CN109238312B - Preparation method of composite fiber-based flexible piezoelectric sensor - Google Patents
Preparation method of composite fiber-based flexible piezoelectric sensor Download PDFInfo
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- CN109238312B CN109238312B CN201811040987.4A CN201811040987A CN109238312B CN 109238312 B CN109238312 B CN 109238312B CN 201811040987 A CN201811040987 A CN 201811040987A CN 109238312 B CN109238312 B CN 109238312B
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- G01D—MEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
- G01D5/00—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable
- G01D5/12—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable using electric or magnetic means
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- 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
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention relates to the field of sensors and discloses a preparation method of a composite fiber-based flexible piezoelectric sensor. Surface functionalization with amino groups is then carried out to ensure covalent coupling with the maleic anhydride molecules in the polymer matrix. After the electroactive carbon ink is coated, the fiber-based flexible piezoelectric sensor is obtained through wet spinning, so that the flexibility and the stability are improved, the application range of the sensor is expanded due to the weavability of the sensor, and the sensor has more excellent detection performance. And finally, compositely twisting the composite fiber-based flexible piezoelectric sensor and the silver nanowires to obtain the composite fiber-based flexible piezoelectric sensor. The sensor has good flexibility, and can be applied to the fields of medical biological monitoring, environmental and health monitoring and the like.
Description
Technical Field
The invention relates to the field of sensors, in particular to a preparation method of a composite fiber-based flexible piezoelectric sensor.
Background
The sensor is an important device which can be used for detecting various kinds of sensory information in the nature by human beings and converting different signals and the sensory information into digitalization and intellectualization. In the process of the rapid development of human civilization information technology, the sensor plays an increasingly important role, and is one of important means for human beings to explore unknown world and understand real world and observe surrounding information. The sensor is an adjustable component which can convert non-electrical signals such as electricity, light, temperature, chemical action and the like into electrical signals.
The lead titanate series electronic ceramic belongs to functional ceramics, mainly has electric functions, such as dielectricity, piezoelectricity, ferroelectricity, pyroelectric property and the like, and some have optical functions. Lead titanate is a ferroelectric material with a Cajuyan structure, and has great anisotropy between transverse and longitudinal electromechanical coupling coefficients due to high Curie point, small relative dielectric constant and large pyroelectric constant, so that the lead titanate is very suitable for manufacturing high-frequency transducers and is widely concerned by people.
In recent years, with the rapid development of flexible wearable electronic products, flexible sensors and flexible energy storage elements have attracted extensive attention. The flexible sensor and the flexible energy storage element are used as important components of the wearable electronic equipment, and have great application prospects in the fields of human motion detection, personalized health monitoring, intelligent human-computer interaction and the like. Among them, the flexible sensor should have high sensitivity, wide detection range, high flexibility and high stability, and the flexible energy storage element should have excellent electrochemical properties, good mechanical flexibility, etc. To date, the preparation of these ideal flexible devices has remained a challenge. The flexible device with excellent comprehensive performance is expected to be obtained by selecting materials and adopting a new preparation technology and a new design idea. The conductive polymer fiber-based flexible piezoelectric sensor has become one of the important directions for the research of flexible devices due to the characteristics of good flexibility, light weight, folding and bending, capability of weaving, low cost, large specific surface area and the like
Disclosure of Invention
In order to solve the technical problem, the invention provides a preparation method of a composite fiber-based flexible piezoelectric sensor. According to the method, samarium-doped lead titanate nanocrystals are prepared, the lead titanate piezoelectric ceramics are modified, the Curie temperature is increased, the lattice anisotropy is increased, the samarium-doped lead titanate nanoparticles are ball-milled into nanoparticles, then the samarium-doped lead titanate nanoparticles are modified by amino groups, surface functionalization is realized by covalent coupling, after electroactive carbon ink is coated, a fiber-based flexible piezoelectric sensor is obtained by wet spinning, and finally the fiber-based flexible piezoelectric sensor is compositely twisted with silver nanowires to obtain the composite fiber-based flexible piezoelectric sensor.
The specific technical scheme of the invention is as follows: a preparation method of a composite fiber-based flexible piezoelectric sensor comprises the following steps:
(1) preparation of samarium-doped lead titanate nanocrystals: adding deionized water into tetrabutyl titanate under the stirring condition to obtain a suspension, sequentially adding aqueous solutions of lead acetate, samarium chloride and sodium hydroxide under the stirring condition, and performing volume fixing by using the deionized water to obtain a mixed solution; adding the mixed solution into a reaction kettle, heating and stirring for 4-5 minutes, raising the temperature, and then keeping the temperature for reaction for 8-10 hours; after the reaction is finished, naturally cooling to room temperature; and taking out the product, soaking to ensure that soluble ions are fully exchanged, filtering and washing the product to remove the soluble ions, drying at the temperature of 80-100 ℃ for 6-8h, and cooling to room temperature to obtain the samarium-doped lead titanate nanocrystal.
The lead titanate series electronic ceramic belongs to functional ceramics, mainly has electric functions, such as dielectricity, piezoelectricity, ferroelectricity, pyroelectric property and the like, and some have optical functions. Lead titanate is a ferroelectric material with a Cajuyan structure, because the lead titanate has high Curie point, small relative dielectric constant, large pyroelectric constant and large anisotropy between transverse and longitudinal electromechanical coupling coefficients, the lead titanate is very suitable for manufacturing high-frequency transducers and is widely concerned by people, but because the lead titanate becomes the crystal boundary energy of ceramics, the tetragonal coercive field is large, and the lattice structure anisotropy is large, the pure lead titanate ceramic material is easy to generate microcracks when passing through the Curie point in the annealing process and is difficult to sinter and compact, and the doping modification is carried out on the lead titanate ceramic material in order to solve the problems. Compared with the lead titanate piezoelectric ceramics widely used at present, the samarium-doped rare earth modified lead titanate piezoelectric ceramics has higher Curie temperature and large electromechanical coupling anisotropy, and is more suitable for manufacturing various transducers working at high temperature.
(2) Preparation of samarium-doped lead titanate nanoparticles: the samarium-doped lead titanate nano-crystal, zirconium dioxide ball and ethanol are ball-milled in a container to prepare samarium-doped lead titanate nano-particles, and the samarium-doped lead titanate nano-particles are dried at 70-80 ℃.
The ball milling method is a mechanical stripping technology, is green and environment-friendly, and has simple operation and low cost. The potential harm to experimental operators and environment caused by using strong acid, hydrazine hydrate and other reducing agents in the redox method is avoided.
(3) Preparing amino-modified samarium-doped lead titanate nanoparticles: respectively ultrasonically dispersing samarium-doped lead titanate nanoparticles and polyethyleneimine into deionized water, and respectively adjusting the pH of the solution to 9-11 to respectively obtain a polyethyleneimine solution and a samarium-doped lead titanate solution; dropwise adding a polyethyleneimine solution into a samarium-doped lead titanate solution, stirring for 1-3h, performing centrifugal separation to obtain amino-modified samarium-doped lead titanate nanoparticles, washing off excessive polyethyleneimine with deionized water, washing with absolute ethyl alcohol to remove distilled water, and centrifuging to obtain pure amino-modified samarium-doped lead titanate nanoparticles.
Samarium doped lead titanate piezoelectric nanoparticles are surface functionalized with amino groups to ensure covalent coupling with maleic anhydride molecules in the polymer matrix. The amino-modified nanoparticles enable a uniform distribution in the polymer composite compared to unmodified nanoparticles and thus improve piezoelectric power generation. The voltage generated during the periodic bending and non-bending motion of a flexible device manufactured based on this unique composite material is significantly increased. Furthermore, this achievement was unprecedented in the rational optimization of flexible devices based on this composite, and represents a method of using chemically reinforced composite systems.
(4) Preparing the fiber-based flexible piezoelectric sensor coated by the electroactive carbon ink: dispersing samarium-doped lead titanate nanoparticles modified by amino in a tetrahydrofuran solution and ultrasonically dispersing for 4-6 h; and then adding the spinning solution into the obtained suspension, stirring for 24-36h at 25-35 ℃, transferring to a reaction kettle for reaction for 9-10h, cooling at room temperature after the reaction is finished to obtain mixed spinning solution, carrying out ultrasonic treatment for 1-2h in a water bath, injecting the mixed spinning solution into an ethanol coagulation bath rotating at 5-10Hz by using a 10-20mL syringe with a 23 # hollow needle, vertically pulling out the obtained fiber, and winding the fiber on a bobbin to obtain the fiber-based flexible piezoelectric sensor coated with the electroactive carbon ink.
Electroactive materials are electron-ion mixed conductors that exhibit insulator characteristics in either a fully oxidized or reduced state, capable of reversibly intercalating and deintercalating ions from solution (ion exchange or charge and discharge processes) into electrical conductors when switched between the oxidized and reduced states. The electric activated carbon ink is a porous carbon-containing substance and has strong adsorption capacity.
(5) Preparing a composite fiber-based flexible piezoelectric sensor: and (3) twisting the fiber-based flexible piezoelectric sensor coated with the electro-activated carbon ink obtained in the step (4) by using a 40-60 mu m silver nanowire, then soaking the fiber-based flexible piezoelectric sensor in an electrolyte, putting the impregnated fiber-based flexible piezoelectric sensor into a transparent and flexible plastic tube, wherein the inner diameter of the plastic tube is 0.6mm, the outer diameter of the plastic tube is 0.7mm, and finally sealing the plastic tube with glue to obtain the composite fiber-based flexible piezoelectric sensor.
Silver is a good electrical conductor, the resistivity is low, the conductivity is high, the collected current is led out by applying the nano silver wire to the conductive layer, and the energy loss can be reduced compared with a TCO semiconductor. The silver nanowire has the characteristics of excellent conductivity, heat transfer property, low surface resistance, extremely high transparency, good biocompatibility and the like.
Preferably, in the step (1), the [ OH ] in the mixed solution is fixed to a constant volume]=1.0-2.0mol·L-1， [3/2Sm+Pb]=0.15-0.20mol·L-l，[Ti]=0.1-0.2mol·L-1。
Preferably, in the step (1), the temperature is raised to 220-300 ℃; cooling, taking out the product, soaking in deionized water and absolute ethyl alcohol, and repeatedly washing for 3-4 times respectively.
Preferably, in the step (2), the ball milling frequency is 15 to 45Hz, and the ball milling time is 60 to 100 minutes.
Preferably, in the step (3), the mass ratio of the polyethyleneimine to the samarium-doped lead titanate is 1: 10.
Preferably, in the step (3), the centrifugal speed is 8000-10000 rpm; washing with deionized water for 1-2 times, and washing with anhydrous ethanol for 3-4 times.
Preferably, in the step (4), the amount of the tetrahydrofuran solution is 20-40mL, and the content is 99%.
Preferably, in step (4), the model of the ultrasonic processor used for the ultrasonic treatment is S-450D-1/2.
Preferably, in the step (4), the spinning solution is prepared by introducing 0.85 wt/v% of electroactive carbon solution into 8 wt/v% of styrene-butadiene-styrene block copolymer solution; wherein the volume ratio of the solvent of the electroactive carbon ink solution is 7: 3 distilled water and ethanol; the solvent of the styrene-butadiene-styrene block copolymer solution is ethanol and dimethylformamide with the volume ratio of 6: 4.
Preferably, in the step (5), the electrolyte is a chloroacetonitrile solution containing 0.6M of 1, 2-dimethyl-3-propylimidazolium iodide, 0.03M of iodine solution, 0.5. mu.M of 4-tert-butylpyridine and 0.03. mu.M of guanidinium isothiocyanate.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the lead titanate piezoelectric ceramics which are widely applied at present, the samarium-doped rare earth modified lead titanate piezoelectric ceramics has higher Curie temperature and larger electromechanical coupling anisotropy, is more suitable for manufacturing various transducers working at high temperature, and is ball-milled into nano particles by a ball mill, so that the contact area is enlarged.
2. Samarium doped lead titanate piezoelectric nanoparticles are surface functionalized with amino groups to ensure covalent coupling with maleic anhydride molecules in the polymer matrix. The amino-modified nanoparticles enable a uniform distribution in the polymer composite compared to unmodified nanoparticles and thus improve piezoelectric power generation.
3. The flexible sensor is spun into a fiber-based sensor by wet spinning after being coated by the electro-activated carbon ink, so that the flexibility and the stability are improved, and the application range of the sensor is expanded due to the knittability of the flexible sensor.
4. The prepared composite fiber-based flexible piezoelectric sensor is compounded with the silver nanowires, so that the conductivity, the heat transfer property and the biocompatibility of the composite fiber-based flexible piezoelectric sensor are improved.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
(1) Preparation of samarium-doped lead titanate nanocrystals:
adding tetrabutyl titanate into a polytetrafluoroethylene reaction kettle, adding deionized water under the stirring condition to obtain a suspension, sequentially adding aqueous solutions of lead acetate, samarium chloride and sodium hydroxide under the stirring condition, using deionized water for all reaction water, and finally fixing the volume to 250ml, wherein [ OH ] is]=1.0mol·L-1， [3/2Sm+Pb]=0.15mol·L-l，[Ti]=0.1mol·L-1,. The reaction kettle is heated and stirred for 4 minutes, stirred for 4 minutes after the temperature is increased, and kept at the temperature of 220 ℃ for 8 hours. After the reaction is finished, the reaction kettle is naturally cooled to room temperature. And taking out the product, soaking for a certain time to fully exchange soluble ions, filtering and washing the product, repeatedly washing the product in deionized water and absolute ethyl alcohol for 3 times respectively to remove the soluble ions, and drying the product in an oven at the temperature of 80 ℃ for 6 hours to obtain the samarium-doped lead titanate nanocrystal.
(2) Preparation of samarium-doped lead titanate nanoparticles:
samarium-doped lead titanate nanocrystals, zirconium dioxide balls and ethanol were ball-milled in a polyethylene bottle using a ball mill at a ball-milling speed of 15Hz for 60 minutes to form samarium-doped lead titanate nanoparticles, which were then dried at 70 ℃.
(3) Preparing amino-modified samarium-doped lead titanate nanoparticles:
ultrasonically dispersing the samarium-doped lead titanate nanoparticles and the polyethyleneimine powder obtained in the step (2) in deionized water respectively, adjusting the pH of the solutions to 10 respectively, then dropwise adding the polyethyleneimine solution into the dispersed samarium-doped lead titanate solution, wherein the ratio of the polyethyleneimine solution dispersed in the mixed solution to the samarium-doped lead titanate solution dispersed in the mixed solution is 1:10, stirring the mixed solution for 1h, separating the prepared amino-modified samarium-doped lead titanate nanoparticles by using a centrifuge with the rotation speed of 8000 revolutions after stirring, washing 1 time by using deionized water to wash away excessive polyethyleneimine, washing 3 times by using absolute ethyl alcohol to remove distilled water, and centrifuging by using a centrifuge with the rotation speed of 8000 revolutions to obtain pure amino-modified samarium-doped lead titanate nanoparticles.
(4) Preparing the fiber-based flexible piezoelectric sensor coated by the electroactive carbon ink:
prepared by wet spinning, the nanoparticles prepared in step (3) are dispersed in 20mL of tetrahydrofuran solution with the content of 99% and dispersed for 4h by using ultrasonic, and the ultrasonic processor is the processor of S-450D-1/2. Then, a spinning solution formulation prepared by introducing a 0.85 wt/v% electroactive carbon solution (prepared with a distilled water: ethanol (7: 3) solution) into an 8 wt/v% styrene-butadiene-styrene block copolymer solution (prepared with ethanol: dimethylformamide = 6: 4) was added to the resulting suspension. The mixture was stirred at 25 ℃ for 24 hours, then the mixture was added to a polytetrafluoroethylene reaction kettle and reacted for 9 hours at high temperature, after the reaction was completed, cooled at room temperature, and finally sonicated in a water bath for 1 hour prior to fiber spinning. The spinning solution was injected into a 5Hz rotating ethanol coagulation bath using a 10mL syringe with a 23 gauge hollow needle, and the resulting fiber was vertically pulled out and wound on a bobbin to obtain an electro-activated carbon ink coated fiber-based flexible piezoelectric sensor.
(5) Preparing a composite fiber-based flexible piezoelectric sensor:
twisting a 40-micron silver nanowire around the fiber-based piezoelectric sensor manufactured in the step (4), impregnating the fiber-based piezoelectric sensor with an electrolyte solution containing 0.6M of 1, 2-dimethyl-3-propyl imidazolium iodide, 0.03M of an iodine solution, 0.5. mu.M of 4-tert-butylpyridine and 0.03. mu.M of guanidinium isothiocyanate, placing the impregnated fiber-based piezoelectric sensor in a transparent and flexible plastic tube with an inner diameter of 0.6mm and an outer diameter of 0.7mm, and finally sealing the tube with glue to obtain the composite fiber-based flexible piezoelectric sensor.
Example 2
(1) Preparation of samarium-doped lead titanate nanocrystals:
adding tetrabutyl titanate into a polytetrafluoroethylene reaction kettle, adding deionized water under the stirring condition to obtain a suspension, sequentially adding aqueous solutions of lead acetate, samarium chloride and sodium hydroxide under the stirring condition, using deionized water as all reaction water, and finally fixing the volume to 300ml, wherein [ OH ] is]= 2.0mol·L-1， [3/2Sm+Pb]= 0.20mol·L-l，[Ti]= 0.2mol·L-1,. The reaction kettle is heated and stirred for 5 minutes, stirred for 4 minutes after the temperature is increased, and kept at the temperature of 220 ℃ for 10 hours. After the reaction is finished, the reaction kettle is naturally cooled to room temperature. And taking out the product, soaking for a certain time to fully exchange soluble ions, filtering and washing the product, repeatedly washing the product in deionized water and absolute ethyl alcohol for 4 times respectively to remove the soluble ions, and drying the product in an oven at the temperature of 80 ℃ for 6 hours to obtain the samarium-doped lead titanate nanocrystal.
(2) Preparation of samarium-doped lead titanate nanoparticles:
samarium-doped lead titanate nanocrystals, zirconium dioxide balls and ethanol were ball-milled in a polyethylene bottle using a ball mill at a ball-milling speed of 15Hz for 100 minutes to form samarium-doped lead titanate nanoparticles, which were then dried at 80 ℃.
(3) Preparing amino-modified samarium-doped lead titanate nanoparticles:
ultrasonically dispersing the samarium-doped lead titanate nanoparticles and polyethyleneimine powder obtained in the step (2) in deionized water respectively, adjusting the pH of the solutions to 10 respectively, then dropwise adding the polyethyleneimine solution into the dispersed samarium-doped lead titanate solution, wherein the ratio of the polyethyleneimine solution dispersed in the mixed solution to the samarium-doped lead titanate solution dispersed in the mixed solution is 1:10, stirring the mixed solution for 3 hours, separating the prepared amino-modified samarium-doped lead titanate nanoparticles by using a centrifuge with the rotation speed of 10000 revolutions after stirring, washing with deionized water for 2 times to remove excessive polyethyleneimine, washing with anhydrous ethanol for 4 times to remove distilled water, and centrifuging by using a centrifuge with the rotation speed of 10000 revolutions to obtain pure amino-modified samarium-doped lead titanate nanoparticles.
(4) Preparing the fiber-based flexible piezoelectric sensor coated by the electroactive carbon ink:
prepared by wet spinning, the nano particles prepared in the step (3) are dispersed in 30mL of tetrahydrofuran solution with the content of 99 percent and dispersed for 5 hours by using ultrasonic, and the ultrasonic processor is the processor of S-450D-1/2. Then, a spinning solution formulation prepared by introducing a 0.85 wt/v% electroactive carbon solution (prepared with a distilled water: ethanol (7: 3) solution) into an 8 wt/v% styrene-butadiene-styrene block copolymer solution (prepared with ethanol: dimethylformamide = 6: 4) was added to the resulting suspension. The mixture was stirred at 30 ℃ for 29 hours, then the mixture was added to a polytetrafluoroethylene reaction kettle and reacted at high temperature for 9.5 hours, after the reaction was completed, cooled at room temperature, and finally sonicated in a water bath for 1.2 hours before fiber spinning. The spinning solution was injected into a 7Hz rotating ethanol coagulation bath using a 16mL syringe with a 23 gauge hollow needle, and the resulting fiber was vertically pulled out and wound on a bobbin to obtain an electro-activated carbon ink-coated fiber-based flexible piezoelectric sensor.
(5) Preparing a composite fiber-based flexible piezoelectric sensor:
twisting a 50-micron silver nanowire around the fiber-based piezoelectric sensor manufactured in the step (4), impregnating the fiber-based piezoelectric sensor with an electrolyte solution containing 0.6M of 1, 2-dimethyl-3-propyl imidazolium iodide, 0.03M of an iodine solution, 0.5. mu.M of 4-tert-butylpyridine and 0.03. mu.M of guanidinium isothiocyanate, placing the impregnated fiber-based piezoelectric sensor in a transparent and flexible plastic tube with an inner diameter of 0.6mm and an outer diameter of 0.7mm, and finally sealing the tube with glue to obtain the composite fiber-based flexible piezoelectric sensor.
Example 3
(1) Preparation of samarium-doped lead titanate nanocrystals:
adding tetrabutyl titanate into a polytetrafluoroethylene reaction kettle, adding deionized water under the stirring condition to obtain a suspension, sequentially adding aqueous solutions of lead acetate, samarium chloride and sodium hydroxide under the stirring condition, using deionized water for all reaction water, and finally fixing the volume to 250ml, wherein [ OH ] is]= 2.0mol·L-1， [3/2Sm+Pb]=0.15mol·L-l，[Ti]=0.1mol·L-1,. And heating the reaction kettle, stirring for 4-5 minutes, heating, stirring for 4 minutes again, and preserving heat at the temperature of 300 ℃ for 8 hours. After the reaction is finished, the reaction kettle is naturally cooled to room temperature. Taking out the product, soaking for a certain time to fully exchange soluble ions, suction filtering and washing the product, and respectively repeatedly washing the product in deionized water and absolute ethyl alcoholWashing for 3 times, removing soluble ions, and then drying in an oven at 100 ℃ for 8h to obtain the samarium-doped lead titanate nanocrystal.
(2) Preparation of samarium-doped lead titanate nanoparticles:
samarium-doped lead titanate nanocrystals, zirconium dioxide balls and ethanol were ball-milled in a polyethylene bottle using a ball mill at a ball-milling speed of 15Hz for 100 minutes to form samarium-doped lead titanate nanoparticles, which were then dried at 70 ℃.
(3) Preparing amino-modified samarium-doped lead titanate nanoparticles:
ultrasonically dispersing the samarium-doped lead titanate nanoparticles and polyethyleneimine powder obtained in the step (2) in deionized water respectively, adjusting the pH of the solutions to 10 respectively, then dropwise adding the polyethyleneimine solution into the dispersed samarium-doped lead titanate solution, wherein the ratio of the polyethyleneimine solution dispersed in the mixed solution to the samarium-doped lead titanate solution dispersed in the mixed solution is 1:10, stirring the mixed solution for 3 hours, separating the prepared amino-modified samarium-doped lead titanate nanoparticles by using a centrifuge with the rotation speed of 10000 revolutions after stirring, washing 1 time by using deionized water to wash away excessive polyethyleneimine, washing 3 times by using absolute ethyl alcohol to remove distilled water, and centrifuging by using a centrifuge with the rotation speed of 10000 revolutions to obtain pure amino-modified samarium-doped lead titanate nanoparticles.
(4) Preparing the fiber-based flexible piezoelectric sensor coated by the electroactive carbon ink:
prepared by wet spinning, the nanoparticles prepared in step (3) are dispersed in 40mL of tetrahydrofuran solution with the content of 99% and dispersed for 6h by using ultrasonic, and the ultrasonic processor is the processor of S-450D-1/2. Then, a spinning solution formulation prepared by introducing a 0.85 wt/v% electroactive carbon solution (prepared with a distilled water: ethanol (7: 3) solution) into an 8 wt/v% styrene-butadiene-styrene block copolymer solution (prepared with ethanol: dimethylformamide = 6: 4) was added to the resulting suspension. The mixture was stirred at 35 ℃ for 36 hours, then the mixture was added to a polytetrafluoroethylene reaction kettle and reacted for 10 hours at high temperature, after the reaction was completed, cooled at room temperature, and finally sonicated in a water bath for 2 hours before fiber spinning. The spinning solution was injected into an ethanol coagulation bath rotating at 10Hz using a 20mL syringe with a 23-gauge hollow needle, and the resulting fiber was vertically pulled out and wound on a bobbin to obtain an electro-activated carbon ink-coated fiber-based flexible piezoelectric sensor.
(5) Preparing a composite fiber-based flexible piezoelectric sensor:
twisting a 60-micron silver nanowire around the fiber-based piezoelectric sensor manufactured in the step (4), impregnating the fiber-based piezoelectric sensor with an electrolyte solution containing 0.6M of 1, 2-dimethyl-3-propyl imidazolium iodide, 0.03M of an iodine solution, 0.5. mu.M of 4-tert-butylpyridine and 0.03. mu.M of guanidinium isothiocyanate, placing the impregnated fiber-based piezoelectric sensor in a transparent and flexible plastic tube with an inner diameter of 0.6mm and an outer diameter of 0.7mm, and finally sealing the tube with glue to obtain the composite fiber-based flexible piezoelectric sensor.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (7)
1. A preparation method of a composite fiber-based flexible piezoelectric sensor is characterized by comprising the following steps:
(1) preparation of samarium-doped lead titanate nanocrystals: adding deionized water into tetrabutyl titanate under the stirring condition to obtain a suspension, sequentially adding aqueous solutions of lead acetate, samarium chloride and sodium hydroxide under the stirring condition, and performing volume fixing by using the deionized water to obtain a mixed solution; in the mixed solution after constant volume [ OH ]]=1.0-2.0mol·L-1， [3/2Sm+Pb]=0.15-0.20mol·L-l，[Ti]=0.1-0.2mol·L-1(ii) a Adding the mixed solution into a reaction kettle, heating and stirring for 4-5 minutes, raising the temperature, and then keeping the temperature for reaction for 8-10 hours; after the reaction is completed, fromThen cooling to room temperature; taking out the product, soaking to fully exchange soluble ions, filtering and washing the product to remove the soluble ions, then drying at 80-100 ℃ for 6-8h, and cooling to room temperature to obtain samarium-doped lead titanate nanocrystals;
(2) preparation of samarium-doped lead titanate nanoparticles: ball-milling samarium-doped lead titanate nanocrystals, zirconium dioxide balls and ethanol in a container to obtain samarium-doped lead titanate nanoparticles, and drying at 70-80 ℃;
(3) preparing amino-modified samarium-doped lead titanate nanoparticles: respectively ultrasonically dispersing samarium-doped lead titanate nanoparticles and polyethyleneimine into deionized water, and respectively adjusting the pH of the solution to 9-11 to respectively obtain a polyethyleneimine solution and a samarium-doped lead titanate solution; dropwise adding a polyethyleneimine solution into a samarium-doped lead titanate solution, stirring for 1-3h, performing centrifugal separation to obtain amino-modified samarium-doped lead titanate nanoparticles, washing off excessive polyethyleneimine with deionized water, washing with absolute ethyl alcohol to remove distilled water, and centrifuging to obtain pure amino-modified samarium-doped lead titanate nanoparticles;
(4) preparing the fiber-based flexible piezoelectric sensor coated by the electroactive carbon ink: dispersing samarium-doped lead titanate nanoparticles modified by amino in a tetrahydrofuran solution and ultrasonically dispersing for 4-6 h; then, adding a spinning solution into the obtained suspension, stirring for 24-36h at 25-35 ℃, transferring to a reaction kettle for reaction for 9-10h, cooling at room temperature after the reaction is finished to obtain a mixed spinning solution, carrying out ultrasonic treatment for 1-2h in a water bath, injecting the mixed spinning solution into an ethanol coagulation bath rotating at 5-10Hz by using a 10-20mL syringe with a 23 # hollow needle, vertically pulling out the obtained fiber, and winding the fiber on a bobbin to obtain the fiber-based flexible piezoelectric sensor coated with the electroactive carbon ink;
the spinning solution is prepared by introducing 0.85 wt/v% of electroactive carbon ink solution into 8 wt/v% of styrene-butadiene-styrene block copolymer solution; wherein the volume ratio of the solvent of the electroactive carbon ink solution is 7: 3 distilled water and ethanol; the solvent of the styrene-butadiene-styrene block copolymer solution is ethanol and dimethylformamide with the volume ratio of 6: 4;
(5) preparing a composite fiber-based flexible piezoelectric sensor: twisting the fiber-based flexible piezoelectric sensor coated with the electro-activated carbon ink obtained in the step (4) by using a 40-60 mu m silver nanowire, soaking the fiber-based flexible piezoelectric sensor in an electrolyte, putting the soaked fiber-based flexible piezoelectric sensor into a transparent and flexible plastic tube, wherein the inner diameter of the plastic tube is 0.6mm, the outer diameter of the plastic tube is 0.7mm, and finally sealing the plastic tube with glue to obtain the composite fiber-based flexible piezoelectric sensor;
the electrolyte was a chloroacetonitrile solution containing 0.6M 1, 2-dimethyl-3-propylimidazolium iodide, 0.03M iodine solution, 0.5. mu.M 4-tert-butylpyridine and 0.03. mu.M guanidinium isothiocyanate.
2. The method for preparing a composite fiber-based flexible piezoelectric sensor as claimed in claim 1, wherein in the step (1), the temperature is raised to 220-300 ℃; cooling, taking out the product, soaking in deionized water and absolute ethyl alcohol, and repeatedly washing for 3-4 times respectively.
3. The method for preparing a composite fiber-based flexible piezoelectric sensor according to claim 1, wherein in the step (2), the ball milling frequency is 15-45Hz, and the ball milling time is 60-100 minutes.
4. The method for preparing a composite fiber-based flexible piezoelectric sensor according to claim 1, wherein in the step (3), the mass ratio of polyethyleneimine to samarium-doped lead titanate is 1: 10.
5. The method for preparing a composite fiber-based flexible piezoelectric sensor according to claim 1, wherein in the step (3), the centrifugal rotation speed is 8000-10000 rpm; washing with deionized water for 1-2 times, and washing with anhydrous ethanol for 3-4 times.
6. The method for preparing a composite fiber-based flexible piezoelectric sensor according to claim 1, wherein in the step (4), the tetrahydrofuran solution is used in an amount of 20-40mL, and the content is 99%.
7. The method for manufacturing a composite fiber-based flexible piezoelectric sensor according to claim 1, wherein in the step (4), the ultrasonic processor used for the ultrasonic processing is of a type S-450D-1/2.
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