CN114044521B - Multiphase composite nanoparticle and method for preparing triboelectric thin film - Google Patents
Multiphase composite nanoparticle and method for preparing triboelectric thin film Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000010409 thin film Substances 0.000 title abstract description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 72
- 239000004005 microsphere Substances 0.000 claims abstract description 55
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- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 44
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- 239000011246 composite particle Substances 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 32
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 24
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- 238000002360 preparation method Methods 0.000 claims abstract description 8
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- 238000003756 stirring Methods 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 40
- 239000008367 deionised water Substances 0.000 claims description 25
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000084 colloidal system Substances 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 15
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 14
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 14
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- 238000005576 amination reaction Methods 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 5
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- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 4
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2518/00—Other type of polymers
- B05D2518/10—Silicon-containing polymers
- B05D2518/12—Ceramic precursors (polysiloxanes, polysilazanes)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2601/00—Inorganic fillers
- B05D2601/20—Inorganic fillers used for non-pigmentation effect
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2601/00—Inorganic fillers
- B05D2601/20—Inorganic fillers used for non-pigmentation effect
- B05D2601/22—Silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2601/00—Inorganic fillers
- B05D2601/20—Inorganic fillers used for non-pigmentation effect
- B05D2601/24—Titanium dioxide, e.g. rutile
Abstract
The invention relates to a multiphase composite nanoparticle and a method for preparing a triboelectric film, wherein the preparation method of the multiphase composite nanoparticle comprises the following steps: 1, siO preparation 2 A microsphere; 2, at SiO 2 Uniformly depositing noble metal nano particles on the surfaces of the microspheres to form composite particles; and 3, wrapping the semiconductor TiO on the outer layer of the composite particle 2 The method comprises the steps of carrying out a first treatment on the surface of the The method for preparing the friction electrification film comprises the following steps: a, adding the multiphase composite nano particles into liquid polydimethylsiloxane to obtain a component A, and then mixing the component A with a curing agent to obtain a component B; b, weighing polydimethylsiloxane again, and adding a curing agent to obtain a component C; c, spin-coating the component C on the surface of the electrode, spin-coating the component B on the surface of the component C when the component C is not completely cured, and finally drying to completely cure the component B and the component C; the invention realizes the wide spectrum regulation of the surface charge density of the triboelectric thin film and improves the dielectric property of the triboelectric thin film.
Description
(one), technical field:
the invention relates to multiphase composite nano particles and a method for preparing a friction electrification film.
(II), background technology:
with the rapid development of new generation information technologies such as the internet of things technology, big data, artificial intelligence and the like,the number of various sensors for interactive communication has increased dramatically. How to solve the problem of power supply of mass sensing nodes has become a bottleneck in the development of modern information technology. The renewable clean energy with abundant reserves and wide distribution in the environment is converted into electric energy through the energy collection technology to supply power for the wireless sensor network nodes, so that the wireless sensor network node is an effective solution way for breaking the limitation of the traditional power supply mode. Friction nano generators (TENG) have proven to be one of the effective ways to achieve environmentally energy efficient harvesting and conversion as a new subverted energy collector with unprecedented output performance and relatively low cost. However, the problem of low output power exists in the process of engineering application of the friction nano generator, and the problem becomes a bottleneck constraint for further popularization and application of the friction nano generator. The surface charge density of the friction material is a key factor affecting the output power of the friction nano-generator. At present, although the existing technologies such as surface appearance modification, high dielectric nanoparticle doping, chemical functional group grafting, charge injection, optical control enhancement and the like optimize the electrification performance of friction materials to a certain extent, friction nano generators still have the bottleneck problems of low surface charge density, serious charge leakage, poor robustness and the like, and the technologies cannot realize effective control on friction surface charges in real time. Although the emerging optical control friction surface charge technology can regulate the output performance of the friction nano generator in real time through illumination to a certain extent, the electrical output is small, the regulation band is narrow (the surface plasmon resonance can only be excited at a specific wavelength, and the wideband semiconductor TiO is used) 2 The photo-generated carrier (hot electron-hole pair) effect can only be excited by ultraviolet light), the light energy utilization efficiency is low, and the like. Semiconductor TiO 2 Is 3.2eV, when irradiated with light having energy larger than the band gap width 2 When an electron in its valence band is excited, it transitions to the conduction band, generating a corresponding hole in the valence band, thereby creating a hot electron-hole pair. Currently, semiconductor TiO 2 Can only be excited by ultraviolet light and generates carriers (hot electron-hole pairs) with a low concentration.
(III), summary of the invention:
the invention is to be understoodThe technical problems of the block are: a multiphase composite nanoparticle comprising noble metal nanoparticles and semiconductor TiO and a method of preparing a triboelectric thin film are provided 2 The noble metal nano particles and semiconductor TiO can be effectively increased by being loaded on the surfaces of SiO2 microspheres 2 And can ensure noble metal nano particles and semiconductor TiO 2 Meanwhile, illumination is fully received, and the friction electrification film is modified by doping multiphase composite nano particles, so that wide spectrum regulation and control of the surface charge density of the friction electrification film are realized, the dielectric property of the friction electrification film is improved, and the friction nano generator adopting the friction electrification film has the advantages of good output performance, wide regulation and control spectrum bandwidth, real time, simplicity and reliability.
The technical scheme of the invention is as follows:
a preparation method of multiphase composite nano particles specifically comprises the following steps:
step 1, preparing SiO 2 The microsphere specifically comprises the following steps:
step 1.1, mixing 2-propanol, ammonia water and deionized water according to a volume ratio of 15-25: 1: mixing according to the proportion of 2-5 to obtain a mixed solution A, and then putting the mixed solution A into an oil bath pot to be heated to 60-80 ℃; wherein, the concentration of the 2-propanol is 99.9 percent, and the concentration of the ammonia water is 20 to 30 percent;
step 1.2, injecting tetraethyl orthosilicate (TEOS) into the mixed solution A within 5-10 seconds to obtain a mixed solution B; wherein, 5-20 mL of tetraethyl orthosilicate is added into every 1mL of ammonia water;
step 1.3, stirring the mixed solution B for 2-5 hours by using a stirrer, and drying the stirred mixed solution B by using a centrifugal dryer to obtain colloid balls; wherein the rotating speed of the stirrer is 800 r/min-1500 r/min;
step 1.4, washing the colloid balls with absolute ethyl alcohol, and drying the colloid balls in air to obtain SiO 2 A microsphere;
step 2, at SiO 2 Noble metal nano particles are uniformly deposited on the microsphere surface to form composite particles, and the composite particles specifically containThe method comprises the following steps:
step 2.1, siO is processed 2 The microspheres are dissolved in 2-propanol to obtain a mixed solution C; wherein, every 1mg of SiO 2 Adding 30-60 mL of 2-propanol into the microspheres, wherein the concentration of the 2-propanol is 99.9%;
step 2.2, mixing the mixed solution C with 3-aminopropyl triethoxysilane (APTES) to obtain a mixed solution D; wherein the volume ratio of the mixed solution C to the 3-aminopropyl triethoxysilane is 60-100:1;
step 2.3, stirring and defoaming the mixed solution D, and then heating in vacuum at 60-120 ℃ for 1-2.5 hours to obtain precipitate, namely aminated SiO 2 Microspheres, the step is to make the silicon surface have amino functional groups;
step 2.4, amination of SiO 2 Washing the microspheres with absolute ethyl alcohol, and drying the microspheres in a vacuum drying oven at 60-70 ℃ for 10-15 hours;
step 2.5, amination of SiO treated in step 2.4 2 Dispersing the microspheres in deionized water to obtain a mixed solution E; wherein, per 1mg of aminated SiO 2 Adding 30-80 mL of deionized water into the microspheres;
2.6, adding 1-10wt.% of noble metal nano particles into the mixed solution E, dispersing by an ultrasonic disperser and drying by a centrifugal dryer in sequence to obtain composite particles; wherein, the particle diameter of the noble metal nano particles is 15 nm-30 nm;
step 3, wrapping the semiconductor TiO on the outer layer of the composite particle 2 Forming multiphase composite nano particles, which specifically comprises the following steps:
step 3.1, dissolving the composite particles obtained in the step 2.6 in absolute ethyl alcohol to obtain a mixed solution F, and dissolving hydroxypropyl cellulose (HPC) in deionized water to obtain a mixed solution G; wherein, 30-80 mL of absolute ethyl alcohol is added into each 1mg of composite particles, and 5-10 mL of deionized water is added into each 100mg of hydroxypropyl cellulose;
step 3.2, adding the mixed solution G into the mixed solution F to obtain a mixed solution H; wherein the volume ratio of the mixed solution G to the mixed solution F is 2-3:1;
step 3.3, dispersing the mixed solution H by adopting an ultrasonic disperser, and then stirring and defoaming the mixed solution H in sequence;
step 3.4, dissolving tetrabutyl titanate (TBOT) in absolute ethyl alcohol to obtain a mixed solution I; wherein, the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is 1: 10-20 parts;
step 3.5, dropwise and slowly dripping the mixed solution I into the mixed solution H treated in the step 3.3, and refluxing in an air environment at 60-120 ℃ for 1.5-2.5 hours to obtain a precipitate; wherein, the volume ratio of the mixed solution I to the mixed solution H is 1:10 to 15 percent;
and 3.6, washing the precipitate obtained in the step 3.5 by using absolute ethyl alcohol, drying for 8-24 hours in a vacuum environment at 60-120 ℃, and finally calcining for 30-180 minutes in an air environment at 450-500 ℃ to obtain the multiphase composite nano particles.
In step 1.3, the stirrer is a magnetic stirrer.
In the step 1.4, the colloid balls are washed by absolute ethyl alcohol for 10 to 15 times;
in step 2.4, the aminated SiO is reacted with 2 Washing the microspheres with absolute ethyl alcohol for 3-5 times;
in the step 3.6, the precipitate obtained in the step 3.5 is washed with absolute ethyl alcohol for 10 times to 15 times.
The noble metal nano particles are Ag nano particles or Au nano particles, and the composite particles are SiO 2 Composite particles of @ Ag or SiO 2 @Au composite particles, wherein the multiphase composite nano particles are SiO 2 @Ag@TiO 2 Multiphase composite nanoparticles or SiO 2 @Au@TiO 2 Multiphase composite nanoparticles.
The multiphase composite nano particles prepared by the preparation method.
A method for preparing a triboelectric film by utilizing the multiphase composite nano particles specifically comprises the following steps:
step a, weighing liquid Polydimethylsiloxane (PDMS) by adopting a balance, adding multiphase composite nano particles into the liquid polydimethylsiloxane according to the mass fraction of 0.05-5 wt.%, performing ultrasonic dispersion, planetary stirring and defoaming treatment to obtain a component A, mixing the component A with a curing agent, and performing secondary stirring and secondary defoaming treatment to obtain a component B;
b, weighing the liquid polydimethylsiloxane again by adopting a balance, adding a curing agent, and performing ultrasonic dispersion, planetary stirring and defoaming treatment to obtain a component C;
and C, spin-coating the component C on the surface of the electrode by adopting a spin-coating instrument, then drying the electrode in an air environment, spin-coating the component B on the surface of the component C by adopting the spin-coating instrument when the component C on the surface of the electrode is not completely cured, and finally drying the electrode in a vacuum environment to completely cure the component B and the component C, thereby obtaining the friction electrification film attached on the surface of the electrode.
In step a: the ultrasonic dispersion time is 5-10 minutes, the planetary stirring time is 3-5 minutes, the defoaming time is 30-120 seconds, the curing agent is a liquid curing agent, and the volume ratio of the component A to the curing agent is 8-12: 1, the time of secondary stirring is 5-10 minutes, and the time of secondary defoaming is 30-120 seconds.
In step b: the curing agent is a liquid curing agent, and the volume ratio of the liquid polydimethylsiloxane to the curing agent is 8-12: 1, the planetary stirring time is 5-10 minutes, and the defoaming time is 30-120 seconds.
In step c: spin-coating the component C on the surface of the electrode by adopting a spin-coating method, wherein the spin-coating method adopts a slow spin-coating and high-speed shaping method, and specifically comprises the following steps: firstly, spin coating is carried out for 100 to 300 seconds under the rotation speed of 80 to 300r/min, and then the spin coating is carried out for 10 to 30 seconds under the rotation speed of 1000 to 2000r/min; when the component B is spin-coated on the surface of the component C, the rotating speed of a spin-coating instrument is 800-2000 r/min; the temperature of the drying treatment in the air environment is 60-80 ℃; the temperature of the drying treatment is 70-80 ℃ under the vacuum environment.
The triboelectric film prepared by the method comprises a two-layer structure: a pure PDMS layer (formed from the C-component) and a doped PDMS layer (formed from the B-component). The pure PDMS layer can effectively block leakage of charges. The doped PDMS layer is positioned on the upper surface, so that the multi-phase composite nano particles can be fully irradiated. The pure PDMS layer and the film forming material of the doped PDMS layer are Polydimethylsiloxane (PDMS), and the interface crosslinking degree of the same substrate material is good.
Because the doped PDMS layer is doped with the multiphase composite nano particles, electrons in the noble metal nano particles (Au and Ag) in the multiphase composite nano particles can be displaced under the action of incident light, so that a polarized electric field is generated. Under the action of the polarized electric field, electrons in the noble metal nano particles vibrate, so that a vibration wave called a plasmon is generated. The surface strong local electromagnetic field generated by the noble metal nano particles can greatly improve the adjacent semiconductor TiO in the multiphase composite nano particles 2 Can also effectively capture photo-generated electrons and accelerate semiconductor TiO 2 The electrons and the holes are separated, thereby achieving the purpose of obviously improving the concentration of the photo-generated carriers in the semiconductor. Meanwhile, the surface plasmon resonance energy sensitized wide band gap semiconductor TiO of the noble metal nano particles 2 The limitation of ultraviolet excitation is broken through, so that photo-generated electron-hole pairs excited by visible light are obtained, the band of photo-generated carriers can be effectively widened, and the hot electron-hole pairs are directionally arranged under the drive of a friction electric field, so that negative charge traps are formed in the friction layer, and the electrification performance of the friction electrification film is enhanced.
The friction nano generator manufactured by the friction electrification film comprises an upper supporting layer, a lower supporting layer, an upper electrode, a lower electrode and the friction electrification film, wherein the upper electrode is stuck on the lower surface of the upper supporting layer, the lower electrode is stuck on the upper surface of the lower supporting layer, the friction electrification film is stuck on the upper surface of the lower electrode, and an air gap is reserved between the upper electrode and the friction electrification film, so that a parallel capacitor plate structure is formed.
The upper supporting layer and the lower supporting layer are made of transparent acrylic materials; the upper electrode is a silver nanowire transparent electrode or an ITO transparent electrode, and the lower electrode is made of copper foil.
The invention has the beneficial effects that:
1, the multiphase composite nanoparticle of the invention combines noble metal nanoparticles with semiconductor TiO 2 The noble metal nano particles and semiconductor TiO can be effectively increased by being loaded on the surfaces of SiO2 microspheres 2 And can ensure noble metal nano particles and semiconductor TiO 2 While fully receiving illumination.
According to the invention, the triboelectric film is modified by doping the multiphase composite nano particles, so that the dielectric property of the triboelectric film is improved, and the surface plasmon resonance of the noble metal nano particles and the semiconductor TiO are excited simultaneously by illumination 2 Is sensitized by surface plasmon resonance of noble metal nanoparticles 2 Break through wide band gap semiconductor TiO 2 The photo-generated carrier (hot electron-hole pair) effect can only be limited by ultraviolet light excitation, so that a photo-generated electron-hole pair excited by visible light is obtained, the band of the photo-generated carrier can be effectively widened, the ultraviolet to visible wide spectrum regulation and control capability on the surface charge density of the friction electrification film is realized, the utilization rate of sunlight and the surface charge density of the friction electrification film are improved, a reverse electric field is constructed in the friction electrification film through the hot electron-hole pair, and the output performance of the friction nano generator is improved; when the friction electrification film is applied to the friction nano generator, the real-time regulation and control of the output performance of the friction nano generator can be realized through illumination, the friction nano generator is simple and reliable to use, and the friction nano generator can be widely applied to the fields of outdoor mechanical vibration energy collection, self-powered wireless sensing systems, intelligent buildings, intelligent transportation and the like.
(IV), description of the drawings:
FIG. 1 is SiO 2 @Ag@TiO 2 Schematic structural diagram of multiphase composite nanoparticles;
FIG. 2 is a schematic diagram of the principle of a noble metal plasmon resonance sensitized semiconductor;
FIG. 3 is a schematic diagram of a friction nano-generator;
FIG. 4 is a schematic diagram of the principle of operation of a friction nano-generator;
FIG. 5 is a schematic diagram of a mechanism of hot electron-hole modulation friction nano generator output;
FIG. 6 is a graph of experimental results of a broad spectrum modulating frictional effect.
(V), specific embodiments:
embodiment one:
SiO 2 @Ag@TiO 2 the preparation method of the multiphase composite nano particle comprises the following steps:
step 1, preparing SiO 2 The microsphere specifically comprises the following steps:
step 1.1, 2-propanol, ammonia water and deionized water are mixed according to the volume ratio of 20:1:4, mixing the materials in proportion to obtain a mixed solution A, and then putting the mixed solution A into an oil bath pot to be heated to 70 ℃; wherein the concentration of 2-propanol is 99.9%, and the concentration of ammonia water is 25%;
step 1.2, tetraethyl orthosilicate (TEOS) is injected into the mixed solution A within 7 seconds to obtain a mixed solution B; wherein, every 1mL of ammonia water is added with 10mL of tetraethyl orthosilicate;
step 1.3, stirring the mixed solution B for 4 hours by using a magnetic stirrer, and drying the stirred mixed solution B by using a centrifugal dryer to obtain colloid balls; wherein the rotating speed of the stirrer is 1000r/min;
step 1.4, washing the colloid balls with absolute ethyl alcohol for 12 times, and drying the colloid balls in air to obtain SiO 2 A microsphere;
step 2, at SiO 2 Uniformly depositing Ag nano particles on the microsphere surface to form SiO 2 The @ Ag composite particle specifically comprises the following steps:
step 2.1, siO is processed 2 The microspheres are dissolved in 2-propanol to obtain a mixed solution C; wherein, every 1mg of SiO 2 50mL of 2-propanol is added into the microsphere, and the concentration of the 2-propanol is 99.9%;
step 2.2, mixing the mixed solution C with 3-aminopropyl triethoxysilane (APTES) to obtain a mixed solution D; wherein the volume ratio of the mixed solution C to the 3-aminopropyl triethoxysilane is 50:1;
step 2.3, stirring and defoaming the mixed solution D, and then heating the mixed solution D in vacuum at 80 ℃ for 2 hoursThe precipitate obtained is the aminated SiO 2 Microspheres, the step is to make the silicon surface have amino functional groups;
step 2.4, amination of SiO 2 Washing the microspheres with absolute ethyl alcohol for 4 times, and drying the microspheres in a vacuum drying oven at 65 ℃ for 12 hours;
step 2.5, amination of SiO treated in step 2.4 2 Dispersing the microspheres in deionized water to obtain a mixed solution E; wherein, per 1mg of aminated SiO 2 Adding 40mL of deionized water into the microspheres;
step 2.6, adding Ag nano particles with mass fraction of 5wt.% into the mixed solution E, dispersing by an ultrasonic disperser and drying by a centrifugal dryer in sequence to obtain SiO 2 Composite particles of @ Ag; wherein, the grain diameter of the Ag nano-particles is 20nm;
step 3, at SiO 2 Semiconductor TiO coated on outer layer of Ag composite particle 2 Forming multiphase composite nano-particle SiO 2 @Ag@TiO 2 The method specifically comprises the following steps:
step 3.1, siO obtained in step 2.6 2 Dissolving @ Ag composite particles in absolute ethyl alcohol to obtain a mixed solution F, and dissolving hydroxypropyl cellulose (HPC) in deionized water to obtain a mixed solution G; wherein, every 1mg of SiO 2 50mL of absolute ethyl alcohol is added into the @ Ag composite particles, and 7mL of deionized water is added into each 100mg of hydroxypropyl cellulose;
step 3.2, adding the mixed solution G into the mixed solution F to obtain a mixed solution H; wherein the volume ratio of the mixed solution G to the mixed solution F is 2.5:1;
step 3.3, dispersing the mixed solution H by adopting an ultrasonic disperser, and then stirring and defoaming the mixed solution H in sequence;
step 3.4, dissolving tetrabutyl titanate (TBOT) in absolute ethyl alcohol to obtain a mixed solution I; wherein, the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is 1:16;
step 3.5, dropwise and slowly dripping the mixed solution I into the mixed solution H treated in the step 3.3, and refluxing in an air environment at 80 ℃ for 2 hours to obtain a precipitate; wherein, the volume ratio of the mixed solution I to the mixed solution H is 1:12;
step 3.6, washing the precipitate obtained in step 3.5 with absolute ethyl alcohol for 12 times, drying for 12 hours in a vacuum environment at 75 ℃, and finally calcining for 120 minutes in an air environment at 480 ℃ to obtain SiO 2 @Ag@TiO 2 Multiphase composite nanoparticles.
SiO 2 @Ag@TiO 2 The structure of the multiphase composite nanoparticle is shown in fig. 1: ag nanoparticles 8 were uniformly supported on SiO 2 The surface of the microsphere 7 is formed with SiO 2 Ag composite particles, semiconductor TiO 2 9 is wrapped in SiO 2 The structure of the outer layer of the Ag composite particle not only can effectively increase Ag nano particles 8 and semiconductor TiO 2 9 and can ensure the contact interface of Ag nano-particles 8 and semiconductor TiO 2 9 while fully receiving illumination.
By SiO 2 @Ag@TiO 2 The method for preparing the triboelectric thin film by the multiphase composite nano particles comprises the following steps:
step a, weighing liquid Polydimethylsiloxane (PDMS) by adopting a balance, and adding SiO (silicon dioxide) 2 @Ag@TiO 2 Adding the multiphase composite nano particles into liquid polydimethylsiloxane according to the mass fraction of 0.1wt.%, performing ultrasonic dispersion, planetary stirring and defoaming treatment to obtain a component A, mixing the component A with a curing agent, and performing secondary stirring and secondary defoaming treatment to obtain a component B;
b, weighing the liquid polydimethylsiloxane again by adopting a balance, adding a curing agent, and performing ultrasonic dispersion, planetary stirring and defoaming treatment to obtain a component C;
and C, spin-coating the component C on the surface of the electrode by adopting a spin-coating instrument, then drying the electrode in an air environment, spin-coating the component B on the surface of the component C by adopting the spin-coating instrument when the component C on the surface of the electrode is not completely cured, and finally drying the electrode in a vacuum environment to completely cure the component B and the component C, thereby obtaining the friction electrification film attached on the surface of the electrode.
In step a: the ultrasonic dispersion time is 7 minutes, the planetary stirring time is 4 minutes, the defoaming time is 60 seconds, the curing agent is a liquid curing agent, and the volume ratio of the component A to the curing agent is 10:1, the time of the secondary stirring was 7 minutes, and the time of the secondary defoaming was 60 seconds.
In step b: the curing agent is a liquid curing agent, and the volume ratio of the liquid polydimethylsiloxane to the curing agent is 10:1, the planetary stirring time was 7 minutes, and the defoaming time was 60 seconds.
In step c: spin-coating the component C on the surface of the electrode by adopting a spin-coating method, wherein the spin-coating method adopts a slow spin-coating and high-speed shaping method, and specifically comprises the following steps: firstly, the spin coater is adjusted to be at the rotating speed of 100r/min and spin coated for 120 seconds, and then the spin coater is adjusted to be at the rotating speed of 1800r/min and spin coated for 15 seconds; when the component B is spin-coated on the surface of the component C, the rotating speed of a spin coater is 1000r/min; the temperature of the drying treatment in the air environment is 70 ℃, and the reference time for drying can be 5-10 minutes; the drying treatment temperature under vacuum environment is 75 ℃, and the reference time for drying can be 1.5-2 hours.
The triboelectric film prepared by the method comprises a two-layer structure: a pure PDMS layer (formed from the C-component) and a doped PDMS layer (formed from the B-component). The pure PDMS layer can effectively block leakage of charges. The doped PDMS layer is arranged on the upper surface and can enable SiO to be formed 2 @Ag@TiO 2 The multiphase composite nanoparticle is fully illuminated. The pure PDMS layer and the film forming material of the doped PDMS layer are Polydimethylsiloxane (PDMS), and the interface crosslinking degree of the same substrate material is good.
Due to doping of SiO in the doped PDMS layer 2 @Ag@TiO 2 Multiphase composite nano particles, under the action of incident light, siO 2 @Ag@TiO 2 Electrons inside the Ag nanoparticles in the multiphase composite nanoparticles are displaced, thereby generating a polarized electric field. Under the action of the polarized electric field, electrons in the Ag nano particles vibrate, so that a vibration wave called a plasmon is generated. The strong local electromagnetic field generated by Ag nano particles can greatly improve SiO 2 @Ag@TiO 2 Adjacent semiconductor TiO in multiphase composite nanoparticles 2 Can also effectively capture photo-generated electrons and accelerate semiconductorsBulk TiO 2 The electrons and the holes are separated, thereby achieving the purpose of obviously improving the concentration of the photo-generated carriers in the semiconductor. Meanwhile, the surface plasmon resonance energy of the Ag nano particles sensitizes the wide band gap semiconductor TiO 2 The limitation of ultraviolet excitation is broken through, so that photo-generated electron-hole pairs excited by visible light are obtained, the band of photo-generated carriers can be effectively widened, and the hot electron-hole pairs are directionally arranged under the drive of a friction electric field, so that negative charge traps are formed in the friction layer, and the electrification performance of the friction electrification film is enhanced.
FIG. 2 is a schematic diagram of the principle of a noble metal plasmon resonance sensitized semiconductor, localized surface plasmon resonance being an enhanced semiconductor TiO 2 An efficient method of absorption spectroscopy. When surface plasmons are localized on Ag nanoparticles corresponding to or smaller than the wavelength of the light wave, charge density waves will be localized on Ag nanoparticles due to the limitation of the particle boundary conditions, and a localized electric field, called localized surface plasmons, will be formed around them. The localized surface plasmons can undergo non-radiative decay by exciting hot electron-hole pairs in the scale of femtosecond scale through Landolt damping, and the decayed hot electrons are injected into semiconductor TiO 2 Thereby sensitizing semiconductor TiO 2 On one hand, the separation speed of hot electron-hole pairs is accelerated, and the recombination of the hot electron-hole pairs is restrained, so that the concentration of carriers is increased, and on the other hand, the semiconductor TiO is improved 2 The visible light absorptivity of the solar energy source is widened, the spectrum range is widened, and the solar energy utilization rate is improved.
As shown in fig. 3: the friction nano generator manufactured by the friction electrification film comprises an upper supporting layer 1, a lower supporting layer 2, an upper electrode 3, a lower electrode 4 and the friction electrification film 5, wherein the upper electrode 3 is stuck on the lower surface of the upper supporting layer 1, the lower electrode 4 is stuck on the upper surface of the lower supporting layer 2, the friction electrification film 5 is stuck on the upper surface of the lower electrode 4, and an air gap is reserved between the upper electrode 3 and the friction electrification film 5, so that a parallel capacitor plate structure is formed.
The upper supporting layer 1 and the lower supporting layer 2 are made of transparent acrylic materials; the upper electrode 3 is a silver nanowire transparent electrode, and the lower electrode 4 is made of copper foil.
Fig. 4 is a schematic diagram of the working principle of the friction nano-generator, when an external force F in a vertical direction acts on the upper supporting layer 1, the upper electrode 3 contacts with the friction electrification film 5, so that negative charges are accumulated on the friction electrification film 5, and positive charges are accumulated on the upper electrode 3; after the acting force F in the vertical direction is removed, the upper electrode 3 is separated from the friction electrification film 5, potential difference is formed between the upper electrode 3 and the lower electrode 4, electrons can flow from the lower electrode 4 to the upper electrode 3, and current I1 is formed on an external load R of the friction nano generator; when the external force F in the vertical direction acts again, the upper electrode 3 contacts the triboelectric thin film 5 again, and electrons flow back, so that a current I2 is formed on the external load R of the triboelectric nano-generator. When the friction nano generator is actually used, the external force F is continuously applied and released, the upper electrode 3 is continuously contacted with and separated from the friction electrification film 5, so that continuous current is formed on an external load R of the friction nano generator, and electric energy is continuously generated.
FIG. 5 is a schematic diagram showing the mechanism of hot electron-hole pair control friction nano generator output, under light irradiation, surface plasmon resonance coupling semiconductor TiO of Ag nanoparticles in multiphase composite nanoparticles 2 Hot electron-hole pairs are accumulated in the triboelectric thin film and tend to be vertically aligned in the triboelectric thin film under the drive of an electric field (electric field E1 formed by the triboelectric effect) from the upper surface of the triboelectric thin film to the lower electrode. On the one hand, the vertically arranged hot electron-hole pairs are similar to the polarization of dipoles, and can be used as negative charge traps in the contact electrification process, so that the charge trapping capacity of the friction electrification film is enhanced, the electrification performance of the friction electrification film is enhanced, and the output performance of the friction nano generator is improved. On the other hand, the vertically aligned hot electron-hole pairs create an electric field (E2) within the triboelectric thin film that is opposite to the electric field E1. The weakening of the total field intensity in the friction electrification film can increase the inherent capacitance C of the friction nano generator, so that the aim of optimizing the output performance of the friction nano generator is fulfilled.
The short-circuit Current (μA) of the friction nano generator is tested under different illumination environments (no illumination, ultraviolet illumination and ultraviolet + visible illumination), and the result is shown in fig. 6, and it can be seen from fig. 6 that the short-circuit Current of the friction nano generator under the ultraviolet illumination is greater than the short-circuit Current of the friction nano generator under the no illumination, and the short-circuit Current of the friction nano generator under the ultraviolet + visible illumination is greater than the short-circuit Current of the friction nano generator under the ultraviolet illumination, which indicates that the composite nano particles realize the wide spectrum regulation function of the friction nano generator.
Embodiment two:
SiO 2 @Au@TiO 2 the preparation method of the multiphase composite nano particle comprises the following steps:
step 1, preparing SiO 2 The microsphere specifically comprises the following steps:
step 1.1, 2-propanol, ammonia water and deionized water are mixed according to the volume ratio of 15:1:2, mixing to obtain a mixed solution A, and then putting the mixed solution A into an oil bath pot to be heated to 60 ℃; wherein the concentration of 2-propanol is 99.9%, and the concentration of ammonia water is 20%;
step 1.2, tetraethyl orthosilicate (TEOS) is injected into the mixed solution A within 5 seconds to obtain a mixed solution B; wherein, 5mL of tetraethyl orthosilicate is added to each 1mL of ammonia water;
step 1.3, stirring the mixed solution B for 2 hours by using a magnetic stirrer, and drying the stirred mixed solution B by using a centrifugal dryer to obtain colloid balls; wherein the rotating speed of the stirrer is 800r/min;
step 1.4, washing the colloid balls with absolute ethyl alcohol for 10 times, and drying the colloid balls in air to obtain SiO 2 A microsphere;
step 2, at SiO 2 Uniformly depositing Au nano particles on the microsphere surface to form SiO 2 The @ Au composite particle specifically comprises the following steps:
step 2.1, siO is processed 2 The microspheres are dissolved in 2-propanol to obtain a mixed solution C; wherein, every 1mg of SiO 2 30mL of 2-propanol is added into the microsphere, and the concentration of the 2-propanol is 99.9%;
step 2.2, mixing the mixed solution C with 3-aminopropyl triethoxysilane (APTES) to obtain a mixed solution D; wherein the volume ratio of the mixed solution C to the 3-aminopropyl triethoxysilane is 60:1;
step 2.3, stirring and defoaming the mixed solution D, and then heating the mixed solution D in vacuum at 60 ℃ for 1 hour to obtain precipitate, namely the aminated SiO 2 Microspheres, the step is to make the silicon surface have amino functional groups;
step 2.4, amination of SiO 2 Washing the microspheres with absolute ethyl alcohol for 3 times, and drying the microspheres in a vacuum drying oven at 60 ℃ for 10 hours;
step 2.5, amination of SiO treated in step 2.4 2 Dispersing the microspheres in deionized water to obtain a mixed solution E; wherein, per 1mg of aminated SiO 2 Adding 30mL of deionized water into the microspheres;
step 2.6, adding Au nano particles with the mass fraction of 1wt.% into the mixed solution E, dispersing by an ultrasonic disperser and drying by a centrifugal dryer in sequence to obtain SiO 2 An @ Au composite particle; wherein, the particle size of the Au nano-particles is 15nm;
step 3, at SiO 2 Semiconductor TiO coated on outer layer of@Au composite particle 2 Forming multiphase composite nano-particle SiO 2 @Au@TiO 2 The method specifically comprises the following steps:
step 3.1, siO obtained in step 2.6 2 Dissolving the@Au composite particles in absolute ethyl alcohol to obtain a mixed solution F, and dissolving hydroxypropyl cellulose (HPC) in deionized water to obtain a mixed solution G; wherein, every 1mg of SiO 2 30mL of absolute ethyl alcohol is added into the @ Au composite particles, and 5mL of deionized water is added into each 100mg of hydroxypropyl cellulose;
step 3.2, adding the mixed solution G into the mixed solution F to obtain a mixed solution H; wherein the volume ratio of the mixed solution G to the mixed solution F is 2:1;
step 3.3, dispersing the mixed solution H by adopting an ultrasonic disperser, and then stirring and defoaming the mixed solution H in sequence;
step 3.4, dissolving tetrabutyl titanate (TBOT) in absolute ethyl alcohol to obtain a mixed solution I; wherein, the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is 1:10;
step 3.5, dropwise and slowly dripping the mixed solution I into the mixed solution H treated in the step 3.3, and refluxing in an air environment at 60 ℃ for 1.5 hours to obtain a precipitate; wherein, the volume ratio of the mixed solution I to the mixed solution H is 1:10;
step 3.6, washing the precipitate obtained in the step 3.5 with absolute ethyl alcohol for 10 times, drying for 8 hours in a vacuum environment at 60 ℃, and finally calcining for 30 minutes in an air environment at 450 ℃ to obtain SiO 2 @Au@TiO 2 Multiphase composite nanoparticles.
By SiO 2 @Au@TiO 2 The method for preparing the triboelectric thin film by the multiphase composite nano particles comprises the following steps:
step a, weighing liquid Polydimethylsiloxane (PDMS) by adopting a balance, and adding SiO (silicon dioxide) 2 @Au@TiO 2 Adding the multiphase composite nano particles into liquid polydimethylsiloxane according to the mass fraction of 0.05wt.%, performing ultrasonic dispersion, planetary stirring and defoaming treatment to obtain a component A, mixing the component A with a curing agent, and performing secondary stirring and secondary defoaming treatment to obtain a component B;
b, weighing the liquid polydimethylsiloxane again by adopting a balance, adding a curing agent, and performing ultrasonic dispersion, planetary stirring and defoaming treatment to obtain a component C;
and C, spin-coating the component C on the surface of the electrode by adopting a spin-coating instrument, then drying the electrode in an air environment, spin-coating the component B on the surface of the component C by adopting the spin-coating instrument when the component C on the surface of the electrode is not completely cured, and finally drying the electrode in a vacuum environment to completely cure the component B and the component C, thereby obtaining the friction electrification film attached on the surface of the electrode.
In step a: the ultrasonic dispersion time is 5 minutes, the planetary stirring time is 3 minutes, the defoaming time is 30 seconds, the curing agent is a liquid curing agent, and the volume ratio of the component A to the curing agent is 8:1, the time of the secondary stirring is 5 minutes, and the time of the secondary defoaming is 30 seconds.
In step b: the curing agent is a liquid curing agent, and the volume ratio of the liquid polydimethylsiloxane to the curing agent is 8:1, the planetary stirring time was 5 minutes, and the defoaming time was 30 seconds.
In step c: spin-coating the component C on the surface of the electrode by adopting a spin-coating method, wherein the spin-coating method adopts a slow spin-coating and high-speed shaping method, and specifically comprises the following steps: firstly, the spin coater is adjusted to be at the rotating speed of 80r/min and spin coated for 100 seconds, and then the spin coater is adjusted to be at the rotating speed of 1000r/min and spin coated for 10 seconds; when the component B is spin-coated on the surface of the component C, the rotating speed of a spin coater is 800r/min; the temperature of the drying treatment in the air environment is 60 ℃, and the reference time for drying can be 5-10 minutes; the drying treatment temperature under vacuum environment is 70 ℃, and the reference time for drying can be 1.5-2 hours.
Embodiment III:
SiO 2 @Ag@TiO 2 the preparation method of the multiphase composite nano particle comprises the following steps:
step 1, preparing SiO 2 The microsphere specifically comprises the following steps:
step 1.1, 2-propanol, ammonia water and deionized water are mixed according to the volume ratio of 25:1:5, mixing the materials in proportion to obtain a mixed solution A, and then putting the mixed solution A into an oil bath pot to be heated to 80 ℃; wherein the concentration of 2-propanol is 99.9%, and the concentration of ammonia water is 30%;
step 1.2, tetraethyl orthosilicate (TEOS) is injected into the mixed solution A within 10 seconds to obtain a mixed solution B; wherein, 20mL of tetraethyl orthosilicate is added to each 1mL of ammonia water;
step 1.3, stirring the mixed solution B for 5 hours by using a magnetic stirrer, and drying the stirred mixed solution B by using a centrifugal dryer to obtain colloid balls; wherein the rotating speed of the stirrer is 1500r/min;
step 1.4, washing the colloid balls with absolute ethyl alcohol for 15 times, and drying the colloid balls in air to obtain SiO 2 A microsphere;
step 2, at SiO 2 Uniformly depositing Ag nano particles on the microsphere surface to form SiO 2 The @ Ag composite particle specifically comprises the following steps:
step 2.1, siO is processed 2 The microspheres are dissolved in 2-propanol to obtain a mixed solutionA liquid C; wherein, every 1mg of SiO 2 60mL of 2-propanol is added into the microsphere, and the concentration of the 2-propanol is 99.9%;
step 2.2, mixing the mixed solution C with 3-aminopropyl triethoxysilane (APTES) to obtain a mixed solution D; wherein the volume ratio of the mixed solution C to the 3-aminopropyl triethoxysilane is 100:1;
step 2.3, stirring and defoaming the mixed solution D, and then heating in vacuum at 120 ℃ for 2.5 hours to obtain precipitate, namely the aminated SiO 2 Microspheres, the step is to make the silicon surface have amino functional groups;
step 2.4, amination of SiO 2 Washing the microspheres with absolute ethyl alcohol for 5 times, and drying the microspheres in a vacuum drying oven at 70 ℃ for 15 hours;
step 2.5, amination of SiO treated in step 2.4 2 Dispersing the microspheres in deionized water to obtain a mixed solution E; wherein, per 1mg of aminated SiO 2 Adding 80mL of deionized water into the microspheres;
step 2.6, adding Ag nano particles with the mass fraction of 10wt.% into the mixed solution E, dispersing by an ultrasonic disperser and drying by a centrifugal dryer in sequence to obtain SiO 2 Composite particles of @ Ag; wherein, the grain diameter of the Ag nano-particles is 30nm;
step 3, at SiO 2 Semiconductor TiO coated on outer layer of Ag composite particle 2 Forming multiphase composite nano-particle SiO 2 @Ag@TiO 2 The method specifically comprises the following steps:
step 3.1, siO obtained in step 2.6 2 Dissolving @ Ag composite particles in absolute ethyl alcohol to obtain a mixed solution F, and dissolving hydroxypropyl cellulose (HPC) in deionized water to obtain a mixed solution G; wherein, every 1mg of SiO 2 80mL of absolute ethyl alcohol is added into the @ Ag composite particles, and 10mL of deionized water is added into each 100mg of hydroxypropyl cellulose;
step 3.2, adding the mixed solution G into the mixed solution F to obtain a mixed solution H; wherein the volume ratio of the mixed solution G to the mixed solution F is 3:1;
step 3.3, dispersing the mixed solution H by adopting an ultrasonic disperser, and then stirring and defoaming the mixed solution H in sequence;
step 3.4, dissolving tetrabutyl titanate (TBOT) in absolute ethyl alcohol to obtain a mixed solution I; wherein, the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is 1:20, a step of;
step 3.5, dropwise and slowly dripping the mixed solution I into the mixed solution H treated in the step 3.3, and refluxing in an air environment at 120 ℃ for 2.5 hours to obtain a precipitate; wherein, the volume ratio of the mixed solution I to the mixed solution H is 1:15;
step 3.6, washing the precipitate obtained in step 3.5 with absolute ethyl alcohol for 15 times, drying for 24 hours in a vacuum environment at 120 ℃, and calcining for 180 minutes in an air environment at 500 ℃ to obtain SiO 2 @Ag@TiO 2 Multiphase composite nanoparticles.
By SiO 2 @Ag@TiO 2 The method for preparing the triboelectric thin film by the multiphase composite nano particles comprises the following steps:
step a, weighing liquid Polydimethylsiloxane (PDMS) by adopting a balance, and adding SiO (silicon dioxide) 2 @Ag@TiO 2 Adding the multiphase composite nano particles into liquid polydimethylsiloxane according to the mass fraction of 5wt.%, performing ultrasonic dispersion, planetary stirring and defoaming treatment to obtain a component A, mixing the component A with a curing agent, and performing secondary stirring and secondary defoaming treatment to obtain a component B;
b, weighing the liquid polydimethylsiloxane again by adopting a balance, adding a curing agent, and performing ultrasonic dispersion, planetary stirring and defoaming treatment to obtain a component C;
and C, spin-coating the component C on the surface of the electrode by adopting a spin-coating instrument, then drying the electrode in an air environment, spin-coating the component B on the surface of the component C by adopting the spin-coating instrument when the component C on the surface of the electrode is not completely cured, and finally drying the electrode in a vacuum environment to completely cure the component B and the component C, thereby obtaining the friction electrification film attached on the surface of the electrode.
In step a: the ultrasonic dispersion time is 10 minutes, the planetary stirring time is 5 minutes, the defoaming time is 120 seconds, the curing agent is a liquid curing agent, and the volume ratio of the component A to the curing agent is 12:1, the time of the secondary stirring is 10 minutes, and the time of the secondary defoaming is 120 seconds.
In step b: the curing agent is a liquid curing agent, and the volume ratio of the liquid polydimethylsiloxane to the curing agent is 12:1, the planetary stirring time was 10 minutes, and the defoaming time was 120 seconds.
In step c: spin-coating the component C on the surface of the electrode by adopting a spin-coating method, wherein the spin-coating method adopts a slow spin-coating and high-speed shaping method, and specifically comprises the following steps: firstly, regulating a spin coater to a rotation speed of 300r/min, spin-coating for 300 seconds, and then regulating the spin coater to a rotation speed of 2000r/min, spin-coating for 30 seconds; when the component B is spin-coated on the surface of the component C, the rotating speed of a spin coater is 2000r/min; the temperature of the drying treatment in the air environment is 80 ℃, and the reference time for drying can be 5-10 minutes; the temperature of the drying treatment under the vacuum environment is 80 ℃, and the reference time for drying can be 1.5 to 2 hours.
Claims (7)
1. A method for preparing a triboelectric film by utilizing multiphase composite nano particles is characterized by comprising the following steps:
step a, weighing liquid polydimethylsiloxane, adding multiphase composite nano particles into the liquid polydimethylsiloxane according to the mass fraction of 0.05-5 wt.%, performing ultrasonic dispersion, planetary stirring and defoaming treatment to obtain a component A, mixing the component A with a curing agent, and performing secondary stirring and secondary defoaming treatment to obtain a component B;
step b, weighing liquid polydimethylsiloxane again, adding a curing agent, and performing ultrasonic dispersion, planetary stirring and defoaming treatment to obtain a component C;
c, spin-coating the component C on the surface of the electrode by adopting a spin-coating instrument, then drying the electrode in an air environment, spin-coating the component B on the surface of the component C by adopting the spin-coating instrument when the component C on the surface of the electrode is not completely cured, and finally drying the electrode in a vacuum environment to completely cure the component B and the component C, thereby obtaining the friction electrification film attached on the surface of the electrode;
the preparation method of the multiphase composite nano particle comprises the following steps:
the step 1 specifically comprises the following steps:
step 1.1, mixing 2-propanol, ammonia water and deionized water according to a volume ratio of 15-25: 1: mixing according to the proportion of 2-5 to obtain a mixed solution A, and then putting the mixed solution A into an oil bath pot to be heated to 60-80 ℃; wherein, the concentration of the 2-propanol is 99.9 percent, and the concentration of the ammonia water is 20 to 30 percent;
step 1.2, injecting tetraethyl orthosilicate into the mixed solution A within 5-10 seconds to obtain a mixed solution B; wherein, 5-20 mL of tetraethyl orthosilicate is added into every 1mL of ammonia water;
step 1.3, stirring the mixed solution B for 2-5 hours by using a stirrer, and drying the stirred mixed solution B by using a centrifugal dryer to obtain colloid balls; wherein the rotating speed of the stirrer is 800 r/min-1500 r/min;
step 1.4, washing the colloid balls with absolute ethyl alcohol, and drying the colloid balls in air to obtain SiO 2 A microsphere;
step 2, specifically comprising the following steps:
step 2.1, siO is processed 2 The microspheres are dissolved in 2-propanol to obtain a mixed solution C; wherein, every 1mg of SiO 2 Adding 30-60 mL of 2-propanol into the microspheres, wherein the concentration of the 2-propanol is 99.9%;
step 2.2, mixing the mixed solution C with 3-aminopropyl triethoxysilane to obtain a mixed solution D; wherein the volume ratio of the mixed solution C to the 3-aminopropyl triethoxysilane is 60-100:1;
step 2.3, stirring and defoaming the mixed solution D, and then heating in vacuum at 60-120 ℃ for 1-2.5 hours to obtain precipitate, namely aminated SiO 2 A microsphere;
step 2.4, amination of SiO 2 Washing the microspheres with absolute ethyl alcohol, and drying the microspheres in a vacuum drying oven at 60-70 ℃ for 10-15 hours;
step 2.5, amination of SiO treated in step 2.4 2 Dispersing the microspheres in deionized water to obtain a mixed solution E; wherein, per 1mg of aminated SiO 2 Microsphere addition 30mL80mL of deionized water;
2.6, adding 1-10wt.% of noble metal nano particles into the mixed solution E, dispersing by an ultrasonic disperser and drying by a centrifugal dryer in sequence to obtain composite particles; wherein, the particle diameter of the noble metal nano particles is 15 nm-30 nm;
step 3, specifically comprising the following steps:
step 3.1, dissolving the composite particles obtained in the step 2.6 in absolute ethyl alcohol to obtain a mixed solution F, and dissolving hydroxypropyl cellulose in deionized water to obtain a mixed solution G; wherein, 30-80 mL of absolute ethyl alcohol is added into each 1mg of composite particles, and 5-10 mL of deionized water is added into each 100mg of hydroxypropyl cellulose;
step 3.2, adding the mixed solution G into the mixed solution F to obtain a mixed solution H; wherein the volume ratio of the mixed solution G to the mixed solution F is 2-3:1;
step 3.3, dispersing the mixed solution H by adopting an ultrasonic disperser, and then stirring and defoaming the mixed solution H in sequence;
step 3.4, tetrabutyl titanate is dissolved in absolute ethyl alcohol to obtain a mixed solution I; wherein, the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is 1: 10-20 parts;
step 3.5, dropwise adding the mixed solution I into the mixed solution H treated in the step 3.3, and refluxing in an air environment at 60-120 ℃ for 1.5-2.5 hours to obtain a precipitate; wherein, the volume ratio of the mixed solution I to the mixed solution H is 1:10 to 15 percent;
and 3.6, washing the precipitate obtained in the step 3.5 by using absolute ethyl alcohol, drying for 8-24 hours in a vacuum environment at 60-120 ℃, and finally calcining for 30-180 minutes in an air environment at 450-500 ℃ to obtain the multiphase composite nano particles.
2. The method for producing a triboelectric film according to claim 1, characterized in that: in the step 1.3, the stirrer is a magnetic stirrer.
3. The method for producing a triboelectric film according to claim 1, characterized in that: in the step 1.4, the colloid balls are washed by absolute ethyl alcohol for 10 to 15 times;
in step 2.4, the aminated SiO is reacted with 2 Washing the microspheres with absolute ethyl alcohol for 3-5 times;
in the step 3.6, the precipitate obtained in the step 3.5 is washed with absolute ethyl alcohol for 10 times to 15 times.
4. The method for producing a triboelectric film according to claim 1, characterized in that: the noble metal nano particles are Ag nano particles or Au nano particles, and the composite particles are SiO 2 Composite particles of @ Ag or SiO 2 @Au composite particles, wherein the multiphase composite nano particles are SiO 2 @Ag@TiO 2 Multiphase composite nanoparticles or SiO 2 @Au@TiO 2 Multiphase composite nanoparticles.
5. The method for producing a triboelectric film according to claim 1, characterized in that: in the step a: the ultrasonic dispersion time is 5-10 minutes, the planetary stirring time is 3-5 minutes, the defoaming time is 30-120 seconds, the curing agent is a liquid curing agent, and the volume ratio of the component A to the curing agent is 8-12: 1, the time of secondary stirring is 5-10 minutes, and the time of secondary defoaming is 30-120 seconds.
6. The method for producing a triboelectric film according to claim 1, characterized in that: in the step b: the curing agent is a liquid curing agent, and the volume ratio of the liquid polydimethylsiloxane to the curing agent is 8-12: 1, the planetary stirring time is 5-10 minutes, and the defoaming time is 30-120 seconds.
7. The method for producing a triboelectric film according to claim 1, characterized in that: in the step c: spin-coating the component C on the surface of the electrode by adopting a spin-coating method, wherein the spin-coating method comprises the following steps: firstly, spin coating is carried out for 100 to 300 seconds under the rotation speed of 80 to 300r/min, and then the spin coating is carried out for 10 to 30 seconds under the rotation speed of 1000 to 2000r/min; when the component B is spin-coated on the surface of the component C, the rotating speed of a spin-coating instrument is 800-2000 r/min; the temperature of the drying treatment in the air environment is 60-80 ℃; the temperature of the drying treatment is 70-80 ℃ under the vacuum environment.
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| CN101229957A (en) * | 2007-12-25 | 2008-07-30 | 山东大学 | SiO2/TiO2 hollow compound structural material as well as preparation method and uses thereof |
| WO2017205658A1 (en) * | 2016-05-25 | 2017-11-30 | The Regents Of The University Of Colorado, A Body Corporate | Atomic layer etching on microdevices and nanodevices |
| CN112420396A (en) * | 2020-10-27 | 2021-02-26 | 安徽大学 | SiO modified by silver nano particles2@TiO2Layered microsphere and preparation method and application thereof |
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| CN101229957A (en) * | 2007-12-25 | 2008-07-30 | 山东大学 | SiO2/TiO2 hollow compound structural material as well as preparation method and uses thereof |
| WO2017205658A1 (en) * | 2016-05-25 | 2017-11-30 | The Regents Of The University Of Colorado, A Body Corporate | Atomic layer etching on microdevices and nanodevices |
| CN112420396A (en) * | 2020-10-27 | 2021-02-26 | 安徽大学 | SiO modified by silver nano particles2@TiO2Layered microsphere and preparation method and application thereof |
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