CN115724460A - Friction nanometer generator based on perovskite material and preparation method thereof - Google Patents
Friction nanometer generator based on perovskite material and preparation method thereof Download PDFInfo
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Abstract
A friction nanometer generator based on perovskite material and a preparation method thereof, the friction nanometer generator comprises a negative friction layer and a positive friction layer; the negative friction layer is a composite nanofiber layer which introduces MXene nano particles, platinum nano wires and perovskite nano particles into the electro-spun PVDF-HFP nano fibers; the perovskite nano particles respectively construct a Schottky junction with the platinum nano wires and the MXene nano particles, and the movement of positive charges from the platinum nano wires and the MXene nano particles to PVDF-HFP is accelerated. The invention can make the cathode material have ideal electromechanical coupling factor, mechanical flexibility, ideal piezoelectric constant and strong ability of obtaining electrons from other materials. And by introducing the noble metal platinum nanowires, MXene nanoparticles and mixed perovskite nanoparticles, an internal Schottky junction is constructed in the negative friction layer, and the output electrical property of the friction nano-generator is effectively improved.
Description
Technical Field
The invention belongs to the technical field of friction nano-generators, and particularly relates to a friction nano-generator based on a perovskite material and a preparation method thereof.
Background
Most wearable electronics have been developed with limited energy supply, requiring periodic battery replacement. Recently, a series of wearable self-driven electronic devices based on a nano generator are developed successfully, and devices such as an acceleration sensor based on the nano generator and a heart rate detector can effectively solve the problem of energy supply.
The nano generator is a novel existing minimum generator for converting mechanical energy into electric energy, and can convert widely existing mechanical energy into electric energy. At present, the nano-generator can be divided into a piezoelectric nano-generator, a friction nano-generator and a pyroelectric nano-generator. According to the coupling mechanism of the triboelectric effect and the electrostatic induction, the friction nano-generator can effectively convert mechanical energy into electric energy. When two different triboelectric polarity materials are in contact friction, electric charges can be generated on a contact surface, and when the positive electrode and the negative electrode are separated, a potential difference can be generated, so that current output of an external circuit is formed. According to different working modes, the friction nano generator is divided into four types, namely a contact type, a spaced type, a single-electrode type and a sliding type. The friction nano-generator comprises the following four basic working modes: a vertical contact-separation mode, a horizontal sliding mode, a single electrode mode, and an independent layer mode.
At present, perovskite materials are widely applied to friction nano-generators and show good performances such as high carrier mobility and excellent dielectric property. And some organic materials such as PVDF (polyvinylidene fluoride), PDMS (polydimethylsiloxane), PTFE (polytetrafluoroethylene), and the like are also gradually applied to the friction nanogenerator. At present, a plurality of research works are carried out on the basis of perovskite friction nano-generator, including types of metal halide perovskite, all-inorganic perovskite, perovskite type oxide and the like, and by adjusting surface potential and dielectric property, the charge capture capacity and charge transmission mechanism of the perovskite are intensively researched, and system analysis is carried out on influence factors of electric properties of the friction nano-generator in various aspects such as capacitance, output voltage, output current and the like. In addition, the influence of factors such as carrier mobility and surface roughness on the output performance of the perovskite type friction nano-generator can be researched by doping metal ions. Besides the factors of controlling the electrode material, the output electrical performance of the friction nano-generator is also influenced by the form of the electrode material, the presence or absence of polarization and other factors.
Problems existing with tribo-nanogenerators: (1) due to the great loss of the friction charge, the output current and the output electric power of the existing friction nano generator under the low-frequency external force are still not ideal. (2) The transmission charge at the interface of the existing friction nanometer generator material is insufficient, and the electrical output of the nanometer generator is greatly limited.
Disclosure of Invention
In order to overcome the drawbacks of the prior art described above, it is an object of the present invention to provide a triboelectric nanogenerator based on perovskite material and a method for manufacturing the same, in order to solve at least one or both of the two problems described above.
In order to achieve the purpose, the invention adopts the technical scheme that:
a friction nano-generator based on perovskite material comprises a negative friction layer and a positive friction layer;
the negative friction layer is a composite nanofiber layer which introduces MXene nano particles, platinum nano wires and perovskite nano particles into electro-spun PVDF-HFP nano fibers; the perovskite nano particles respectively construct a Schottky junction with the platinum nano wires and the MXene nano particles, and the movement of positive charges from the platinum nano wires and the MXene nano particles to PVDF-HFP is accelerated.
In one embodiment, the mass ratio of the MXene nanoparticles, platinum nanowires and perovskite nanoparticles to electrospun PVDF-HFP nanofibers is 0.05:0.05:0.05:1.
in one embodiment, the perovskite nanoparticles are mixed nanoparticles composed of barium titanate nanocrystals and organic-inorganic hybrid perovskite nanocrystals in a mass ratio of 1:1.
In one embodiment, the positive friction layer is a gold nichrome foil.
The invention also provides a preparation method of the friction nano-generator based on the perovskite material, which comprises the following steps:
adding PVDF-HFP particles into a mixed solution of DMF and acetone to obtain a PVDF-HFP mixed solution;
respectively adding MXene nano particles, platinum nano wires and perovskite nano particles into the PVDF-HFP mixed solution to serve as electrostatic spinning coating;
and (3) carrying out electrostatic spinning by using the coating to obtain the nanofiber membrane, namely the negative friction layer.
And fixing the negative friction layer and the positive friction layer on the substrate to obtain the friction nano generator.
In one embodiment, the MXene nanoparticles are prepared by:
mixing Ti 3 AlC 2 And LiF are dissolved in HCl, washed by deionized water, decanted until the pH value of the supernatant is 6, ultrasonically treated and centrifuged under protective gas, finally the supernatant is freeze-dried to prepare MXene precipitate, and then the MXene precipitate is obtainedCutting MXene precipitate with nanometer frame to obtain MXene micro-nano particles, wherein Ti 3 AlC 2 And LiF in a mass ratio of 1:1.4 to 1.7.
In one embodiment, ti is added 3 AlC 2 And after LiF was dissolved in HCl, it was centrifuged at 3500rpm for 10min and then decanted; after decantation, sonication under protective gas and centrifugation at 4500rpm for 30min.
In one embodiment, the perovskite nanoparticles are mixed nanoparticles composed of barium titanate nanocrystals and organic-inorganic hybrid perovskite nanocrystals in a mass ratio of 1:1;
the barium titanate nanocrystals were prepared as follows:
dripping magnesium titanate into nitric acid to prepare titanium liquid, and dissolving barium hydroxide octahydrate in ionized water to prepare barium liquid; slowly dripping the titanium liquid (which can affect the solubility and has negative influence on the generation of the precipitate) into the barium liquid to generate a white precipitate, filtering, washing and drying the white precipitate to obtain a barium titanate crystal, and then carrying out nano grinding on the crystal to prepare the barium titanate nano crystal;
the organic-inorganic hybrid perovskite nanocrystal is prepared by the following steps:
will PbI 2 、PbCl 2 And dissolving CsI in DMF to obtain a solution I, dissolving MAI and FAI in a mixed solution of IPA and DMF to obtain a solution II, mixing the solution I and the solution II, evaporating and concentrating, separating, washing and drying precipitated crystals, and then carrying out nano grinding to obtain the organic-inorganic hybrid perovskite nano crystal.
In one embodiment, the mass ratio of the MXene nanoparticles, the platinum nanowires, the perovskite nanoparticles and the PVDF-HFP particles in the PVDF-HFP mixed solution is 0.05:0.05:0.05:1.
in one embodiment, the coating is transferred to an injector during the electrospinning process, the voltage of the electrospinning device is set to 10-20kV, the temperature is 35 ℃, the humidity is 40%, and the flow rate is set to 0.12ml h -1 Pushing and adjusting simultaneouslyThe distance between the joint injection needle and the collector is 10cm for spinning, and the nanofiber membrane collected on the aluminum foil (the aluminum foil is used as the collector) is the negative friction layer.
Compared with the prior art, the polyvinylidene fluoride hexafluoropropylene (PVDF-HFP) material is used on the negative electrode, and the material is polarized by using the electrostatic spinning technology, so that the material has ideal electromechanical coupling factor, mechanical flexibility, ideal piezoelectric constant and strong capability of acquiring electrons from other materials. And an internal Schottky junction is constructed in the negative friction layer by introducing the noble metal platinum nanowires, MXene nanoparticles and mixed perovskite nanoparticles, so that the output electrical property of the friction nano-generator is effectively improved. And the anode adopts gold-nickel-chromium alloy foil, so that the corrosion resistance and the oxidation resistance of the anode are ensured to be improved simultaneously.
Drawings
Fig. 1 is a schematic structural view of the frictional nano-generator of the present invention.
FIG. 2 is a schematic flow chart of the preparation method of the present invention.
FIG. 3 is an internal Schottky schematic of the negative friction layer electrode of the present invention.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the drawings and examples.
As shown in fig. 1, the invention is a friction nano-generator based on perovskite material, comprising a positive friction layer 1 and a negative friction layer 2. The contribution of the present invention is mainly to the improvement of the negative friction layer 2. That is, the negative friction layer 2 of the present invention is a composite nanofiber layer incorporating MXene nanoparticles, platinum nanowires (PtNWs) and perovskite nanoparticles into electrospun PVDF-HFP nanofibers. In the composite nanofiber layer, perovskite nanoparticles and platinum nanowires and MXene nanoparticles respectively construct a Schottky junction, and the positive charges can be accelerated to move from the platinum nanowires and the MXene nanoparticles to PVDF-HFP. Meanwhile, the dielectric property of the PVDF-HFP material is improved through an electrostatic spinning technology, so that the capacitance of the friction nano generator is increased, and the charge capture capacity is enhanced.
The positive friction layer 1 of the present invention is made of gold-nickel-chromium alloy foil, and in the structure shown in fig. 1, it is disposed on the first glass plate 51 through the first foam tape 41, the negative friction layer 2 is disposed on the aluminum foil 3, the aluminum foil is disposed on the second glass plate 52 through the second foam tape 42, and the positive friction layer 1 and the negative friction layer 2 are disposed opposite to each other.
In one embodiment of the present invention, the mass ratio of the MXene nanoparticles, the platinum nanowires, the perovskite nanoparticles to the electrospun PVDF-HFP nanofibers is 0.05:0.05:0.05:1.
in this embodiment, the MXene nanoparticles, the platinum nanowires and the perovskite nanoparticles are used in equal amounts, the collection amount of the electrospun PVDF-HFP nanofibers increases with the increase of the spraying rate and the spraying time, the thickness of the film gradually becomes thicker, the thickness of the film has an influence on the output electrical performance of the experiment, the film is too thin, which may result in insufficient contact with the positive friction layer, but the thickness of the film cannot be too thick due to the fact that the good air permeability of the electrospun PVDF-HFP nanofiber film is also ensured during the experiment, and thus the above ratio parameters are selected.
In one embodiment of the present invention, the perovskite nano-particles are mixed nano-particles composed of barium titanate nano-crystals and organic-inorganic hybrid perovskite nano-crystals according to a mass ratio of 1:1, and the particle size of both nano-crystals in the mixed nano-particles should be about l0nm.
Barium titanate nanocrystals belong to oxide perovskites, which can increase the dielectric constant of the material and thus the surface charge density. The organic-inorganic hybrid perovskite nano crystal is perovskite with ideal output performance measured by experiments, and the organic-inorganic hybrid perovskite nano crystal is added to form mixed perovskite nano particles with oxidized perovskite. With the mixed perovskite nano-particles, higher dielectric constant can be obtained, thereby improving the surface charge density of the material and storing more triboelectric charges. In the structure, barium titanate nanocrystals and organic-inorganic hybrid perovskite nanocrystals form Schottky junctions with platinum nanowires; the barium titanate nanocrystal and the organic-inorganic hybrid perovskite nanocrystal form Schottky junction with MXene. Thereby accelerating the movement of positive charges from PVDF-HFP and slowing down the dissipation of electrons, thereby effectively promoting the charge trapping capability.
Referring to fig. 2, the method of manufacturing the friction nanogenerator of the invention can be described as follows:
And 2, respectively adding MXene nano particles, platinum nano wires and perovskite nano particles into the PVDF-HFP mixed solution to serve as the electrostatic spinning coating.
And 3, carrying out electrostatic spinning by using the coating to obtain the nanofiber membrane, namely the negative friction layer.
And 4, fixedly assembling a negative friction layer and a positive friction layer on the substrate to obtain the friction nano generator.
In one example, step 1, PVDF-HFP particles are added to DMF and acetone and heated with stirring until dissolved, resulting in a PVDF-HFP mixed solution. Wherein the volume ratio of DMF to acetone is preferably 1:1. for example, in a more specific example, PVDF-HFP particles were added to 12ml of N, N-Dimethylformamide (DMF) and acetone in a 1:1 part of the mixed solution and stirring was continued at 70 ℃ until dissolved.
The MXene nano particles and the perovskite nano particles are prepared by self-making, specifically, in one embodiment, the perovskite nano particles are mixed nano particles formed by barium titanate nano crystals and organic-inorganic hybrid perovskite nano crystals according to the mass ratio of 1:1, and the preparation of the perovskite nano particles comprises the synthesis of BaTiO 3 Nanocrystals and synthetic organic-inorganic hybrid perovskite nanocrystals are described in detail as follows:
(1) Preparation of organic-inorganic hybrid perovskite nanocrystals
Will PbI 2 、PbCl 2 Adding CsI and the mixture into DMF, and heating and stirring to promote dissolution to obtain a solution I; IPA and DMF were added to MAI and FAI and stirred to promote dissolution, giving solution II. Illustratively, in solution I, pbI 2 、PbCl 2 And CsI is as follows: 3.3-3.5: 1, and DMF is taken as a solvent to meet the requirement of dissolution. Weight of MAI and FAI in solution IIThe ratio is 7:3; the volume ratio of IPA to DMF is preferably 100:1.
and mixing the solution I and the solution II, evaporating and concentrating, separating, washing and drying the precipitated perovskite crystal, and then carrying out nano grinding to obtain the organic-inorganic hybrid perovskite nano crystal. Illustratively, the dosage ratio of the solution I to the solution II is 5:2.
for example, in one more specific embodiment: weighing 630mg of PbI 2 67mg of PbCl 2 And 20mg of CsI, dissolved in 1000. Mu.L of N, N-Dimethylformamide (DMF) and stirred at 75 ℃ for 30 minutes, denoted as solution I; 210mg of Methyl Amine Iodide (MAI) and 90mg of formamidine hydroiodide (FAI) were weighed out, 3mL of isopropyl alcohol (IPA) and 30. Mu.L of N, N-Dimethylformamide (DMF) were added, and stirred at room temperature for 1 hour, labeled as solution II, and solution I and solution II were mixed, and after sufficient reaction, the perovskite crystals were precipitated by evaporation concentration using the property that the solubility of the perovskite crystals decreased with increasing temperature. Separating, washing and drying the perovskite crystal to obtain the organic-inorganic hybrid perovskite nano crystal. And then, placing the organic-inorganic hybrid perovskite nano crystal in a closed grinding chamber by using a medium grinding method, driving a paddle to rotate at a high speed by a grinding rod, and continuously and strongly impacting the organic-inorganic hybrid perovskite nano crystal and the wall of the device, thereby preparing the final organic-inorganic hybrid perovskite nano crystal.
(2) Preparation of BaTiO 3 Nanocrystals
Magnesium orthotitanate is dropped into nitric acid to prepare titanium liquid as a titanium source, and barium hydroxide octahydrate is dissolved in deionized water to prepare barium liquid as a barium source. Slowly dripping the titanium liquid into the barium liquid to generate white precipitate, filtering, washing and drying the precipitate to obtain barium titanate crystals, and then carrying out nano grinding to obtain the barium titanate nanocrystals. Illustratively, the weight ratio of magnesium orthotitanate to nitric acid is 1:8; the weight ratio of barium hydroxide octahydrate to deionized water is 1:14; the weight ratio of the titanium liquid to the barium liquid is 1:1.
among them, the hotter titanium liquid affects the solubility and has a negative effect on the formation of precipitates. Therefore, the barium sulfate can be cooled and added into the barium solution in the form of titanium dioxide solution.
For example, in one more specific embodiment: magnesium titanate was slowly dropped into ice-cold nitric acid at a temperature lower than l 0c, and the solution was used as a titanium source. Meanwhile, ba (OH) 2 8H2O in CO-free solution 2 The pH of the ion-exchanged water was adjusted to greater than 13.0 with KOH, and the solution was used as a barium source. Slowly dripping the glacial titanium solution with the pH value of less than 1.0 into the barium solution to quickly generate white precipitate, filtering and washing the precipitate, and drying at 75 ℃ for 15h to obtain BaTiO 3 And (4) carrying out nano grinding on the crystals. BaTiO with a particle size of about l0nm can be obtained by this method 3 A nanocrystal.
Mixing the organic-inorganic hybrid perovskite nano crystal and the barium titanate nano crystal according to a required proportion to obtain the perovskite nano particle.
In one embodiment, MXene (Ti) 3 C 2 Tx) nanoparticles were prepared as follows:
mixing Ti 3 AlC 2 And LiF is added into HCl, heated and stirred to promote dissolution, and then washed by deionized water to remove ionic impurities in the water. The supernatant was then decanted to a pH of 6. Further carrying out ultrasonic treatment and centrifugation under protective gas. And finally, freeze-drying the supernatant to prepare MXene precipitate, and cutting the MXene precipitate by a nano-frame to obtain MXene nanoparticles.
Illustratively, ti 3 AlC 2 And LiF in a mass ratio of 1:1.4 to 1.7.
Further, in the present example, ti was added 3 AlC 2 And LiF to be added in HCl, stirred for 24 hours to be dissolved, then centrifuged at 3500rpm for 10min, and then decanted; after decantation, sonication under protective gas and centrifugation at 4500rpm for 30min. The method has the advantages of simple process operation, reduced preparation cost, improved preparation efficiency, and ensured experimental safety by protective gas.
For example, in one more specific embodiment: 2.0g LiF was dissolved in 40ml 9Mol/L HCl. However, the device is not suitable for use in a kitchenThen, 2.0g of Ti was added under ice-cold water temperature 3 AlC 2 The powder was added to the above solution and stirred at 45 ℃ for 24 hours. Then, the mixture was centrifuged at 3500rpm for 10min, i.e., the resulting product was washed several times with deionized water and decanted to a supernatant having a pH of 6. The mixture was then sonicated under a protective gas of argon for 40min and the temperature was kept below 40 ℃ and then centrifuged at 4500rpm for 30min. Finally, the supernatant was lyophilized for 12h to obtain MXene precipitate, which was cut through a nano-frame to obtain MXene nanoparticles.
In one embodiment of the present invention, in the PVDF-HFP mixed solution, the mass ratio of the MXene nanoparticles, the platinum nanowires, the perovskite nanoparticles, and the PVDF-HFP particles is 0.05:0.05:0.05:1.
for example, in one more specific embodiment: a mixture containing 100mg of composite perovskite nanocrystals, 100mg of PtNWs and 100mg of MXene was added to the mixed solvent to obtain a filler concentration of 5%. The mixed solution was stirred at 70 ℃ for 4 hours to completely disperse the filler.
In one embodiment of the present invention, the specific process of electrospinning can be described as follows:
transferring the prepared coating into an injector, installing the injector in an electrostatic spinning pump, spinning after setting the voltage, temperature, humidity, material pushing flow rate and other options of electrostatic spinning equipment, and collecting the nanofiber membrane on a collector, namely an aluminum foil, namely a negative friction layer. Illustratively, the voltage of the electrospinning device was set to 10-20kV, the temperature was 35 ℃, the humidity was 40%, and the flow rate was set to 0.12ml h -1 And pushing materials, adjusting the distance between the injection needle and the collector to be 10cm at the same time to perform spinning, moving left and right, performing electrostatic spinning for 5 hours, and collecting the nanofiber membrane deposited on the aluminum foil. If the distance between the injection needle and the collector is adjusted, the material pushing flow rate is adjusted according to the distance.
In one embodiment, step 4, adhering the foam adhesive tape to the back surface of the aluminum foil with the collected negative friction layer, and then fixing the foam adhesive tape on a glass plate; the gold-nickel-chromium alloy foil is also stuck on the foam adhesive tape and then fixed on a glass plate, namelyAnd finishing fixing the positive friction layer and the negative friction layer. At this point the device fabrication is complete. Illustratively, the area of the PVDF-HFP composite fiber layer, the gold-nickel-chromium alloy foil, and the foam tape and glass plate used for fixing in the positive and negative friction layers should be limited to 5 × 5cm 2 The thickness of the PVDF-HFP nanofibers was about 230nm.
The internal schottky schematic of the negative friction electrode of the present invention is shown in fig. 3, which shows PVDF-HFP11, perovskite nanoparticles 12, MXene nanoparticles 13, and platinum nanoparticles 14. The following detailed description of the principles of the invention follows:
(1) PVDF-HFP composite fiber is selected as the negative friction layer
Polyvinylidene fluoride (PVDF) is ferroelectric, belongs to a dielectric medium, has a strong piezoelectric effect, becomes a ferroelectric polymer after polarization, has good piezoelectric property and pyroelectric property, and is generally regarded as an ideal friction negative electrode base material. The doping of the electrode nano material is one of important ways for regulating and controlling the performance of the friction nano generator, so that polyvinylidene fluoride hexafluoropropylene (PVDF-HFP) is selected. The polyvinylidene fluoride hexafluoropropylene (PVDF-HFP) has strong capability of acquiring electrons from other materials, mechanical flexibility and good biocompatibility, and has higher electromechanical coupling factor and more ideal piezoelectric constant, so the PVDF-HFP composite fiber is selected as the negative friction electrode. Since PVDF-HFP has a higher electron affinity than Jin Niege alloy foil, the surface of PVDF-HFF fiber mat will accumulate negative charges in the positive and negative tribo-polar contact state, leaving an equal amount of positive charges in Jin Niege alloy foil.
(2) The negative friction layer material adopts the advantage of electrostatic spinning process
PVDF-HFP has a high electromechanical coupling factor and a relatively ideal piezoelectric constant, and the surface friction coefficient and the effective contact area of the PVDF-HFP can be improved through an electrostatic spinning process. The PVDF-HFP fiber membrane prepared by the electrostatic spinning method has the advantages of simple and convenient operation, low cost and the like, is soft and light, particularly has excellent wear resistance and air permeability, and is an ideal idea for preparing flexible devices. Also, the electrospinning process integrates polarization and stretching. The uniaxial stretching of the polymer chain in the electrostatic spinning process promotes the formation of the strongly oriented beta-phase PVDF-HFP with the maximum spontaneous polarization, and the surface charge density of the nano-generator can be improved.
(3) Negative friction layer doped perovskite nano particle structure
Compared with other conventional triboelectric materials, perovskites have excellent piezoelectric properties, low-temperature processability and good biocompatibility, and have ferroelectricity, so that the perovskite nano-particles are doped into the negative friction layer. And the mixed perovskite nano particles are used, so that higher dielectric constant can be obtained, the surface charge density of the material is improved, and more friction charges are stored. Perovskite nano particles of the negative friction layer in the structure can respectively establish Schottky junctions with platinum nano particles and MXene, and perovskite and the materials are prevented from reacting. The barium titanate nanocrystal and the organic-inorganic hybrid perovskite nanocrystal and the platinum nanowire form a Schottky junction; the barium titanate nanocrystal and the organic-inorganic hybrid perovskite nanocrystal form a Schottky junction with MXene, so that the movement of positive charges from platinum nanoparticles and Mxene to PVDF-HFP is accelerated, the dissipation of electrons is slowed down, and the charge capture capability is effectively promoted.
(4) The advantage of adopting platinum nano-wire instead of silver, gold and other metal nano-wires
According to the invention, the platinum nanowires are adopted instead of other metal nanowires such as silver and the like, so that the reaction between metals such as silver and the organic-inorganic hybrid perovskite is avoided, the platinum has stable chemical properties and does not react with the perovskite, and meanwhile, the work function of the platinum is larger than that of metals such as gold and silver, so that the potential energy of the established Schottky junction is larger, and the output electrical property of the friction nano-generator can be greatly improved in PVDF-HFP nanofibers due to the effective capture of friction charges and the increase of the surface electrical charge potential difference.
(5) The advantage of establishing Schottky junction inside the device
Due to the difference of work functions between the metal and the semiconductor, when the semiconductor is contacted with the metal, a Schottky junction is established at an interface, namely a metal/semiconductor built-in electric field is generated at the contact interface, so that the charge transfer between the mixed fillers is remarkably promoted, the surface charge density is improved under the generated electric field, and the power output of the friction nano-generator is improved. The principle diagram of the invention is shown in fig. 3. At present, the technology of constructing the Schottky junction between the metal and the semiconductor is gradually used in the nano generator, and the technology can effectively promote the dynamic charge transfer phenomenon in the friction nano generator, thereby improving the output performance of the generator. In order to improve the electric output of the friction nano generator, the invention adopts a method that the platinum nano wire and MXene are simultaneously hybridized with the mixed perovskite nano crystal, the platinum nano wire and the MXene can respectively establish Schottky junction with the perovskite oxide barium titanate nano crystal and the organic-inorganic hybrid perovskite nano crystal, and the reaction with the perovskite is avoided. Under the action of the generated electric field, the energy barrier at the interface of the hybrid filler can remarkably promote charge migration and increase charge density, thereby improving the output power of the synthetic nano generator.
(6) The positive friction layer adopts an alloy structure
The Jin Niege alloy is a ternary alloy containing Ni and Cr, and has lower contact resistance than Pt and Pd base alloys, and is stable and reliable. Because the gold-nickel-chromium alloy has excellent wear resistance and corrosion resistance and ideal oxidation resistance, the application of the gold-nickel-chromium alloy in engineering is gradually widened.
Claims (10)
1. A friction nano-generator based on perovskite materials is characterized by comprising a negative friction layer and a positive friction layer;
the negative friction layer is a composite nanofiber layer which introduces MXene nano particles, platinum nano wires and perovskite nano particles into electro-spun PVDF-HFP nano fibers; the perovskite nano particles respectively construct a Schottky junction with the platinum nano wires and the MXene nano particles, and the movement of positive charges from the platinum nano wires and the MXene nano particles to PVDF-HFP is accelerated.
2. The perovskite material-based triboelectric nanogenerator of claim 1, wherein the mass ratio of the MXene nanoparticles, platinum nanowires, and perovskite nanoparticles to electrospun PVDF-HFP nanofibers is 0.05:0.05:0.05:1.
3. the triboelectric nanogenerator based on perovskite material of claim 1, wherein the perovskite nanoparticles are mixed nanoparticles composed of barium titanate nanocrystals and organic-inorganic hybrid perovskite nanocrystals in a mass ratio of 1:1.
4. The perovskite material-based triboelectric nanogenerator of claim 1, wherein the positive friction layer is a gold-nickel-chromium alloy foil.
5. The process for the preparation of triboelectric nanogenerators based on perovskite materials according to claim 1, characterized in that it comprises the following steps:
adding PVDF-HFP particles into a mixed solution of DMF and acetone to obtain a PVDF-HFP mixed solution;
respectively adding MXene nano particles, platinum nano wires and perovskite nano particles into the PVDF-HFP mixed solution to serve as electrostatic spinning coating;
and (3) carrying out electrostatic spinning by using the coating to obtain the nanofiber membrane, namely the negative friction layer.
And fixing the negative friction layer and the positive friction layer on the substrate to obtain the friction nano generator.
6. The preparation method of claim 5, wherein the MXene nanoparticles are prepared by:
mixing Ti 3 AlC 2 And dissolving LiF in HCl, washing with deionized water, decanting until the pH value of the supernatant is 6, performing ultrasonic treatment and centrifugation under protective gas, freeze-drying the supernatant to obtain MXene precipitate, and cutting the MXene precipitate through a nano-frame to obtain MXene micro-nano particles, wherein Ti is contained in the MXene micro-nano particles 3 AlC 2 And LiF in a mass ratio of 1:1.4 to 1.7.
7. The production method according to claim 6, wherein Ti is added 3 AlC 2 And after LiF was dissolved in HCl, it was centrifuged at 3500rpm for 10min and then decanted; after decantation, sonication under protective gas and centrifugation at 4500rpm for 30min.
8. The production method according to claim 5, wherein the perovskite nano-particles are mixed nano-particles composed of barium titanate nano-crystals and organic-inorganic hybrid perovskite nano-crystals in a mass ratio of 1:1;
the barium titanate nanocrystals were prepared as follows:
dripping magnesium orthotitanate into nitric acid to prepare titanium liquid, and dissolving barium hydroxide octahydrate into ionized water to prepare barium liquid; slowly dripping the titanium liquid into the barium liquid to generate white precipitate, filtering, washing and drying the white precipitate to obtain barium titanate crystals, and then carrying out nano grinding on the crystals to obtain barium titanate nano crystals;
the organic-inorganic hybrid perovskite nanocrystal is prepared by the following steps:
will PbI 2 、PbCl 2 And dissolving CsI in DMF to obtain a solution I, dissolving MAI and FAI in a mixed solution of IPA and DMF to obtain a solution II, mixing the solution I and the solution II, evaporating and concentrating, separating, washing and drying precipitated crystals, and then carrying out nano grinding to obtain the organic-inorganic hybrid perovskite nano crystal.
9. The preparation method according to claim 5, wherein the mass ratio of the MXene nanoparticles, the platinum nanowires, the perovskite nanoparticles, and the PVDF-HFP particles in the PVDF-HFP mixed solution is 0.05:0.05:0.05:1.
10. the method of any one of claims 6 to 9, wherein the coating material is transferred to injection during the electrospinning processThe electrostatic spinning equipment is set to have the voltage of 10-20kV, the temperature of 35 ℃, the humidity of 40 percent and the flow rate of 0.12ml h -1 And pushing materials, adjusting the distance between the injection needle and the collector to be 10cm at the same time to carry out spinning, and collecting the nanofiber membrane on the aluminum foil to be the negative friction layer.
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