i.e. electric circuits therefor
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- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/04—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons
- D10B2321/042—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons polymers of fluorinated hydrocarbons, e.g. polytetrafluoroethene [PTFE]
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- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
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- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention belongs to the technical field of piezoelectric nano materials, and discloses a composite piezoelectric nano fiber membrane and a preparation method thereof, and a flexible sensor and a preparation method thereof. According to the invention, the polyvinylidene fluoride is blended with a small amount of crystalline polymer (poly-L-lactic acid) or amorphous polymer (polyacrylonitrile) to regulate and control the structure and performance of the polyvinylidene fluoride, and meanwhile, a rare earth fluorescent terbium complex can be doped, so that the appearance, mechanics, dielectric, piezoelectric, fluorescence and other properties of the composite nanofiber film are further improved, and the polyvinylidene fluoride blended composite film with yellow-green fluorescence performance and high beta crystal content is prepared. The electrostatic spinning method adopted by the invention has the advantages of simple process and convenient operation, and is beneficial to large-scale production.
Description
Technical Field
The invention relates to the technical field of piezoelectric nano materials, in particular to a composite piezoelectric nano fiber membrane and a preparation method thereof, and a flexible sensor and a preparation method thereof.
Background
With the rapid and continuous expansion of intelligent terminal equipment such as artificial intelligence products and touch display, the exploration of flexible, light, high-performance, high-sensitivity and high-durability pressure sensors is stimulated. To date, pressure sensors based on various mechanisms have been developed, namely piezoelectric, piezoresistive, triboelectric, capacitive and optical sensing mechanisms. In particular, pressure sensors based on the piezoelectric effect are receiving more and more attention due to their advantages of ultra-fast response time and low power consumption. In addition, the piezoelectric sensor has simple and various structures, good flexibility and mechanical stability, and is beneficial to integration, implantation and miniaturization. In general, the implementation of high performance flexible piezoelectric sensors relies heavily on advanced sensing materials.
Polyvinylidene fluoride (PVDF) is a polar crystalline high polymer material with high dielectric constant, and has a great application prospect in the practical application of flexible sensors. However, the melt processability of PVDF film is difficult, and the α crystal of PVDF film undergoes irreversible phase transition under high electric field, resulting in poor cyclability of the sensor. In order to meet the performance requirements of sensors, PVDF materials are generally modified, and researchers provide various modification methods, such as chemical crosslinking, copolymerization, blending, and doping with nanomaterials.
Therefore, how to prepare the high-performance composite piezoelectric film by a simple modification method has important significance for the development of the field of flexible sensors.
Disclosure of Invention
The invention aims to provide a composite piezoelectric nanofiber membrane and a preparation method thereof, a flexible sensor and a preparation method thereof, and solves the problem that a polyvinylidene fluoride piezoelectric membrane provided by the prior art is poor in recycling performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a composite piezoelectric nanofiber membrane, which comprises the following steps:
mixing polyvinylidene fluoride, an additional polymer and a solvent, and heating and stirring to obtain a spinning solution;
carrying out electrostatic spinning on the spinning solution to obtain a composite piezoelectric nanofiber membrane;
wherein the additional polymer is poly-L-lactic acid or polyacrylonitrile.
Preferably, in the preparation method of the composite piezoelectric nanofiber membrane, the polyvinylidene fluoride, the additional polymer and the solvent are mixed, heated and stirred, and then the rare earth complex is added;
the preparation method of the rare earth complex comprises the following steps: the method comprises the following steps of (1-3) mixing an anhydrous ethanol solution of 2-thenoyltrifluoroacetone, an anhydrous ethanol solution of terbium nitrate hexahydrate and an anhydrous ethanol solution of triphenylphosphine oxide according to a volume ratio of: 1-4: 1-2, obtaining a mixed solution, stirring, filtering and drying the mixed solution to obtain a rare earth complex;
wherein the pH value of the absolute ethanol solution of the 2-thenoyltrifluoroacetone is neutral; the molar ratio of terbium nitrate hexahydrate, 2-thenoyltrifluoroacetone to triphenylphosphine oxide in the mixed solution is 1-2: 2-5: 1 to 3.
Preferably, in the preparation method of the composite piezoelectric nanofiber membrane, the mass ratio of the additional polymer to the polyvinylidene fluoride is 0.02-0.1: 1; the mass ratio of the rare earth complex to the polyvinylidene fluoride is 0.02-0.15: 1; the mass volume ratio of the polyvinylidene fluoride to the solvent is 0.1-0.16 g: 1 mL.
Preferably, in the preparation method of the composite piezoelectric nanofiber membrane, the average molecular weight of the polyvinylidene fluoride is 500000-600000; the average molecular weight of the additional polymer is 80000-150000.
Preferably, in the above method for preparing a composite piezoelectric nanofiber membrane, the solvent comprises a solvent in a volume ratio of 4: 6-6: 4 and a second solvent; the first solvent is N, N-dimethylformamide; the second solvent is tetrahydrofuran or acetone.
Preferably, in the preparation method of the composite piezoelectric nanofiber membrane, the heating and stirring temperature is 50-70 ℃; the heating and stirring time is 4-8 h.
Preferably, in the preparation method of the composite piezoelectric nanofiber membrane, the spinning voltage of electrostatic spinning is 14-20 kV; the spinning temperature of the electrostatic spinning is 20-28 ℃; the environment humidity of the electrostatic spinning is 40-50%; the injection speed of the electrostatic spinning is 0.4-0.5 mL/min; the receiving distance of the electrostatic spinning is 15-18 cm.
The invention also provides a composite piezoelectric nanofiber membrane prepared by the preparation method.
The invention also provides a preparation method of the flexible sensor, which comprises the following steps:
and (3) taking the composite piezoelectric nanofiber membrane as a functional layer, respectively sticking aluminum foils on two sides of the functional layer, and finally packaging with a polyethylene glycol terephthalate film to obtain the flexible sensor.
The invention also provides a flexible sensor prepared by the preparation method.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
according to the invention, the polyvinylidene fluoride is blended with a small amount of crystalline polymer (poly-L-lactic acid) or amorphous polymer (polyacrylonitrile) to regulate and control the structure and performance of the polyvinylidene fluoride, and meanwhile, a rare earth fluorescent terbium complex can be doped, so that the appearance, mechanics, dielectric, piezoelectric, fluorescence and other properties of the composite nanofiber film are further improved, and the polyvinylidene fluoride blended composite film with yellow-green fluorescence performance and high beta crystal content is prepared. The electrostatic spinning method adopted by the invention has the advantages of simple process and convenient operation, and is beneficial to large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is an infrared spectrum of piezoelectric nanofiber membranes of examples 2, 4, 5, 6 and comparative example 1;
FIG. 2 is an infrared spectrum of piezoelectric nanofiber membranes of examples 7, 8, 9 and comparative example 2;
fig. 3 is an XRD spectrum of the piezoelectric nanofiber films of examples 2, 4, 5, 6 and comparative example 1;
FIG. 4 is an emission spectrum of the composite piezoelectric nanofiber membrane of example 5;
FIG. 5 is a tensile stress-strain curve for the piezoelectric nanofiber membranes of examples 7, 8, 9 and comparative example 2;
FIG. 6 is an AFM amplitude image of the piezoelectric nanofiber membrane of example 3;
FIG. 7 is an AFM phase image of the piezoelectric nanofiber membrane of example 3;
fig. 8 is a schematic structural view of the flexible sensor according to embodiment 4.
Detailed Description
The invention provides a preparation method of a composite piezoelectric nanofiber membrane, which comprises the following steps:
mixing polyvinylidene fluoride, an additional polymer and a solvent, and heating and stirring to obtain a spinning solution;
carrying out electrostatic spinning on the spinning solution to obtain a composite piezoelectric nanofiber membrane;
wherein the additional polymer is poly-L-lactic acid or polyacrylonitrile.
In the invention, the polyvinylidene fluoride, the additional polymer and the solvent are mixed, heated and stirred, and then the rare earth complex is added;
the preparation method of the rare earth complex comprises the following steps: the method comprises the following steps of (1-3) mixing an anhydrous ethanol solution of 2-thenoyltrifluoroacetone, an anhydrous ethanol solution of terbium nitrate hexahydrate and an anhydrous ethanol solution of triphenylphosphine oxide according to a volume ratio of: 1-4: 1-2, obtaining a mixed solution, stirring, filtering and drying the mixed solution to obtain a rare earth complex;
among them, the pH value of the absolute ethanol solution of 2-thenoyltrifluoroacetone is preferably neutral.
In the invention, the molar ratio of terbium nitrate hexahydrate, 2-thenoyltrifluoroacetone and triphenylphosphine oxide in the mixed solution is preferably 1-2: 2-5: 1 to 3, and more preferably 1.1 to 1.9: 2.3-4.7: 1.2 to 2.6, more preferably 1.4: 3.2: 2.1.
in the invention, the stirring temperature of the mixed solution is preferably 25-60 ℃, more preferably 29-52 ℃, and more preferably 43 ℃; the stirring time is preferably 12 to 24 hours, more preferably 14 to 21 hours, and even more preferably 17 hours.
In the invention, the mass ratio of the additional polymer to the polyvinylidene fluoride is preferably 0.02-0.1: 1, more preferably 0.04 to 0.08: 1, more preferably 0.06: 1.
in the invention, the mass ratio of the rare earth complex to the polyvinylidene fluoride is preferably 0.02-0.15: 1, more preferably 0.07 to 0.13: 1, more preferably 0.11: 1.
in the invention, the mass volume ratio of the polyvinylidene fluoride to the solvent is preferably 0.1-0.16 g: 1mL, more preferably 0.11 to 0.15 g: 1mL, more preferably 0.14 g: 1 mL.
In the present invention, the average molecular weight of polyvinylidene fluoride is preferably 500000 to 600000, more preferably 520000 to 580000, and even more preferably 534000.
In the present invention, the average molecular weight of the polymer to be added is preferably 80000 to 150000, more preferably 85000 to 120000, and even more preferably 97000.
In the present invention, the solvent preferably contains a solvent in a volume ratio of 4: 6-6: 4, more preferably 5: 6-5: 4, more preferably 5: 5.2.
in the present invention, the first solvent is preferably N, N-dimethylformamide.
In the present invention, the second solvent is preferably tetrahydrofuran or acetone, and more preferably tetrahydrofuran.
In the invention, the heating and stirring temperature is preferably 50-70 ℃, more preferably 53-69 ℃, and more preferably 62 ℃; the heating and stirring time is preferably 4 to 8 hours, more preferably 5 to 7 hours, and even more preferably 6.7 hours.
In the invention, the spinning voltage of electrostatic spinning is preferably 14-20 kV, more preferably 15-18 kV, and more preferably 17 kV; the spinning temperature of electrostatic spinning is preferably 20-28 ℃, more preferably 21-27 ℃, and more preferably 24 ℃; the environmental humidity of electrostatic spinning is preferably 40-50%, more preferably 42-49%, and even more preferably 47%; the injection speed of electrostatic spinning is preferably 0.4-0.5 mL/min, more preferably 0.42-0.48 mL/min, and even more preferably 0.45 mL/min; the receiving distance of the electrostatic spinning is preferably 15-18 cm, more preferably 15.4-17.1 cm, and even more preferably 16.2 cm.
The invention also provides a composite piezoelectric nanofiber membrane prepared by the preparation method.
The invention also provides a preparation method of the flexible sensor, which comprises the following steps:
shearing the composite piezoelectric nanofiber membrane into 4 x 4cm by taking the composite piezoelectric nanofiber membrane as a functional layer2And (3) respectively sticking aluminum foils on two sides of the functional layer, and finally packaging with a polyethylene glycol terephthalate film to obtain the flexible sensor.
The invention also provides a flexible sensor prepared by the preparation method.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In the present invention, the raw materials used in the following examples are commercially available products, and the solvents are all analytically pure.
Example 1
The embodiment provides a composite piezoelectric nanofiber membrane, and a preparation method thereof comprises the following steps:
dissolving 1.176g of polyvinylidene fluoride (with average molecular weight of 534000) and 0.024g of poly-L-lactic acid (with average molecular weight of 100000) in 5mL of mixed solution of N, N-dimethylformamide and 5mL of tetrahydrofuran, and stirring in a water bath at 60 ℃ for 6h to uniformly mix to obtain a spinning solution; and then filling the spinning solution into a 10mL injector and installing the injector on a spinning machine, wherein the receiving distance of the spinning machine is 16cm, the spinning temperature is 26 ℃, the environmental humidity is 42%, the positive voltage is +14kV, the negative voltage is-2 kV, the injection speed is 0.4mL/min, and the composite piezoelectric nanofiber membrane is obtained by electrostatic spinning. The content of beta-crystal obtained by infrared spectroscopic analysis was 87.1%.
Example 2
The present example provides a composite piezoelectric nanofiber membrane, specifically referring to example 1, except that polyvinylidene fluoride is 1.14g, and poly-l-lactic acid is 0.06 g. The content of beta-crystal obtained by infrared spectroscopic analysis was 89.2%.
Example 3
The present example provides a composite piezoelectric nanofiber membrane, specifically referring to example 1, except that polyvinylidene fluoride is 1.104g, and poly-l-lactic acid is 0.096 g. The content of beta-crystal obtained by infrared spectroscopic analysis was 88%.
Example 4
The embodiment provides a composite piezoelectric nanofiber membrane, and a preparation method thereof comprises the following steps:
with terbium (Tb) nitrate hexahydrate (NO)3)3·6H2O) is taken as a luminescent matrix, 2-thenoyltrifluoroacetone (TTA) and triphenylphosphine oxide (TPPO) are taken as ligands, and the molar ratio of the three is 1:3: 2; dissolving 2-thenoyl trifluoroacetone in absolute ethyl alcohol, adjusting the pH value to be neutral by using 1mol/L NaOH, and then adding an absolute ethyl alcohol solution of terbium nitrate hexahydrate and an absolute ethyl alcohol solution of triphenylphosphine oxide with equal volumes to obtain a mixed solution; stirring the mixed solution at 60 ℃ for 12h, filtering and drying to obtain a rare earth complex Tb (TTA)3(TPPO)2；
Dissolving 1.176g of polyvinylidene fluoride (with average molecular weight of 534000) and 0.024g of poly-L-lactic acid (with average molecular weight of 100000) in 5mL of mixed solution of N, N-dimethylformamide and 5mL of tetrahydrofuran, stirring in a water bath at 60 ℃ for 6h to mix uniformly, and then adding 0.025g of rare earth complex to obtain a spinning solution;
and (3) putting the spinning solution into a 10mL injector and installing the injector on a spinning machine, wherein the receiving distance of the spinning machine is 16cm, the spinning temperature is 26 ℃, the environmental humidity is 42%, the positive voltage is +14kV, the negative voltage is-2 kV, the injection speed is 0.4mL/min, and the composite piezoelectric nanofiber membrane is obtained through electrostatic spinning.
The content of beta-crystal obtained by infrared spectroscopic analysis was 94.3%.
The composite piezoelectric nanofiber membrane is used as a functional layer and is cut into 4 multiplied by 4cm2Respectively sticking aluminum foils with the same size on two sides of the functional layer as a positive electrode and a negative electrode; and finally, packaging with a polyethylene terephthalate film to obtain the flexible sensor, wherein the structural schematic diagram of the flexible sensor is shown in fig. 8.
Example 5
This example provides a composite piezoelectric nanofiber membrane, see example 4 for details, except that the rare earth complex is 0.06 g. The content of beta-crystal obtained by infrared spectroscopic analysis was 95.5%.
Example 6
This example provides a composite piezoelectric nanofiber membrane, see example 4 for details, except that the rare earth complex is 0.12 g. The content of beta-crystal obtained by infrared spectroscopic analysis was 96%.
Example 7
The embodiment provides a composite piezoelectric nanofiber membrane, and a preparation method thereof comprises the following steps:
dissolving 1.33g of polyvinylidene fluoride (with average molecular weight of 534000) and 0.07g of polyacrylonitrile (with average molecular weight of 150000) in 6mL of mixed solution of N, N-dimethylformamide and 4mL of acetone, and stirring in a water bath at 60 ℃ for 6h to uniformly mix the materials to obtain a spinning solution;
and (3) putting the spinning solution into a 10mL injector and installing the injector on a spinning machine, wherein the receiving distance of the spinning machine is 16cm, the spinning temperature is 25 ℃, the environmental humidity is 47%, the positive voltage is +15kV, the negative voltage is-2 kV, the injection speed is 0.5mL/min, and the composite piezoelectric nanofiber membrane is obtained through electrostatic spinning.
The content of beta-crystal obtained by infrared spectroscopic analysis was 96.3%.
Example 8
The present example provides a composite piezoelectric nanofiber membrane, specifically referring to example 7, except that polyvinylidene fluoride is 1.288g, and polyacrylonitrile is 0.112 g. The content of beta-crystal obtained by infrared spectroscopic analysis was 96%.
Example 9
The present example provides a composite piezoelectric nanofiber membrane, specifically referring to example 7, except that polyvinylidene fluoride is 1.26g, and polyacrylonitrile is 0.14 g. The content of beta-crystal obtained by infrared spectroscopic analysis was 95.5%.
Comparative example 1
This comparative example provides a piezoelectric nanofiber membrane, specifically referring to example 1, except that polyvinylidene fluoride (pvdf) was 1.2g and poly (l-lactic acid) was not included. The content of beta-crystal obtained by infrared spectroscopic analysis was 88%.
Comparative example 2
A comparative example provides a piezoelectric nanofiber membrane, specifically referring to example 7, except that 1.4g of polyvinylidene fluoride, does not contain polyacrylonitrile. The content of beta-crystal obtained by infrared spectroscopic analysis is 89%.
The piezoelectric nanofiber films of examples 2, 4, 5, 6, 7, 8, 9 and comparative examples 1, 2 were subjected to an infrared test, and the results are shown in fig. 1 to 2.
Calculating the beta phase crystal content F (beta) of the polyvinylidene fluoride in an infrared spectrogram by using the following formula:
F(β)＝Aβ/(1.26Aα+Aβ)
wherein A isαAnd AβRespectively corresponding to the wave number of 763cm in the infrared spectrogram-1And 840cm-1The absorption strength of (2).
As shown in fig. 1 and 2, the rare earth complex has a positive effect of increasing the content of the beta phase in the composite piezoelectric nanofiber membrane added with the rare earth complex and the polymer blend compared with the pure polyvinylidene fluoride nanofiber membrane. This positive effect of F (β) is mainly due to hydrogen bonding interactions between the-OH groups and the polyvinylidene fluoride chains generated during crystallization, favoring the formation of the β phase.
XRD tests were performed on the piezoelectric nanofiber films of examples 2, 4, 5, 6 and comparative example 1, and the results are shown in fig. 3. As can be seen from fig. 3, the X-ray diffraction peaks of the pure polyvinylidene fluoride nanofiber membrane are both α (18.3 °) and β (20.3 °) and β (36.2 °) phases, indicating that mixed crystals of α and β phases exist in the electrospun polyvinylidene fluoride. With the increase of the dosage of the rare earth complex, the alpha phase of the polyvinylidene fluoride is gradually converted to the beta phase until the content of the rare earth complex reaches 10 wt%, and the output performance of the final device is further improved by the synergistic piezoelectric effect of the rare earth complex and the polyvinylidene fluoride.
The composite piezoelectric nanofiber membrane of example 5 was subjected to emission spectrum test, and the results are shown in fig. 4. As can be seen from FIG. 4, the wavelength at 494nm is5D4-7F6A transition peak at 547nm5D4-7F5And (4) a transition peak indicates that the prepared nanofiber membrane has good yellow-green fluorescence property and high fluorescence intensity.
The piezoelectric nanofiber films of examples 7, 8, 9 and comparative example 2 were subjected to tensile property test, and the results are shown in fig. 5. As can be seen from fig. 5, the mechanical properties of the pure polyvinylidene fluoride nanofiber membrane are the worst and are not durable in the periodic contact and separation process. With the increase of the content of polyacrylonitrile, the tensile strength of the composite nanofiber membrane is in an increasing trend, which shows that the introduction of the polyacrylonitrile can greatly improve the mechanical property of the composite piezoelectric nanofiber membrane.
The results of atomic force microscopic analysis of the piezoelectric nanofiber membrane of example 3 are shown in fig. 6 to 7. As can be seen from FIGS. 6 to 7, the spherical crystal morphology of the polyvinylidene fluoride is clearly shown to belong to the alpha phase crystal, and the granular crystal morphology is shown to belong to the beta or gamma phase crystal.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the composite piezoelectric nanofiber membrane is characterized by comprising the following steps of:
mixing polyvinylidene fluoride, an additional polymer and a solvent, and heating and stirring to obtain a spinning solution;
performing electrostatic spinning on the spinning solution to obtain a composite piezoelectric nanofiber membrane;
wherein the additional polymer is poly-L-lactic acid or polyacrylonitrile.
2. The method for preparing the composite piezoelectric nanofiber membrane as claimed in claim 1, wherein the steps of mixing, heating and stirring polyvinylidene fluoride, additional polymer and solvent further comprise adding rare earth complex;
the preparation method of the rare earth complex comprises the following steps: the method comprises the following steps of (1-3) mixing an anhydrous ethanol solution of 2-thenoyltrifluoroacetone, an anhydrous ethanol solution of terbium nitrate hexahydrate and an anhydrous ethanol solution of triphenylphosphine oxide according to a volume ratio of: 1-4: 1-2, obtaining a mixed solution, stirring, filtering and drying the mixed solution to obtain a rare earth complex;
wherein the pH value of the absolute ethanol solution of the 2-thenoyltrifluoroacetone is neutral; the molar ratio of terbium nitrate hexahydrate, 2-thenoyltrifluoroacetone to triphenylphosphine oxide in the mixed solution is 1-2: 2-5: 1 to 3.
3. The preparation method of the composite piezoelectric nanofiber membrane as claimed in claim 2, wherein the mass ratio of the additional polymer to polyvinylidene fluoride is 0.02-0.1: 1; the mass ratio of the rare earth complex to the polyvinylidene fluoride is 0.02-0.15: 1; the mass volume ratio of the polyvinylidene fluoride to the solvent is 0.1-0.16 g: 1 mL.
4. The method for preparing a composite piezoelectric nanofiber membrane as claimed in any one of claims 1 to 3, wherein the average molecular weight of the polyvinylidene fluoride is 500000-600000; the average molecular weight of the additional polymer is 80000-150000.
5. The method according to claim 4, wherein the solvent comprises a solvent in a volume ratio of 4: 6-6: 4 and a second solvent; the first solvent is N, N-dimethylformamide; the second solvent is tetrahydrofuran or acetone.
6. The preparation method of the composite piezoelectric nanofiber membrane as claimed in claim 1, 3 or 5, wherein the temperature of heating and stirring is 50-70 ℃; the heating and stirring time is 4-8 h.
7. The preparation method of the composite piezoelectric nanofiber membrane as claimed in claim 6, wherein the spinning voltage of the electrostatic spinning is 14-20 kV; the spinning temperature of the electrostatic spinning is 20-28 ℃; the environment humidity of the electrostatic spinning is 40-50%; the injection speed of the electrostatic spinning is 0.4-0.5 mL/min; the receiving distance of the electrostatic spinning is 15-18 cm.
8. A composite piezoelectric nanofiber membrane prepared by the preparation method of any one of claims 1 to 7.
9. A method for preparing a flexible sensor is characterized by comprising the following steps:
the flexible sensor is obtained by taking the composite piezoelectric nanofiber membrane as claimed in claim 8 as a functional layer, respectively adhering aluminum foils to two sides of the functional layer, and finally packaging with a polyethylene terephthalate film.
10. A flexible sensor produced by the production method according to claim 9.
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