CN109756146B - Nano generator containing micro-nano textured fibroin friction layer and preparation method - Google Patents
Nano generator containing micro-nano textured fibroin friction layer and preparation method Download PDFInfo
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- CN109756146B CN109756146B CN201910008586.9A CN201910008586A CN109756146B CN 109756146 B CN109756146 B CN 109756146B CN 201910008586 A CN201910008586 A CN 201910008586A CN 109756146 B CN109756146 B CN 109756146B
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Abstract
The invention discloses a nano generator containing a micro-nano textured fibroin friction layer and a preparation method thereof, and the nano generator comprises a first polar plate and a second polar plate, wherein the first polar plate is opposite to the second polar plate, the first polar plate comprises a first flexible PET substrate and a first silver nanowire output electrode layer which are sequentially distributed from top to bottom, the second polar plate comprises a fibroin friction layer, a second flexible PET substrate and a second silver nanowire output electrode layer which are sequentially distributed from top to bottom, and the fibroin friction layer is opposite to the first flexible PET substrate; the upper surface of the fibroin friction layer is in a lattice-shaped micro-nano texture, the generator has the characteristics of high transmittance performance and winding electrode performance, and the preparation method has the characteristics of low cost and large-area manufacturing.
Description
Technical Field
The invention belongs to the field of nano friction power generation, and relates to a nano generator containing a micro-nano textured fibroin friction layer and a preparation method thereof.
Background
When two different materials are contacted, the surfaces of the two different materials generate positive and negative static charges due to contact electrification, and when the two different materials are separated, the contact charges correspondingly generate an induced potential difference between the upper electrode and the lower electrode of the materials, so that the conversion of mechanical energy into electric energy is realized. The invention of the nanometer friction generator based on the principle is a milestone discovery in the fields of mechanical energy power generation and self-driving systems. Thus, a completely new mode is provided for effectively collecting mechanical energy (whether organic material or inorganic material). The surface power density of the nano generator can reach 500W/m2The instantaneous energy conversion efficiency reaches about 70 percent, and the micro-power energy conversion device can be used as a sustainable micro-power supply for self-power supply of micro-miniature equipment (such as electronic skin, implantable medical devices and the like); the sensor is used as a self-driven sensor for health monitoring, biosensing, man-machine interaction, environment monitoring, infrastructure safety and the like; and as a basic network unit, the seawater motion energy is collected at low frequency until the great dream of blue pollution-free energy is realized. The energy system of the nanometer generator lays a solid theory and technology for realizing the integration of nanometer devices and large-scale energy supply from the energy collection of the micro scale to the power generation of the macroscopic high energy density from the mechanical vibration of the smile to the vast oceanThe method is technically basic, can be applied to the fields of Internet of things, health care, medical science, national defense safety, artificial intelligence and the like, and can possibly influence the aspects of human social life.
The friction nano generator has multiple working modes, wherein the vertical contact separation mode has the advantages of simple preparation and design, high instantaneous output power, easy realization of multilayer integration and the like. The electron gaining and losing capability and the surface structure design of the friction layer material are the core problems of the power generation performance, and the friction layer with micro-nano texturing can obtain higher electric energy conversion efficiency; meanwhile, the selection of the substrate material and the electrode material can provide guarantee for the stability and the multifunctional integration of the device. The use of green pollution-free materials is also an important requirement for realizing the practical production and commercialization of the friction nano generator as soon as possible, meanwhile, the transparency of the generator itself also determines the wide degree of the application scene of the generator, and the existing research direction rarely takes the high transmittance performance as the improvement target.
Generally speaking, the friction nano-generator based on the green, environment-friendly and biocompatible friction layer material and the transparent and flexible electrode material has less research, and an integrated preparation process with low cost and large-area manufacturing potential is lacked.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a nano generator containing a micro-nano textured fibroin friction layer and a preparation method thereof.
In order to achieve the purpose, the nano generator with the micro-nano textured fibroin friction layer comprises a first polar plate and a second polar plate, wherein the first polar plate is opposite to the second polar plate, the first polar plate comprises a first flexible PET substrate and a first silver nanowire output electrode layer which are sequentially distributed from top to bottom, the second polar plate comprises a fibroin friction layer, a second flexible PET substrate and a second silver nanowire output electrode layer which are sequentially distributed from top to bottom, and the fibroin friction layer is opposite to the first flexible PET substrate;
the upper surface of the fibroin friction layer is in a lattice-shaped micro-nano texture.
The thickness of the first flexible PET substrate and the thickness of the second flexible PET substrate are both 10-1000 microns.
The thickness of the fibroin rubbing layer is 0.1-100 micrometers.
The diameter of the micro-nano texture is 0.05-10 micrometers, and the center distance between two adjacent micro-nano textures is 0-10 micrometers.
The preparation method of the nano generator containing the micro-nano textured fibroin friction layer comprises the following steps:
1) scraping nanowire solution on the upper surface of the first flexible PET substrate in a scraper coating mode, then carrying out thermal annealing or mechanical compression process treatment to obtain a first silver nanowire output electrode layer, meanwhile, scraping nanowire solution on the lower surface of the second flexible PET substrate in a scraper coating mode, and then carrying out thermal annealing and mechanical compression process treatment to obtain a second silver nanowire output electrode layer;
2) coating fibroin solution on the upper surface of the second flexible PET substrate in a blade coating mode, and then air-drying at normal temperature and normal pressure to obtain a fibroin friction layer;
3) depositing micro-nano particle size deionized water formed by electrohydrodynamic atomization on the fibroin friction layer, so as to dissolve and etch a lattice-shaped micro-nano texture on the upper surface of the fibroin friction layer;
4) and placing the first polar plate above the second polar plate, and simultaneously ensuring a gap between the first flexible PET substrate and the fibroin friction layer to form the nano generator containing the micro-nano textured fibroin friction layer.
In the step 1), during blade coating, the first flexible PET substrate and the second flexible PET substrate are adsorbed on the substrate of a blade coating machine in a vacuum adsorption mode, and meanwhile, the heating function of the blade coating machine is started.
The specific operation of the step 3) is as follows:
atomizing deionized water into micro-nano-sized fog drops by an electrohydrodynamic atomization principle, and depositing the fog drops on the upper surface of the fibroin friction layer, so that a lattice-shaped micro-nano texture is dissolved and etched on the upper surface of the fibroin friction layer, wherein the size of the fog drops is determined according to the size of the required micro-nano texture.
The method also comprises the following steps between the step 3) and the step 4): the fibroin friction layer is modified by adopting a mixed solution of ethanol and water, a mixed solution of methanol and water or high-temperature water vapor.
An isolation layer is inserted between the fibroin friction layer and the first flexible PET substrate.
The isolation layer is an ultrathin adhesive tape or an adhesive water layer.
The invention has the following beneficial effects:
the nano generator with the micro-nano textured fibroin friction layer comprises a first polar plate and a second polar plate, wherein the first polar plate comprises a first flexible PET substrate and a first silver nanowire output electrode layer which are sequentially distributed from top to bottom, the second polar plate comprises a fibroin friction layer, a second flexible PET substrate and a second silver nanowire output electrode layer which are sequentially distributed from top to bottom, and the fibroin friction layer is good in biocompatibility and has the characteristics of being environment-friendly and wearable by a human body. The first silver nanowire output electrode layer and the second silver nanowire output electrode layer have transparency and flexibility, so that the generator has the characteristics of high flexibility and high transparency. In addition, the upper surface of the fibroin friction layer is in a lattice-shaped micro-nano texture, so that the electrification efficiency of the surface of the fibroin friction layer is improved, and the power generation capacity of the generator is improved. Meanwhile, in the preparation process of the friction generator, a scraper coating mode is mainly used, in addition, micro-nano particle size deionized water formed through electrohydrodynamic atomization is deposited on the fibroin friction layer, so that a lattice-shaped micro-nano texture structure is dissolved and etched on the upper surface of the fibroin friction layer, the energy consumption of an electrospray process is low, the forming range is large, and the manufacturing advantages of low cost and large area are achieved.
Drawings
Fig. 1 is a schematic diagram of micro-nano particle size deionized water 2 formed by electrohydrodynamic atomization when being deposited on a fibroin friction layer 21;
fig. 2a is a schematic structural diagram of the first plate 10 according to the present invention;
FIG. 2b is a schematic structural diagram of a second plate 20 according to the present invention;
FIG. 3 is a schematic structural view of the present invention;
FIG. 4 is a schematic drawing of an atomic force microscope showing the structure of the fibroin rubbing layer 21;
FIG. 5a is a graph showing the maximum open circuit voltage of the triboelectric nanogenerator according to the first embodiment;
fig. 5b is a graph of the test result of the maximum short-circuit current of the tribo-nanogenerator according to the first embodiment.
The device comprises a needle head, a micro-nano particle size deionized water layer, a micro-nano texture layer, a first polar plate layer, a first flexible PET substrate layer, a first silver nanowire output electrode layer, a second polar plate layer, a fibroin friction layer, a second flexible PET substrate layer, a second silver nanowire output electrode layer, a first silver nanowire output electrode layer, a second polar plate layer, a fibroin friction layer, a second flexible PET substrate layer and a second silver nanowire output electrode layer, wherein the needle head is 1, the.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings:
referring to fig. 2a, 2b and 3, the nano-generator with the micro-nano textured fibroin friction layer according to the present invention includes a first polar plate 10 and a second polar plate 20, wherein the first polar plate 10 faces the second polar plate 20, the first polar plate 10 includes a first flexible PET substrate 11 and a first silver nanowire output electrode layer 12 which are sequentially distributed from top to bottom, the second polar plate 20 includes a fibroin friction layer 21, a second flexible PET substrate 22 and a second silver nanowire output electrode layer 23 which are sequentially distributed from top to bottom, and the fibroin friction layer 21 faces the first flexible PET substrate 11; the upper surface of the fibroin friction layer 21 is in a lattice-shaped micro-nano texture 3.
The thickness of the first flexible PET substrate 11 and the second flexible PET substrate 22 are both 10-1000 microns; the thickness of the fibroin rubbing layer 21 is 0.1-100 micrometers; the diameter of the micro-nano texture 3 is 0.05-10 micrometers, and the center distance between two adjacent micro-nano textures 3 is 0-10 micrometers.
The preparation method of the nano generator containing the micro-nano textured fibroin friction layer comprises the following steps:
1) scraping nanowire solution on the upper surface of the first flexible PET substrate 11 by adopting a scraper coating mode, then carrying out thermal annealing and mechanical compression process treatment to obtain a first silver nanowire output electrode layer 12, meanwhile, scraping nanowire solution on the lower surface of the second flexible PET substrate 22 by adopting a scraper coating mode, and then carrying out thermal annealing and mechanical compression process treatment to obtain a second silver nanowire output electrode layer 23;
2) scraping fibroin solution on the upper surface of the second flexible PET substrate 22 by adopting a scraper coating mode, and then air-drying at normal temperature and normal pressure to obtain a fibroin friction layer 21;
3) depositing micro-nano particle size deionized water 2 formed by electrohydrodynamic atomization on the fibroin friction layer 21, and dissolving and etching a lattice-shaped micro-nano texture 3 on the upper surface of the fibroin friction layer 21;
4) the first polar plate 10 is placed above the second polar plate 20, and meanwhile, a gap is ensured between the first flexible PET substrate 11 and the fibroin friction layer 21, so that the nano generator containing the micro-nano textured fibroin friction layer is formed.
In the step 1), during blade coating, the first flexible PET substrate 11 and the second flexible PET substrate 22 are adsorbed on the substrate of the blade coating machine in a vacuum adsorption mode, and meanwhile, the heating function of the blade coating machine is started.
The specific operation of the step 3) is as follows:
through an electrohydrodynamic atomization principle, deionized water is atomized into micro-nano-sized fog drops, and then the fog drops are deposited on the upper surface of the fibroin friction layer 21, so that the lattice-shaped micro-nano texture 3 is dissolved and etched on the upper surface of the fibroin friction layer 21, wherein the size of the fog drops is determined according to the size of the micro-nano texture 3.
The method also comprises the following steps between the step 3) and the step 4): the fibroin frictional layer 21 is modified by using a mixed solution of ethanol and water, a mixed solution of methanol and water, or high-pressure steam.
An isolation layer is inserted between the fibroin rubbing layer 21 and the first flexible PET substrate 11, wherein the isolation layer is an ultrathin adhesive tape or an adhesive water layer.
The first flexible PET substrate 11 and the first flexible PET substrate 11 are made of polyethylene terephthalate (PET), Polyimide (PI), and polyvinylidene fluoride (PVDF).
Example one
The preparation method of the nano generator containing the micro-nano textured fibroin friction layer comprises the following steps:
1) selecting and cleaning a first flexible PET substrate 11 and a first flexible PET substrate 11, wherein the first flexible PET substrate 11 and the first flexible PET substrate 11 are made of polyethylene terephthalate (PET), ethanol and deionized water are sequentially adopted for ultrasonic cleaning for 10min during cleaning, and then an infrared lamp is used for baking;
scraping nanowire solution on the upper surface of the first flexible PET substrate 11 by adopting a scraper coating mode, then carrying out thermal annealing or mechanical compression process treatment to obtain a first silver nanowire output electrode layer 12, meanwhile, scraping nanowire solution on the lower surface of the second flexible PET substrate 22 by adopting a scraper coating mode, and then carrying out thermal annealing and mechanical compression process treatment to obtain a second silver nanowire output electrode layer 23;
in the scraping process, the distance between the scraper and the substrate is 200 microns, the scraping speed is 15 mm/min, the silver nanowire solution takes deionized water as a dispersion system, the concentration is 10mg/ml, the diameter of the contained silver nanowires is about 100nm, the length is about 30 microns, the first silver nanowire output electrode layer 12 and the second silver nanowire output electrode layer 23 are integrally arranged and distributed in a single-piece mode, and are partially overlapped, so that the whole plane is conductive, and the transmittance is guaranteed as far as possible; after blade coating is finished, placing a sample on a heating table at 100-140 ℃, heating and sintering the silver nanowires for half an hour, then placing the sample at room temperature, and cooling the sample to room temperature, wherein the sheet resistance of the first silver nanowire output electrode layer 12 is lower than 10 omega/square;
2) scraping fibroin solution on the upper surface of the second flexible PET substrate 22 by adopting a scraper coating mode, and then air-drying at normal temperature and normal pressure to obtain a fibroin friction layer 21;
3) depositing micro-nano particle size deionized water 2 formed by electrohydrodynamic atomization on the fibroin friction layer 21, and dissolving and etching a lattice-shaped micro-nano texture 3 on the upper surface of the fibroin friction layer 21;
referring to fig. 1, an atomized solution is a mixed solution of water and ethanol, wherein the volume ratio of deionized water to ethanol is 9:1, the atomization voltage is 6KV, the distance between a needle 1 and a ground electrode is 6cm, the inner diameter of the needle 1 is 200 μm, the solution supply speed is 200 μ l/min, a fibroin friction layer 21 is placed at the central position right below a fog field, micro-nano-sized droplets generated by electrostatic atomization generate a process of local dissolution and evaporation on the surface of the fibroin friction layer 21, each droplet induces the fibroin friction layer 21 to generate a crater-shaped micro-nano structure with a low middle and a high periphery under the action of a coffee ring effect, wherein the electrostatic atomization is continuously induced for 5min, and the micro-nano structure covers the whole surface of the fibroin friction layer 21 to generate the micro-nano-textured fibroin friction layer 21.
In order to prolong the service life of the fibroin friction layer 21 in a humidity environment, the fibroin friction layer 21 is modified for 5 hours by adopting a mixed solution of absolute ethyl alcohol and deionized water with a volume ratio of 70% to 30% so as to improve the content of hydrophobic β folding groups in the fibroin friction layer 21 and reduce the water solubility of the fibroin friction layer 21.
4) The first polar plate 10 is placed above the second polar plate 20, and meanwhile, a gap is ensured between the first flexible PET substrate 11 and the fibroin friction layer 21, so that the nano generator containing the micro-nano textured fibroin friction layer is formed.
The specific operation of the step 4) is as follows: the first polar plate 10 is placed above the second polar plate 20, a gap is ensured between the first flexible PET substrate 11 and the fibroin friction layer 21, and the fibroin friction layer 21 is bonded with the isolation layer to form the nano generator containing the micro-nano textured fibroin friction layer.
When the electric energy meter works specifically, after the first polar plate 10 is pressed, the first polar plate 10 approaches to the second polar plate 20, the fibroin friction layer 21 and the first flexible PET substrate 11 generate contact friction, negative charges are generated on the first flexible PET substrate 11, positive charges with the same electric quantity are generated on the fibroin friction layer 21, and the fibroin electric energy meter is opposite to the fibroin electric energy meter, positive charges are carried on the first silver nanowire output electrode layer 12, positive charges are carried on the second silver nanowire output electrode layer 23, potential difference is generated between the first silver nanowire output electrode layer 12 and the second silver nanowire output electrode layer 23, and therefore voltage and current are output, and corresponding electric energy output effects are achieved according to the size and frequency of applied pressing force.
The friction generator can be applied to various self-driven systems as an energy supply device, and is particularly suitable for the fields of flexible touch screens, flexible display and the like due to high transparency; meanwhile, the fibroin has good light transmission, strong biocompatibility, no toxicity, harmlessness and degradability, can be used for biological implantation type equipment, and has higher potential application value.
The foregoing embodiments are merely illustrative of the principles of the present invention and its efficacy, and are not to be construed as limiting the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which come within the spirit and scope of the invention as defined by the appended claims be embraced thereby.
Claims (9)
1. A preparation method of a nano generator containing a micro-nano textured fibroin friction layer is characterized in that the nano generator containing the micro-nano textured fibroin friction layer comprises a first polar plate (10) and a second polar plate (20), wherein the first polar plate (10) is opposite to the second polar plate (20), the first polar plate (10) comprises a first flexible PET substrate (11) and a first silver nanowire output electrode layer (12) which are sequentially distributed from top to bottom, the second polar plate (20) comprises a fibroin friction layer (21), a second flexible PET substrate (22) and a second silver nanowire output electrode layer (23) which are sequentially distributed from top to bottom, and the fibroin friction layer (21) is opposite to the first flexible PET substrate (11);
the upper surface of the fibroin friction layer (21) is in a lattice-shaped micro-nano texture (3);
the method comprises the following steps:
1) scraping nanowire solution on the upper surface of a first flexible PET substrate (11) in a scraper coating mode, carrying out thermal annealing or mechanical pressurization process treatment to obtain a first silver nanowire output electrode layer (12), meanwhile, scraping nanowire solution on the lower surface of a second flexible PET substrate (22) in a scraper coating mode, carrying out thermal annealing and mechanical pressurization process treatment to obtain a second silver nanowire output electrode layer (23);
2) scraping fibroin solution on the upper surface of a second flexible PET substrate (22) by adopting a scraper coating mode, and then air-drying at normal temperature and normal pressure to obtain a fibroin friction layer (21);
3) depositing micro-nano particle size deionized water (2) formed by electrohydrodynamic atomization on a fibroin friction layer (21), and dissolving and etching a lattice-shaped micro-nano texture (3) on the upper surface of the fibroin friction layer (21);
4) the first polar plate (10) is placed above the second polar plate (20), and meanwhile, a gap is ensured between the first flexible PET substrate (11) and the fibroin friction layer (21) to form the nano generator containing the micro-nano textured fibroin friction layer.
2. The method for preparing a nano-generator containing a micro-nano textured fibroin friction layer according to claim 1, wherein the thickness of each of the first flexible PET substrate (11) and the second flexible PET substrate (22) is 10-1000 μm.
3. The method for preparing a nanogenerator comprising a micro-nano textured fibroin friction layer according to claim 1, wherein the thickness of the fibroin friction layer (21) is 0.1-100 μm.
4. The preparation method of the nano-generator containing the micro-nano textured fibroin friction layer according to claim 1, is characterized in that the diameter of the micro-nano texture (3) is 0.05-10 micrometers, and the center distance between two adjacent micro-nano textures (3) is 0-10 micrometers.
5. The method for preparing the nano-generator containing the micro-nano textured fibroin friction layer according to claim 1, characterized in that in the step 1), during blade coating, the first flexible PET substrate (11) and the second flexible PET substrate (22) are adsorbed on the substrate of a blade coating machine in a vacuum adsorption mode, and the heating function of the blade coating machine is started simultaneously.
6. The method for preparing the nano-generator containing the micro-nano textured fibroin friction layer according to claim 1, is characterized in that the specific operation of the step 3) is as follows:
through an electrohydrodynamic atomization principle, deionized water is atomized into micro-nano-sized fog drops, and then the fog drops are dropped on the upper surface of the fibroin friction layer (21), so that lattice-shaped micro-nano textures (3) are dissolved and etched on the upper surface of the fibroin friction layer (21), wherein the size of the fog drops is determined according to the size of the micro-nano textures (3).
7. The method for preparing the nano-generator with the micro-nano textured fibroin friction layer according to claim 1, is characterized by further comprising the following steps between the step 3) and the step 4): the fibroin friction layer (21) is modified by using a mixed solution of ethanol and water, a mixed solution of methanol and water, or high-temperature water vapor.
8. The method for preparing a nano-generator comprising a micro-nano textured fibroin friction layer according to claim 1, wherein an isolation layer is interposed between the fibroin friction layer (21) and the first flexible PET substrate (11).
9. The method for preparing a nano-generator containing a micro-nano textured fibroin friction layer according to claim 8, wherein the isolation layer is an ultrathin adhesive tape or an adhesive water layer.
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