CN115118176A - Tensile insensitive friction nano generator - Google Patents
Tensile insensitive friction nano generator Download PDFInfo
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- CN115118176A CN115118176A CN202210764786.9A CN202210764786A CN115118176A CN 115118176 A CN115118176 A CN 115118176A CN 202210764786 A CN202210764786 A CN 202210764786A CN 115118176 A CN115118176 A CN 115118176A
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- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Polymerisation Methods In General (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
The invention relates to a friction nano generator insensitive to stretching. The friction nano generator with the sandwich structure based on the elastomer polymer is provided, a friction layer, a middle electrode and an encapsulation layer are sequentially arranged from top to bottom, a mixed solution of liquid organic micromolecule monomers, a cross-linking agent and a photoinitiator is infiltrated into a surface film of the friction nano generator, and then part of the surface film is irradiated by ultraviolet light, so that the irradiated part of the micromolecule monomers in the mixed solution form a cross-linked network and are embedded into the elastomer polymer to form an interpenetrating network, and the mechanical strength of the local area of the film is greatly enhanced. The invention effectively ensures that the friction nano generator carries out stable triboelectric output under the stretching deformation by providing the friction charge induction area which is not easy to be stretched and deformed.
Description
Technical Field
The invention relates to the field of friction nano-generators, in particular to a friction nano-generator insensitive to stretching.
Background
As a renewable energy technology, a friction nano generator (TENG) can convert mechanical energy into electric energy through contact electrification and static electricity induction, and has great application value in energy collection and human motion signal acquisition. The stretchable friction nano generator has the characteristics of lightness, flexibility, durability and the like, and can be applied to self-powered wearable electronic equipment. The common stretchable friction nano generator completes signal and energy collection by pressing contact electrification and can maintain triboelectric output under the condition of stretching deformation, so that the stretchable friction nano generator can be applied to the self-powered wearable field. Because the tensile deformation influences the output of the friction nanometer generator, the characteristic of ensuring that the friction nanometer generator is in a stable working state and realizing the insensitive stretching of the device becomes an important research object.
Disclosure of Invention
The invention aims to provide a friction nano generator insensitive to stretching, which realizes the stability of the output characteristics of the friction nano generator in different stretching states.
In order to realize the purpose, the technical scheme of the invention is as follows: a friction nanometer generator insensitive to stretching is of a sandwich structure and sequentially comprises a friction layer, an electrode and an encapsulation layer from top to bottom; penetrating a mixed solution of a liquid organic micromolecule monomer, a cross-linking agent and a photoinitiator into a polymer film of a friction layer and an encapsulation layer, and performing ultraviolet irradiation treatment to form a cross-linked interpenetrating network on the part irradiated by ultraviolet light, so as to greatly increase the modulus of a local area, namely forming a high-modulus area; when the friction nano generator is subjected to strain generated by transverse stress, the high-modulus region and the unmodified part have larger strain difference, and stable triboelectric output can be obtained by applying quantitative pressure to the high-modulus region under different stretching states.
In one embodiment of the present invention, the friction layer and the encapsulation layer are based on stretchable elastomeric polymers, wherein the elastomeric polymer as the friction layer is capable of increasing the surface charge density of the elastomeric polymer by adding an electronegative material.
In one embodiment of the invention, the electrode is a stretchable conductive material.
In one embodiment of the invention, the cross-linked interpenetrating network can be selectively generated by the shape and size of a photomask, so that the high modulus area which is not influenced by tension can be flexibly controlled on the friction nano-generator.
In one embodiment of the invention, the friction nano-generator is prepared by the following steps:
step S11, performing OTS modification on the glass or the glass slide; depositing a layer of electrode on the glass slide by a spraying method;
step S12, preparing an elastomer polymer raw material solution, and standing in vacuum;
step S13, preparing a layer of elastomer polymer film with the thickness of 100 mu m to 250 mu m on the electrode by a solution method through a spin coating process, and forming a polymer with a net structure as a friction layer through a thermal crosslinking reaction;
step S14, transferring the electrode on the glass slide by the polymer film, coating a layer of elastic polymer on one side of the electrode by spin coating, and performing thermal crosslinking to form a film to be used as a packaging layer to obtain the friction nano-generator with a sandwich structure;
step S15, standing the friction nanogenerator in a mixed solution of a liquid organic small molecule monomer (the liquid organic small molecule monomer solution may adopt methacrylic acid (MAA), hydroxyethyl methacrylate (HEMA) or Methyl Methacrylate (MMA)), a crosslinking agent and a photoinitiator, wherein the ratio of the photoinitiator to Ethylene Glycol Dimethacrylate (EGDMA) is 1: 3 is completely dissolved in the liquid organic micromolecular monomer solution according to the mass ratio;
step S16, lightly wiping the redundant solution on the surface of the friction nano generator by using dust-free cloth;
step S17, irradiating the polymer film on the friction nano generator permeated with the liquid organic small molecular monomer solution by ultraviolet light under a photomask to enable the exposed part to generate a photo-crosslinking reaction to form a crosslinking interpenetrating network;
step S18, drying the friction nano generator in the air, and volatilizing redundant solution;
and step S19, stripping the dried friction nano generator from the photomask.
In an embodiment of the present invention, the raw material of the elastomeric polymer is dissolved in a predetermined ratio by using a corresponding solvent (the raw material of the elastomeric polymer is dissolved in a predetermined ratio by using a corresponding solvent, and MXene and BaCO may be added 3 The like to increase the triboelectric negativity of the elastic polymer as a friction layer); stirring uniformly, standing in a vacuum environment until no bubbles exist, spin-coating the mixture on the electrode, and annealing.
In one embodiment of the invention, the elastomeric polymer film has a thickness of 100 μm to 250 μm.
In one embodiment of the present invention, the crosslinking agent is Ethylene Glycol Dimethacrylate (EGDMA).
In one embodiment of the invention, ultraviolet light is used for irradiating for a preset time within a preset range from the surface of the friction nano generator, and the liquid organic small molecule monomer is fully crosslinked to form a polymer network which is embedded in the elastomer polymer film of the friction nano generator.
In one embodiment of the present invention, the photomask can selectively generate regions of cross-linked interpenetrating networks, controlling the shape and area of the high modulus region.
Compared with the prior art, the invention has the following beneficial effects: the cross-linked interpenetrating network provided by the invention can effectively prevent the local area of the friction nano generator from deforming under a stretching state, and realize the effect of strain isolation, so that the contact friction electrification of the friction nano generator in the area can be stably carried out, and the output stability in actual work is ensured. The method has very strong universality and compatibility, is simple, convenient and low in cost, can be used for patterning, and is a very effective solution for realizing stable output of the friction nano generator under tensile deformation.
Drawings
FIG. 1 is a schematic diagram of the structural principle of a tension insensitive friction nano-generator in embodiment 1 of the present invention;
FIG. 2 is a schematic diagram of the structural principle of a tension insensitive friction nano-generator in embodiment 2 of the present invention;
fig. 3 shows triboelectric outputs of the tension-insensitive friction nano-generator in example 1 of the present invention in three different tension states.
In the figure: a 100-Polydimethylsiloxane (PDMS) film as a friction layer; 110-single-walled carbon nanotube electrodes; a 120-Polydimethylsiloxane (PDMS) film is used as an encapsulation layer; 130-interpenetrating network portions of MAA produced in Polydimethylsiloxane (PDMS); 140-Polydimethylsiloxane (PDMS)/MXene film as a friction layer; 150-portion of interpenetrating network produced by MAA in Polydimethylsiloxane (PDMS)/MXene.
Detailed Description
The technical scheme of the invention is specifically explained below with reference to the accompanying drawings.
The friction nano generator insensitive to stretching is of a sandwich structure and sequentially comprises a friction layer, an electrode and an encapsulation layer from top to bottom; penetrating a mixed solution of a liquid organic micromolecule monomer, a cross-linking agent and a photoinitiator into a polymer film of a friction layer and an encapsulation layer, and performing ultraviolet irradiation treatment to form a cross-linked interpenetrating network on the part irradiated by ultraviolet light, so as to greatly increase the modulus of a local area, namely forming a high-modulus area; when the friction nano generator is subjected to strain generated by transverse stress, the high-modulus region and the unmodified part have larger strain difference, and stable triboelectric output can be obtained by applying quantitative pressure to the high-modulus region under different stretching states.
The following are specific embodiments of the present invention.
The invention provides a tensile insensitive friction nano generator, which is provided with a sandwich structure friction nano generator based on PDMS elastomer polymer, wherein a friction layer, a middle electrode and an encapsulation layer are sequentially arranged from top to bottom, a mixed solution of liquid organic micromolecule monomer, cross-linking agent and photoinitiator is infiltrated into a surface film of the friction nano generator, and a partial area is irradiated by ultraviolet light, so that the micromolecule monomer in the irradiated part of the mixed solution forms a cross-linked network to be embedded into the elastomer polymer, an interpenetrating network is formed, and the mechanical strength of the partial area of the film is greatly enhanced. As shown in fig. 1, 100 (140) and 120 are the rubbing layer and the encapsulating layer of the PDMS film, 110 is the single-walled carbon nanotube electrode, and 130 (150) is the cross-linked interpenetrating network, respectively.
In this embodiment, the single-walled carbon nanotube solution is treated with a stock solution and deionized water in a ratio of 1:10, diluting, spraying the solution onto an OTS modified glass sheet, and depositing to form a film. PDMS with curing agent 15:1, spin-coating the glass sheet on the glass sheet at a rotation speed of 400 rpm, and annealing at 75 ℃ for 5 hours. The carbon nanotube film was transferred from the thermally cured PDMS film, and PDMS was spin coated again on one side of the carbon nanotube film and annealed at 75 ℃ for 5 h. Irgacure 651 photoinitiator in 1% by mass and EGDMA cross-linking agent in 3% by mass are completely dissolved in the liquid organic small molecule monomer solution, wherein EGDMA functions as the cross-linking agent. And the double-layer PDMS sandwich carbon nanotube sample is kept still in the mixed solution for a certain time. And then irradiating by using 365 nm ultraviolet light to enable the liquid organic small molecular monomer in the irradiated treatment area to be fully crosslinked to form a polymer network embedded in the PDMS film.
The invention also provides a preparation method of the strain isolated stretchable substrate, which comprises the following steps:
step S11, performing OTS modification on the glass or the glass slide; a layer of electrode was deposited on the slide by spray coating.
Step S12, the elastomeric polymer raw material solution is prepared and left to stand in vacuum.
And step S13, preparing a layer of elastomer polymer film with the thickness of 100 microns to 250 microns on the electrode by a solution method through a spin coating process, and forming a polymer with a net structure as a friction layer through a thermal crosslinking reaction.
And step S14, transferring the electrode on the glass slide by the polymer film, coating a layer of elastic polymer on one side of the electrode by spin coating, and forming a film by thermal crosslinking to serve as an encapsulation layer, wherein the encapsulation layer is the stretchable friction nano generator with a sandwich structure.
Step S15, standing the stretchable friction nano generator in a mixed solution of a liquid organic micromolecule monomer, a cross-linking agent and a photoinitiator.
And step S16, lightly wiping the redundant solution on the surface of the friction nano generator by using dust-free cloth.
And step S17, irradiating the polymer film on the friction nano generator infiltrated with the liquid organic micromolecule monomer solution by ultraviolet light under a photomask to enable the exposed part to generate a photo-crosslinking reaction to form an interpenetrating network.
And step S18, drying the friction nano generator in the air, and volatilizing the redundant solution.
And step S19, stripping the dried friction nano generator from the photomask.
To further illustrate the technical effects of the present invention, the following description specifically refers to different embodiments.
Example 1
1) Carrying out 1: and (5) diluting by 10.
2) And (3) scrubbing the cut glass with the size of 2 cm multiplied by 6 cm for three times by acetone, carrying out OTS modification after plasma treatment, and then drying by using nitrogen to obtain a clean glass sheet.
3) And spraying the prepared single-walled carbon nanotube solution onto the OTS glass by a spray gun.
4) PDMS was mixed with curing agent at 15:1, after bubbles are removed, covering the single-walled carbon nanotubes formed on the glass at the rotating speed of 400 rpm (60 s) in a spin coating mode, and then moving the glass sheet to a heating table for annealing at 75 ℃ (5 h) to prepare a PDMS film with the thickness of 200 microns as a friction layer of a device.
5) And tearing off the thermosetting PDMS, transferring the single-wall carbon nanotube conductive film, and spin-coating a layer of PDMS on one side of the conductive film as an encapsulation layer of the device.
6) Immersing the prepared friction nano generator with the sandwich structure into a mixed solution of methacrylic acid (MAA) micromolecule monomer, cross-linking agent and photoinitiator, wherein the MAA liquid micromolecule monomer: EGDMA: and (3) standing the photoinitiator irgacure 651=96:3:1 for 80 min, and then lightly wiping off the redundant small molecular monomer solution on the surface of the film by using a dust-free cloth.
7) A Philips ultraviolet lamp of 40W-BL type is prepared, a sample is placed under the ultraviolet lamp in a range of 1 cm to 5 cm with a mask (the pattern of the light transmission part is a rectangle of 1 cm multiplied by 1.5 cm), and ultraviolet light with a wavelength of 365 nm is used for irradiating the friction layer and the encapsulation layer for thirty minutes respectively.
8) The exposed sample was dried in air for 3 hours and then peeled from the glass substrate.
Example 2
1) The high-purity single-walled carbon nanotubes were diluted 1:10 with deionized water.
2) And (3) scrubbing the cut glass with the size of 2 cm multiplied by 6 cm for three times by acetone, carrying out OTS modification after plasma treatment, and then drying by using nitrogen to obtain a clean glass sheet.
3) And spraying the prepared single-walled carbon nanotube solution onto the OTS glass by a spray gun.
4) Preparing PDMS and a curing agent according to a mass ratio of 15:1, mixing the mixed solution with MXene with the concentration of 5mg/ml according to a mass ratio of 6:1, removing bubbles, covering the single-walled carbon nanotubes formed on the glass by a spin coating mode at a rotating speed of 400 rpm (60 s), and then transferring the glass sheet to a heating table to perform annealing at 75 ℃ (5 h) to prepare a PDMS film with the thickness of 200 microns as a friction layer of a device.
5) And tearing off the thermosetting PDMS, transferring the single-wall carbon nanotube conductive film, and spin-coating a layer of PDMS on one side of the conductive film as an encapsulation layer of the device.
6) Immersing the prepared friction nano generator with the sandwich structure into a mixed solution of methacrylic acid (MAA) micromolecule monomer, cross-linking agent and photoinitiator, wherein the MAA liquid micromolecule monomer: EGDMA: and (3) allowing the photoinitiator irgacure 651=96:3:1 to stand for 80 min, and then slightly wiping off the redundant small-molecule monomer solution on the surface of the film by using a dust-free cloth.
7) A40W-BL Philips ultraviolet lamp was prepared, and the rubbing layer and the encapsulating layer were irradiated with 365 nm ultraviolet light for thirty minutes while the sample was placed under the ultraviolet lamp with a mask (a pattern of a light transmitting portion was a rectangle of 1 cm. times.1.5 cm) within a distance of 1 cm to 5 cm.
8) The exposed sample was dried in air for 3 hours and then peeled from the glass substrate.
The structural diagrams of the embodiments 1 and 2 are shown in fig. 1 and 2, and since the liquid organic small molecule monomer solution is distributed in the friction layer and the encapsulation layer of the friction nano-generator in a penetrating manner, the exposed cross-linked network can penetrate through the whole film, so as to improve the local mechanical strength, further realize the characteristic of insensitive stretching of the region of the friction nano-generator, and apply quantitative pressure to the high modulus region in different stretching states to obtain stable triboelectric output. Fig. 3 shows triboelectric outputs of the tension insensitive friction nano-generator in example 1 under three different tension states.
The above are preferred embodiments of the present invention, and all changes made according to the technical scheme of the present invention that produce functional effects do not exceed the scope of the technical scheme of the present invention belong to the protection scope of the present invention.
Claims (10)
1. A friction nanometer generator insensitive to stretching is characterized in that the friction nanometer generator is of a sandwich structure and sequentially comprises a friction layer, an electrode and an encapsulation layer from top to bottom; penetrating a mixed solution of a liquid organic micromolecule monomer, a cross-linking agent and a photoinitiator into a polymer film of a friction layer and an encapsulation layer, and performing ultraviolet irradiation treatment to form a cross-linked interpenetrating network on the part irradiated by ultraviolet light, so as to greatly increase the modulus of a local area, namely forming a high-modulus area; when the friction nano generator is subjected to strain generated by transverse stress, the high-modulus region and the unmodified part have larger strain difference, and stable triboelectric output can be obtained by applying quantitative pressure to the high-modulus region under different stretching states.
2. A stretch insensitive triboelectric nanogenerator according to claim 1, wherein the friction layer and the encapsulation layer are both based on stretchable elastomeric polymers, wherein the elastomeric polymer as friction layer is capable of increasing the surface charge density of the elastomeric polymer by the addition of electronegative materials.
3. The tension insensitive friction nanogenerator of claim 1, wherein the electrode is a stretchable conductive material.
4. The tension insensitive friction nanogenerator of claim 1, wherein the cross-linked interpenetrating network can be selectively created by the shape and size of a photomask to flexibly control the high modulus region that is not affected by tension on the friction nanogenerator.
5. The tension insensitive friction nanogenerator of claim 1, wherein the friction nanogenerator is prepared by the steps of:
step S11, performing OTS modification on the glass or the glass slide; depositing a layer of electrode on the glass slide by a spraying method;
step S12, preparing an elastomer polymer raw material solution, and standing in vacuum;
step S13, preparing a layer of elastomer polymer film with the thickness of 100 mu m to 250 mu m on the electrode by a solution method through a spin coating process, and forming a polymer with a net structure as a friction layer through a thermal crosslinking reaction;
step S14, transferring the electrode on the glass slide by the polymer film, coating a layer of elastic polymer on one side of the electrode by spin coating, and performing thermal crosslinking to form a film to be used as a packaging layer to obtain the friction nano-generator with a sandwich structure;
step S15, standing the friction nano generator in a mixed solution of a liquid organic small molecular monomer, a cross-linking agent and a photoinitiator;
step S16, lightly wiping the redundant solution on the surface of the friction nano generator clean by using dust-free cloth;
step S17, irradiating the polymer film on the friction nano generator infiltrated with the liquid organic micromolecule monomer solution by ultraviolet light under a photomask to enable the exposed part to generate a photo-crosslinking reaction to form a crosslinking interpenetrating network;
step S18, drying the friction nano generator in the air, and volatilizing redundant solution;
and step S19, stripping the dried friction nano generator from the photomask.
6. A tension insensitive friction nanogenerator according to claim 5, wherein the elastomeric polymer raw material is dissolved with the corresponding solvent in a predetermined ratio; stirring uniformly, standing in a vacuum environment until no bubbles exist, spin-coating the mixture on the electrode, and annealing.
7. A stretch insensitive triboelectric nanogenerator according to claim 5, wherein the elastomeric polymer film has a thickness of 100 to 250 μm.
8. The tension insensitive friction nanogenerator of claim 5, wherein the crosslinker is ethylene glycol dimethacrylate.
9. The tension insensitive friction nanogenerator of claim 5, wherein ultraviolet light is used to irradiate a predetermined time within a predetermined range from the surface of the friction nanogenerator, and the liquid organic small molecule monomer is sufficiently crosslinked to form a polymer network embedded in the elastomer polymer film of the friction nanogenerator.
10. The tension insensitive friction nanogenerator of claim 5, wherein the photomask selectively creates regions of cross-linked interpenetrating network, controlling the shape and area of the high modulus region.
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