CN113957608B - Fluorescent friction nano generator based on Janus nano belt - Google Patents

Fluorescent friction nano generator based on Janus nano belt Download PDF

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CN113957608B
CN113957608B CN202111260685.XA CN202111260685A CN113957608B CN 113957608 B CN113957608 B CN 113957608B CN 202111260685 A CN202111260685 A CN 202111260685A CN 113957608 B CN113957608 B CN 113957608B
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pmma
janus
solution
phen
pvdf
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CN113957608A (en
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谢云蕊
董相廷
于文生
霍昕彤
胡曜麟
马千里
李丹
姜会林
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Changchun University of Science and Technology
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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
    • D04H1/70—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • D01F6/52—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 of polymers of unsaturated carboxylic acids or unsaturated esters
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • 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
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825—Composite fibres
    • D04H1/43832—Composite fibres side-by-side
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N1/00—Electrostatic generators or motors using a solid moving electrostatic charge carrier
    • H02N1/04—Friction generators

Abstract

The invention relates to a fluorescence friction nano generator based on Janus nanobelts, and belongs to the technical field of nano material preparation. The invention comprises six steps: (1) Precipitation method for preparing Tb (BA) 3 phen complex; (2) preparing polymethyl methacrylate (PMMA); (3) preparing spinning solution; (4) Parallel electrospinning technology for preparing [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]A Janus nanoribbon array; (5) preparing PVDF/PVP composite fiber membrane by uniaxial electrospinning technology; and (6) assembling the fluorescent friction nano generator. The Janus nanoribbon array has good friction charge generation capability and charge trapping capability, and is used as a charge generation layer and a charge trapping layer without adding an additional charge trapping layer. The method is simple and feasible, and can be used for batch production, and the novel fluorescent friction nano generator has wide application prospect.

Description

Fluorescent friction nano generator based on Janus nano belt
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a fluorescent friction nano generator based on Janus nano belts.
Background
The development of new energy materials and devices is one of the important actions to solve the problem of energy shortage, and has attracted a great deal of attention. The friction nano generator can utilize small mechanical energy in life, and development of a novel friction nano generator plays an important role in promoting the development of the energy field, and becomes one of the leading-edge hot research subjects of material science. The nanocomposite has the advantages of larger specific surface area, controllable morphology, easy processing, easy modification, easy functionalization and the like, and is favorable for promoting the development of nano devices to the directions of miniaturization, intellectualization, integration and multifunctionalization. The efficient construction of high-quality nano materials and the development of high-performance novel friction nano generators are one of leading research hotspots in the field of energy and material science.
Friction nano-generators, named Triboelectric Nanogerator, TENG for short, are generally composed of four basic parts: a charge generation layer, a charge trapping layer, a charge collection layer, and a charge storage layer. The method can effectively improve the output performance of the friction nano generator by increasing the surface charge quantity of the charge generation layer; the charge trapping layer is designed and added between the charge generating layer and the charge storage layer, so that the neutralization of induced charges and frictional charges can be blocked, the frictional charges are stabilized, the accumulation of the frictional charges is promoted, and the output performance of the friction nano generator is improved. At present, a charge trapping layer is needed to be additionally added to stabilize friction charges, and how to simplify the manufacturing process of the friction nano generator and improve the output performance of the friction nano generator is an urgent problem to be solved.
The Janus material refers to two kinds of materials with different chemical compositions or one kind of materials with different chemical compositions, the materials have typical asymmetric structures and definite partition structures, different functional substances are assembled in different areas, and the Janus material can obtain dual properties, such as hydrophilicity/hydrophobicity, fluorescence/conductivity and the like, and is one of the leading edge and hot spot research directions in the field of material science. Janus nanoribbon refers to nanoribbon of two specific structures with well-defined zonal structure in the same nanoribbon, e.g. one side of nanoribbon is [ PANI/CNTs/PMMA ]]Composite nanoribbon, the other side is [ Tb (BA) 3 phen/PMMA]The composite nanobelts, two nanobelts are combined together side by side to form the [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]Janus nanoribbons, such asymmetric Janus nanoribbons would have particular properties and applications.
Park et al have prepared Fe using electrospinning 3 O 4 Nanoparticle/polyvinylidene fluoride PVDF composite nanofiber and method for combining sameThe aluminum film forms a friction nano generator [ ACS appl. Mater. Interfaces,2018,10 (30): 25660-25665)]The method comprises the steps of carrying out a first treatment on the surface of the Mandal et al prepared an organic lead halide perovskite type green luminescent PVDF electrospun nanofiber by electrospinning technology and used for assembling a friction Nano generator [ Nano Energy,2018,49:380-392 ]]The method comprises the steps of carrying out a first treatment on the surface of the Dong Xiangting et al prepared Eu (BA) using a parallel electrospinning technique 3 phen/PVP// PANI/PVP photoelectric dual-functional two-strand parallel nanofiber bundle [ national invention patent, application number: 201210407369.5]The method comprises the steps of carrying out a first treatment on the surface of the Cui et al, adding an aromatic polymer film between the PVDF layer and the electrode to capture triboelectric charges [ ACS Nano,2016,10 (6): 6131-6138]The method comprises the steps of carrying out a first treatment on the surface of the Kim et al increased a polydimethylsiloxane PDMS thin layer underneath the charge generation layer to increase the output power of the tribo-Nano-generator [ Nano Energy,2018,50:192-200]. At present, no report is found on the assembly of a friction nano-generator by using Janus nano-belts.
When the electrospinning technology is used for preparing the nano material, the types of raw materials, the molecular weight of the high molecular template agent, the composition of spinning solution, spinning process parameters and the structure of a spinneret have important influences on the shape and the size of a final product. The invention firstly prepares two spinning solutions, namely polyaniline PANI/carbon nano tube CNTs/polymethyl methacrylate PMMA/chloroform CHCl 3 The mixed solution of N, N-dimethylformamide DMF is a spinning solution, tb (BA) 3 phen/PMMA/CHCl 3 The mixed solution of DMF is another spinning solution, and the viscosity of the spinning solution is very important to control; two spinning solutions are filled into two injectors, a positive high-voltage direct current power supply is adopted, an aluminum rotary drum is used as a receiving device, and the PANI/CNTs/PMMA is prepared by using a parallel electrospinning technology under the optimal spinning process condition]//[Tb(BA) 3 phen/PMMA]A Janus nanoribbon array; preparing a spinning solution, namely a mixed solution of polyvinylidene fluoride PVDF/polyvinylpyrrolidone PVP/acetone/DMF, filling the spinning solution into a syringe, adopting a positive high-voltage direct current power supply, using an aluminum rotary drum as a receiving device, and preparing the PVDF/PVP composite fiber membrane by utilizing a single-shaft electrospinning technology under the optimal spinning process condition; then [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]And assembling the Janus nanoribbon array and the PVDF/PVP composite fiber membrane into the fluorescent friction nano generator. At the fluorescenceIn the optical friction nano generator, the Janus nano band array has good charge generation capacity and charge trapping capacity, can be used as a charge generation layer and a charge trapping layer, and does not need to add an additional charge trapping layer, so that friction charge is stabilized and the output performance of TENG is improved; the fluorescent friction nano generator has important application prospect.
Disclosure of Invention
The invention adopts the parallel-axis electrospinning technology to prepare [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]And then preparing a PVDF/PVP composite fiber membrane by adopting a single-shaft electrospinning technology, and assembling the PVDF/PVP composite fiber membrane and the PVDF/PVP composite fiber membrane into the fluorescent friction nano generator.
The invention is realized by firstly preparing two spinning solutions, namely polyaniline PANI, carbon nanotube CNTs, polymethyl methacrylate PMMA and chloroform CHCl 3 And N, N-dimethylformamide DMF as a spinning solution, tb (BA) 3 phen、PMMA、CHCl 3 And DMF as another spinning solution, it is important to control the viscosity of the spinning solution. Filling two spinning solutions into two injectors, adopting a positive high-voltage direct current power supply, using an aluminum rotary drum as a receiving device, and preparing [ PANI/CNTs/PMMA ] by using a parallel electrospinning technology under the optimal spinning process condition]//[Tb(BA) 3 phen/PMMA]Janus nanoribbon array. Then preparing a spinning solution, namely mixing polyvinylidene fluoride PVDF, polyvinylpyrrolidone PVP, acetone and DMF to obtain the spinning solution. The spinning solution is filled into a syringe, a positive high-voltage direct current power supply is adopted, an aluminum rotary drum is used as a receiving device, and under the optimal spinning process condition, PVDF/PVP composite fiber membrane is prepared by utilizing a single-shaft electrospinning technology. Then, the [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]The Janus nanoribbon array and the PVDF/PVP composite fiber membrane are assembled into the fluorescent friction nano generator, and the adopted working mode is a vertical contact-separation mode. The method comprises the following steps:
(1) Precipitation method for preparing Tb (BA) 3 phen complex
1.8650g Tb 4 O 7 Dissolving in 15mL concentrated nitric acid, heating and steamingDrying to obtain Tb (NO) 3 ) 3 Adding 20mL of absolute ethyl alcohol into the crystal to prepare Tb (NO) 3 ) 3 Is a solution of (a) in ethanol; 3.6640g of benzoic acid HBA and 1.8000g of phenanthroline phen are added into 200mL of absolute ethyl alcohol to prepare a mixed ligand solution, and Tb (NO) is added under the condition of continuous stirring 3 ) 3 Dropwise adding ethanol solution of (2) into the mixed ligand solution, and adding concentrated NH 3 ·H 2 O is adjusted to pH 6.5-7.0, after heating to 60 ℃, the reaction is carried out for 3 hours, the obtained precipitate is washed with water and ethanol for 3 times in sequence, and finally is dried for 12 hours in a drying oven at 60 ℃ to obtain Tb (BA) 3 phen complex;
(2) Bulk polymerization method for preparing polymethyl methacrylate PMMA
Weighing 100g of methyl methacrylate MMA and 0.1g of dibenzoyl peroxide BPO, adding the mixture into a 250mL three-necked bottle with a reflux device, stirring uniformly, vigorously stirring the solution at the temperature of 90-95 ℃ and refluxing the solution until the solution has a certain viscosity, stopping heating and naturally cooling to room temperature while continuing stirring after the viscosity is similar to that of glycerin, pouring the solution into a test tube with the pouring height of 5-7cm, standing for 2h until the solution in the test tube has no bubble after pouring, transferring the test tube into a 50 ℃ drying box, standing for 48h, hardening the liquid in the test tube into transparent solid, finally raising the temperature of the drying box to 110 ℃ and preserving heat for 2h, finishing the polymerization reaction, and naturally cooling to room temperature to obtain polymethyl methacrylate PMMA;
(3) Preparing spinning solution
0.03g CNTs was added to 14.00g CHCl 3 Ultrasonic treatment is carried out for 90min at normal temperature, then 0.06g of CSA and 0.05g of ANI are added into the system, and magnetic stirring is carried out for 30min at room temperature to form solution 1; simultaneously, 0.10g of APS is added into 2.00g of DMF and magnetically stirred at room temperature for 30min to form solution 2; placing the solution 1 and the solution 2 into a refrigerator at 0 ℃ for standing for 20min, placing the solution 1 into an ice-water bath, slowly adding the solution 2 into the solution 1, magnetically stirring for 3.5h, adding 1.00g PMMA into the mixed system, and stirring for 12h at normal temperature to obtain spinning solution, namely spinning solution A; will 0.15g Tb (BA) 3 phen and 1.00g PMMA was added to 2.00g of DMF and 14.00g of CHCl 3 Magnetically stirring the mixture for 12 hours at room temperature to obtain spinning solution, namely spinning solution B; 2.00g PVDF is added into a mixed solvent of 4.00g DMF and 3.00g acetone, and stirred for 30min under 50 ℃ heating until PVDF is completely dissolved; then 0.60g PVP is added into the mixture and stirred for 12 hours at room temperature, and a spinning solution called spinning solution C is obtained;
(4) Parallel electrospinning technology for preparing [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]Janus nanoribbon array
Transferring the spinning solution A and the spinning solution B into two plastic injectors with parallel spinning nozzles respectively, and adopting an aluminum roller with the diameter of 10cm and the length of 20cm as a receiving device, wherein the rotating speed is 1200 r.min -1 The method comprises the steps of carrying out a first treatment on the surface of the Applying 10kV direct current voltage between the spinneret and a receiving device, wherein the distance between the receiving device and the tip of the spinneret is 15cm, and performing parallel electrospinning at room temperature to obtain [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]A Janus nanoribbon array;
(5) Single-shaft electrospinning technology for preparing PVDF/PVP composite fiber membrane
Injecting the spinning solution C into a plastic injector, using a plastic needle as a spinneret, and using an aluminum roller with a diameter of 10cm and a length of 20cm as a receiving device, wherein the rotating speed is 1200 r.min -1 The method comprises the steps of carrying out a first treatment on the surface of the Applying a direct-current voltage of 14kV between the spinneret and a receiving device, wherein the distance between the receiving device and the tip of the spinneret is 15cm, and performing uniaxial electrospinning at room temperature to obtain a PVDF/PVP composite fiber film;
(6) Assembled fluorescent friction nano generator
Respectively mix [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]Cutting Janus nanoribbon array and PVDF/PVP composite fiber membrane into square with the size of 3cm multiplied by 3cm, respectively pasting Cu electrodes with the same area on the surfaces of the square, and respectively using double faced adhesive tape to respectively prepare [ PANI/CNTs/PMMA (polymethyl methacrylate) with the Cu electrodes]//[Tb(BA) 3 phen/PMMA]And the Janus nanobelt array and the PVDF/PVP composite fiber film are fixed on two glass plates to assemble the fluorescent friction nano generator.
The [ PANI/CNTs/PMMA ] prepared by the above process]//[Tb(BA) 3 phen/PMMA]Janus nanoribbonThe thickness of the array is 142 mu m, the thickness of the PVDF/PVP composite fiber film is 143 mu m, the width of the Janus nano belt is 8.38+/-0.87 mu m, the diameter of the single PVDF/PVP nano fiber is 0.65+/-0.14 mu m, the fluorescent friction nano generator can generate higher and stable output performance due to the good charge generation capacity and charge capturing capacity of the Janus nano belt array, the maximum output voltage is 155V, the maximum output current is 6.20 mu A, the fluorescent friction nano generator can continuously and stably work for 2 hours, and the fluorescent friction nano generator can circularly 10800 circles and continuously output the output current of about 6.00 mu A, so that the purpose of the invention is realized.
Drawings
FIG. 1 is [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]SEM photographs of Janus nanoribbon arrays;
FIG. 2 is [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]A width distribution histogram of Janus nanoribbons;
FIG. 3 is an SEM photograph of PVDF/PVP composite fiber film;
FIG. 4 is a histogram of the diameter distribution of PVDF/PVP nanofibers;
FIG. 5 is [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]EDS line analysis spectrogram of Janus nanoribbon, which is also used as abstract drawing;
FIG. 6 is a graph of the output current of a fluorescent friction nano-generator;
FIG. 7 is a graph of the output voltage of a fluorescent friction nano-generator;
FIG. 8 is a graph of output stability test of a fluorescent friction nano-generator;
FIG. 9 is [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]An emission spectrum of the Janus nanoribbon array;
FIG. 10 is [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]Photographs of hydrophobic properties of Janus nanoribbon arrays;
FIG. 11 is a photograph of the hydrophobic properties of PVDF/PVP composite fiber film;
FIG. 12 is [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]A flexible photograph of a Janus nanoribbon array;
FIG. 13 is a photograph of the flexibility of a PVDF/PVP composite fiber film;
FIG. 14 is [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]Light-weight photographs of Janus nanoribbon arrays.
Detailed Description
The carbon nano tube with the length of 50nm, methyl methacrylate, dibenzoyl peroxide, polyvinylidene fluoride with the molecular weight of 400000, polyvinylpyrrolidone with the molecular weight of 1300000, terbium oxide, benzoic acid, phenanthroline, aniline, camphorsulfonic acid, ammonium persulfate, chloroform, acetone and N, N-dimethylformamide are all commercially available analytically pure products; self-making in a deionized water laboratory; the glassware and equipment used was the equipment and equipment commonly used in the laboratory.
Examples: 1.8650g Tb 4 O 7 Dissolving in 15mL concentrated nitric acid, heating, and evaporating to obtain Tb (NO) 3 ) 3 Adding 20mL of absolute ethyl alcohol into the crystal to prepare Tb (NO) 3 ) 3 Is a solution of (a) in ethanol; 3.6640g of benzoic acid HBA and 1.8000g of phenanthroline phen are added into 200mL of absolute ethyl alcohol to prepare a mixed ligand solution, and Tb (NO) is added under the condition of continuous stirring 3 ) 3 Dropwise adding ethanol solution of (2) into the mixed ligand solution, and adding concentrated NH 3 ·H 2 O is adjusted to pH 6.5-7.0, after heating to 60 ℃, the reaction is carried out for 3 hours, the obtained precipitate is washed with water and ethanol for 3 times in sequence, and finally is dried for 12 hours in a drying oven at 60 ℃ to obtain Tb (BA) 3 phen complex; weighing 100g of methyl methacrylate MMA and 0.1g of dibenzoyl peroxide BPO, adding the mixture into a 250mL three-necked bottle with a reflux device, stirring uniformly, vigorously stirring the solution at the temperature of 90-95 ℃ and refluxing the solution until the solution has a certain viscosity, stopping heating and naturally cooling to room temperature while continuing stirring after the viscosity is similar to that of glycerin, pouring the solution into a test tube with the pouring height of 5-7cm, standing for 2h until the solution in the test tube has no bubble after pouring, transferring the test tube into a 50 ℃ drying box, standing for 48h, hardening the liquid in the test tube into transparent solid, finally raising the temperature of the drying box to 110 ℃ and preserving heat for 2h, finishing the polymerization reaction, and naturally cooling to room temperature to obtain polymethyl methacrylate PMMA; 0.03g CNTs was added to 14.00g CHCl 3 Ultrasonic treatment at normal temperature for 90min, and then treating 0.06Adding CSA and ANI (0.05 g) into the system, and magnetically stirring at room temperature for 30min to form a solution 1; simultaneously, 0.10g of APS is added into 2.00g of DMF and magnetically stirred at room temperature for 30min to form solution 2; placing the solution 1 and the solution 2 into a refrigerator at 0 ℃ for standing for 20min, placing the solution 1 into an ice-water bath, slowly adding the solution 2 into the solution 1, magnetically stirring for 3.5h, adding 1.00g PMMA into the mixed system, and stirring for 12h at normal temperature to obtain spinning solution, namely spinning solution A; will 0.15g Tb (BA) 3 phen and 1.00g PMMA were added to 2.00g DMF and 14.00g CHCl 3 Magnetically stirring the mixture for 12 hours at room temperature to obtain spinning solution, namely spinning solution B; 2.00g PVDF is added into a mixed solvent of 4.00g DMF and 3.00g acetone, and stirred for 30min under 50 ℃ heating until PVDF is completely dissolved; then adding 0.60g PVP into the mixture and stirring the mixture for 12 hours at room temperature to obtain spinning solution, namely spinning solution C; transferring the spinning solution A and the spinning solution B into two plastic injectors with parallel spinning nozzles respectively, and adopting an aluminum roller with the diameter of 10cm and the length of 20cm as a receiving device, wherein the rotating speed is 1200 r.min -1 Applying a direct current voltage of 10kV between the spinneret and a receiving device, wherein the distance between the receiving device and the tip of the spinneret is 15cm, and performing parallel electrospinning at room temperature to obtain [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]A Janus nanoribbon array; injecting the spinning solution C into a plastic injector, using a plastic needle as a spinneret, and using an aluminum roller with a diameter of 10cm and a length of 20cm as a receiving device, wherein the rotating speed is 1200 r.min -1 Applying a direct-current voltage of 14kV between the spinneret and a receiving device, wherein the distance between the receiving device and the tip of the spinneret is 15cm, and performing uniaxial electrospinning at room temperature to obtain a PVDF/PVP composite fiber film; respectively mix [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]Cutting Janus nanoribbon array and PVDF/PVP composite fiber membrane into square with the size of 3cm multiplied by 3cm, respectively pasting Cu electrodes with the same area on the surfaces of the square, and respectively using double faced adhesive tape to respectively prepare [ PANI/CNTs/PMMA (polymethyl methacrylate) with the Cu electrodes]//[Tb(BA) 3 phen/PMMA]And the Janus nanobelt array and the PVDF/PVP composite fiber film are fixed on two glass plates to assemble the fluorescent friction nano generator. [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]The Janus nanoribbon array has a thickness of 142 μm, the Janus nanoribbon surfaces are smooth and closely arranged along the same direction to form an array, as shown in FIG. 1, and the width is 8.38+ -0.87 μm, as shown in FIG. 2; the thickness of the PVDF/PVP composite fiber film is 143 mu m, the surface of the PVDF/PVP nanofiber is smooth and has uniform size, the diameter of the PVDF/PVP nanofiber film is 0.65+/-0.14 mu m as shown in figure 3, and the diameter of the PVDF/PVP nanofiber film is shown in figure 4; tb element and S element respectively represent Tb (BA) 3 phen and PANI are respectively distributed on two sides of Janus nanoribbon, as shown in FIG. 5, which is similar to [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]The structure of the Janus nanoribbon is consistent; the maximum output current generated by the fluorescent friction nano-generator is 6.20 mu A, as shown in figure 6, and the maximum output voltage is 155V, as shown in figure 7; the fluorescent friction nano generator can continuously and stably work for 2 hours, circularly 10800 circles and continuously output about 6.00 mu A of output current, as shown in FIG. 8; [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]The Janus nanoribbon array can emit green fluorescence, as shown in fig. 9; the Janus nanoribbon array has good hydrophobicity, the water contact angle is 100 degrees, and the Janus nanoribbon array is shown in figure 10; the PVDF/PVP nanofiber membrane is a hydrophobic material, has certain moisture resistance, and has a water contact angle of 134 degrees, as shown in figure 11; the Janus nanoribbon array has good flexibility, and can still recover to the original state after being bent 500 times, and obvious wrinkling, breakage and fracture phenomena are not observed, as shown in fig. 12; PVDF/PVP nanofiber membranes can be easily bent into a shape without breaking and breakage, as shown in fig. 13; the Janus nanoribbon array is placed over the pistil of a lily, which is not broken, indicating that the Janus nanoribbon array is lightweight and has very light weight, as shown in FIG. 14.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention, as will be apparent to those skilled in the art, without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (2)

1. The preparation method of the fluorescent friction nano generator based on the Janus nano belt is characterized in that a positive high-voltage direct current power supply is adopted, an aluminum rotary drum is used as a receiving device, a parallel electrospinning technology and a single-shaft electrospinning technology are respectively utilized to prepare a flexible Janus nano belt array and a composite nano fiber membrane, and the flexible Janus nano belt array and the composite nano fiber membrane are further assembled into the fluorescent friction nano generator, and the preparation method comprises the following steps:
(1) Precipitation method for preparing Tb (BA) 3 phen complex
1.8650g Tb 4 O 7 Dissolving in 15mL concentrated nitric acid, heating and evaporating to obtain Tb (NO) 3 ) 3 Adding 20mL absolute ethanol into the crystal to prepare Tb (NO) 3 ) 3 Is a solution of (a) in ethanol; adding 3.6640g benzoic acid HBA and 1.8000g phenanthroline phen into 200mL absolute ethanol to prepare mixed ligand solution, and stirring to obtain Tb (NO) 3 ) 3 Dropwise adding ethanol solution of (2) into the mixed ligand solution, and adding concentrated NH 3 ·H 2 O is adjusted to pH 6.5-7.0, after heating to 60 ℃, the reaction is carried out 3h, the obtained precipitate is washed with water and ethanol for 3 times in sequence, and finally is dried in a drying oven at 60 ℃ for 12h, thus obtaining Tb (BA) 3 phen complex;
(2) Bulk polymerization method for preparing polymethyl methacrylate PMMA
Weighing 100g methyl methacrylate MMA and 0.1g dibenzoyl peroxide BPO, adding the mixture into a 250mL three-necked bottle with a reflux device, stirring the mixture uniformly, vigorously stirring the mixture at the temperature of 90-95 ℃ and refluxing the mixture until the mixture has a certain viscosity, stopping heating and naturally cooling the mixture to room temperature while continuing stirring after the viscosity is similar to that of glycerin, pouring the mixture into a test tube with the pouring height of 5-7cm, standing the mixture for 2h until the solution in the test tube has no bubble, transferring the test tube into a 50 ℃ drying box, placing the test tube in the 48h, hardening the liquid in the test tube into a transparent solid, and finally raising the temperature of the drying box to 110 ℃ and preserving the temperature of 2h to finish the polymerization reaction, and naturally cooling the mixture to room temperature to obtain polymethyl methacrylate PMMA;
(3) Preparing spinning solution
0.03g CNTs was added to 14.00g CHCl 3 Ultrasonic treatment at normal temperature for 90min, adding 0.06g CSA and 0.05g ANIAdding the solution into the system, and magnetically stirring the solution for 30min at room temperature to form a solution 1; simultaneously, 0.10g of APS is added into 2.00g of DMF and magnetically stirred at room temperature for 30min to form solution 2; placing the solution 1 and the solution 2 into a refrigerator at 0 ℃ for standing for 20min, placing the solution 1 into an ice-water bath, slowly adding the solution 2 into the solution 1, magnetically stirring 3.5 and h, adding 1.00g of PMMA into the mixed system, and stirring 12 and h at normal temperature to obtain a spinning solution called spinning solution A; will 0.15g Tb (BA) 3 phen and 1.00g PMMA were added to 2.00g DMF and 14.00g CHCl 3 Magnetically stirring 12h at room temperature to obtain a spinning solution, namely spinning solution B; 2.00g PVDF is added into a mixed solvent of 4.00g DMF and 3.00g g acetone, and stirred for 30min under 50 ℃ heating until PVDF is completely dissolved; then 0.60g PVP was added thereto and stirred at room temperature for 12h to obtain a spinning solution called spinning solution C;
(4) Parallel electrospinning technology for preparing [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]Janus nanoribbon array
Transferring the spinning solution A and the spinning solution B into two plastic injectors with parallel spinning nozzles respectively, and adopting an aluminum roller with the diameter of 10cm and the length of 20cm as a receiving device, wherein the rotating speed is 1200r min -1 The method comprises the steps of carrying out a first treatment on the surface of the Applying a direct current voltage of 10kV between the spinneret and a receiving device, wherein the distance between the receiving device and the tip of the spinneret is 15cm, and performing parallel electrospinning at room temperature to obtain [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]A Janus nanoribbon array;
(5) Single-shaft electrospinning technology for preparing PVDF/PVP composite fiber membrane
Injecting spinning solution C into a plastic injector, using a plastic needle as spinneret, and using aluminum roller with diameter of 10cm and length of 20cm as receiving device, wherein the rotation speed is 1200r min -1 The method comprises the steps of carrying out a first treatment on the surface of the Applying direct current voltage of 14kV between the spinneret and a receiving device, wherein the distance between the receiving device and the tip of the spinneret is 15cm, and performing uniaxial electrospinning at room temperature to obtain a PVDF/PVP composite fiber film;
(6) Assembled fluorescent friction nano generator
Respectively mix [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]Cutting Janus nanoribbon array and PVDF/PVP composite fiber membrane into square with the size of 3cm multiplied by 3cm, respectively adhering Cu electrodes with the same area on the surfaces of the square, and respectively adhering [ PANI/CNTs/PMMA ] with the Cu electrodes by using double faced adhesive tape]//[Tb(BA) 3 phen/PMMA]The Janus nanobelt array and the PVDF/PVP composite fiber film are fixed on two glass plates to assemble a fluorescent friction nano generator; prepared [ PANI/CNTs/PMMA ]]//[Tb(BA) 3 phen/PMMA]The Janus nanoribbon array has a thickness of 142 mu m, the PVDF/PVP composite fiber film has a thickness of 143 mu m, the Janus nanoribbon has a width of 8.38+/-0.87 mu m, the single PVDF/PVP nanofiber has a diameter of 0.65+/-0.14 mu m, and the fluorescent friction nano generator can generate high and stable output performance, has a maximum output voltage of 155V and a maximum output current of 6.20 mu A due to good charge generating capacity and charge capturing capacity of the Janus nanoribbon array, can continuously and stably operate for 2h, circulates 10800 circles and continuously outputs an output current of about 6.00 mu A.
2. The Janus nanoribbon-based fluorescent friction nanogenerator prepared by the preparation method of claim 1 is characterized in that a special asymmetric Janus nanoribbon structure is utilized, and the Janus nanoribbon array has good charge generation capacity and charge trapping capacity, can be used as a charge generation layer and a charge trapping layer, does not need to be added with an additional charge trapping layer, so that friction charge is stabilized, the output performance of the fluorescent friction nanogenerator is improved, and the purpose of the invention is achieved.
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