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CN117584578B - A self-healing luminescent-power generating elastic film and its preparation method and application - Google Patents

A self-healing luminescent-power generating elastic film and its preparation method and application Download PDF

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CN117584578B
CN117584578B CN202410072353.6A CN202410072353A CN117584578B CN 117584578 B CN117584578 B CN 117584578B CN 202410072353 A CN202410072353 A CN 202410072353A CN 117584578 B CN117584578 B CN 117584578B
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conductive
elastic film
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healing
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CN117584578A (en
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熊佳庆
芦泽仁
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Donghua University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29DPRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00Producing flat articles, e.g. films or sheets
    • B29D7/01Films or sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • HELECTRICITY
    • H02GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02NELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N1/00Electrostatic generators or motors using a solid moving electrostatic charge carrier
    • H02N1/04Friction generators
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/20Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51Elastic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54Yield strength; Tensile strength
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • B32B2457/20Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208Touch screens

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Abstract

The invention belongs to the field of functional materials, and relates to a self-healing luminous-power generation elastic film, a preparation method and application thereof, wherein the elastic film comprises a force luminous-power generation layer, a conductive layer and a packaging layer from top to bottom; the mechanoluminescence-generating layer is composed of mechanoluminescence powder and dielectric elastic polymer; the conductive layer consists of solid conductive filler, conductive liquid and dielectric elastic polymer; the encapsulation layer is composed of a dielectric elastic polymer; the conductive liquid deforms along with the dielectric elastic polymer in the stretching process of the dielectric elastic polymer, and autonomous repair and dynamic compensation of the conductive path are realized through active deformation and permeation. The invention can realize stress luminescence and friction power generation, and realize overall high stretchability and self-healing property, and can be applied to the fields of man-machine interaction, electronic skin, energy, sensing, display or national defense and military industry.

Description

Self-healing luminous-power generation elastic film and preparation method and application thereof
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a self-healing luminous-power generation elastic film, and a preparation method and application thereof.
Background
The rise of concepts and technologies such as "artificial intelligence", "internet of things" and "internet of everything" has led to a dramatic increase in demand for flexible electronic products. The electronic skin is a novel flexible electronic device for simulating human skin to realize environmental adaptation and stimulus perception, and is hopeful to construct a new type of interconnection carrier among human bodies, machines and environments, so that the interaction effect among different life or non-life individuals is improved. Mechanical stimulation is the most common form in the human-machine-environment interaction process, and the diversification of the sensing function of the electronic skin on the mechanical stimulation is always a target commonly pursued in the field. A sensing material capable of converting mechanical stimulus into optical and electrical signals simultaneously is developed, a visual sensing technology is realized, and mechanical sensing capability and interaction effect can be remarkably improved. Meanwhile, the stretchability and the self-healing capability of the sensing material are endowed with great significance for improving the substrate adaptability and application scene of the electronic skin.
The traditional technology adopts the modes of spin coating, hot pressing or directly using adhesive to paste, and the like to realize the mutual combination between different functional layers, and finally forms the luminous or power generation film with a layered structure. Therefore, the traditional device has single function and complex processing mode, the corresponding material is easy to be destroyed under larger strain, and the structure and the property of the traditional device can not be actively healed and recovered. The damage is not only caused by the functional singleness of each functional layer, but also has important relation with the physical irreversible slippage and interlayer peeling between layers. This greatly limits their applicability in areas with high demands on high deformation and self-healing, and the feasibility of implementation of the relevant multifunctional electronic skin and complex scene applications. It can be seen that currently, various electronic skin materials can only realize single force-electricity conversion or force-light conversion, and meanwhile, challenges exist in realizing the luminescence-power generation effect under the mechanical action. And, achieving high stretchability and self-healing properties of electronic skin while giving consideration to the luminescence-power generation effect faces a great challenge.
Disclosure of Invention
The invention aims to solve the technical problem of providing a self-healing luminous-power generation elastic film, and a preparation method and application thereof, so as to overcome the defects that the luminous-power generation performance of materials is difficult to consider and the elastic deformation and the self-healing performance are lacked in the prior art.
The invention provides a self-healing luminous-generating elastic film, which comprises a force luminous-generating layer, a conducting layer and a packaging layer from top to bottom; the mechanoluminescence-generating layer is composed of mechanoluminescence powder and dielectric elastic polymer; the conductive layer consists of solid conductive filler, conductive liquid and dielectric elastic polymer; the encapsulation layer is composed of a dielectric elastic polymer; the solid conductive filler is combined with the dielectric elastic polymer to form a stretchable polymer conductive matrix, the conductive liquid is combined with the dielectric elastic polymer to form a stretchable polymer conductive conductor, and the conductive liquid deforms along with the dielectric elastic polymer in the stretching process of the dielectric elastic polymer, so that autonomous repair and dynamic compensation of a conductive path are realized through active deformation and permeation.
Preferably, the dielectric elastic polymer comprises one or more of polyester, polyethylene, polyvinyl alcohol, polyvinyl acetal Ding Quanzhi, polyvinylpyrrolidone, polydimethylsiloxane, styrene-isoprene-styrene block copolymer, ethylene-vinyl acetate copolymer, isoprene copolymer, polybutylene terephthalate, and styrene-butadiene-styrene block copolymer.
More preferably, the dielectric elastic polymer is a blend of an ethylene-vinyl acetate copolymer and a styrene-isoprene-styrene block copolymer, and the mass ratio of the blend is 1:10-10:1. Ethylene-vinyl acetate copolymers, as a thermoplastic elastomer, can self-heal after a certain temperature rise, in addition to excellent melt processability, low temperature flexibility, reversible actuation, transparency and good affinity with fillers. The molecules and segments derived from EVA migrate and dynamically crosslink under thermal effects and macroscopically manifest as repair and healing of cracks. The styrene-isoprene-styrene block copolymer has excellent elasticity and stretchability, and the interfacial region formed by blending the styrene-isoprene-styrene block copolymer and the ethylene-vinyl acetate copolymer can effectively ensure the recovery after stretching while endowing the film with self-healing property.
Preferably, the mechanoluminescence powder comprises one or more of ZnS/CaZnOS:Mn2+、MgF2:Mn2+、ZnS:Cu2+、SrAl2O4:Dy3+:Eu2+、LiGa5O8、CaF2:Er3+、Al2O3:Tb3+、Li2BaP2O7:Eu3+、CaAl2SiO8:Eu2+、ZnAl2O4:Mn2+、ZnGa2O4:Mn2+、ZrO2:Ti4+.
More preferably, the mechanoluminescence powder is ZnS/CaZnOS: mn 2+、MgF2:Mn2+.
Preferably, the solid conductive filler comprises one or more of a zero-dimensional conductive filler, a one-dimensional conductive filler and a two-dimensional conductive filler; the conductive liquid comprises one or more of liquid metal, liquid alloy and ionic liquid.
More preferably, the zero-dimensional conductive filler comprises one or more of silver micro-nano particles, copper micro-nano particles and gold micro-nano particles; the one-dimensional conductive filler comprises one or more of silver nanowires, copper nanowires, gold nanowires, carbon nanotubes and carbon microfibers; the two-dimensional conductive filler comprises one or more of silver nano-sheets, copper nano-sheets, gold nano-sheets and aluminum nano-sheets.
More preferably, the liquid metal comprises one or more of gallium, rubidium, mercury. The liquid alloy comprises one or more of gallium indium tin alloy, gallium indium alloy and gallium zinc alloy; the ionic liquid comprises one or more of lithium bis (trifluoromethane) sulfonyl imide salt, ethyl-3-methylimidazole bis (trifluoromethane sulfonyl) imide salt and ethyl 1-ethyl-3-methylimidazole sulfate.
Most preferably, the solid conductive filler is silver micro-nano particles and the liquid metal is gallium indium alloy.
The solid conductive filler is used as a rigid conductive material with excellent conductivity, is combined with the dielectric elastic polymer to form a stretchable polymer conductive matrix, and can provide additional mechanical properties while bringing excellent conductivity to the dielectric elastic polymer. The conductive liquid is used as a flexible conductive material, has excellent fluidity, is combined with the dielectric elastic polymer to form a stretchable polymer conductive conductor, particularly, the surface oxide layer of the conductive liquid and the ethylene-vinyl acetate copolymer are easy to form hydrogen bond action, and the action stability between the conductive filler and the dielectric elastic polymer is enhanced. Meanwhile, by adding the conductive liquid, gaps between the solid conductive fillers can be filled so as to improve conductivity, the conductive liquid can be deformed together with the dielectric elastic polymer in the stretching process of the dielectric elastic polymer, and meanwhile, the rigid conductive materials which are originally separated are recombined through active deformation and permeation so as to realize autonomous repair and dynamic compensation of a conductive path, namely 'self-healing', so that the conductive stability under stretching is realized. By combining a solid conductive filler with a conductive liquid in combination with the dielectric elastomeric polymer, it is achieved that the polymer conductor maintains a low resistance in the stretched state and maintains even more than the original conductivity after cutting and self-healing.
Preferably, the elastic finger film can be subjected to reversible stretching deformation, and the deformation range is 1% -2000%; after the self-healing finger film is partially or completely damaged, the self-healing finger film can recover to an original film structure through healing treatment; the healing condition is that the temperature is 5-150 ℃ and the time is 1-500 min.
The invention also provides a preparation method of the self-healing luminous-power generation elastic film, which comprises the following steps:
(1) Adding an elastic polymer into a solvent, and uniformly stirring to obtain a polymer solution A; mixing the polymer solution A with the mechanoluminescence powder, stirring, performing ultrasonic dispersion and defoaming to obtain a polymer solution B; pouring the polymer solution B into a mould for heat treatment to obtain a semi-cured mechanoluminescence-power generation elastic film;
(2) Mixing solid conductive filler, conductive liquid and polymer solution A, stirring and defoaming to obtain polymer solution C, placing the polymer solution C on a semi-cured power-induced luminescence-power generation elastic film in a mold, and performing heat treatment to obtain a semi-cured conductive elastic film;
(3) And casting the polymer solution A on the semi-solidified conductive elastic film, and performing heat treatment until the solvent in the three layers of films is completely volatilized, thereby obtaining the self-healing luminous-power generation elastic film.
Preferably, the solvent comprises one or more of deionized water, toluene, ethanol, acetone, isopropanol, diethyl ether, dichloromethane, tetrahydrofuran, chloroform, N-dimethylformamide and thionyl chloride.
Preferably, the mass ratio of the polymer solution A to the mechanoluminescence powder is 1:10-100:1.
Preferably, the mass ratio of the conductive liquid to the solid conductive filler is 1:50-10:1.
Preferably, the mass ratio of the total mass of the conductive liquid to the solid conductive filler to the mass of the polymer solution A is 1:50-100:1.
Preferably, the mass ratio of the polymer solution A to the polymer solution B to the polymer solution C is 1:50:500-500:50:1.
Preferably, the heat treatment temperature in the steps (1) - (3) is 10-150 ℃ and the heat treatment time is 1-720 min.
The invention also provides application of the self-healing luminous-generating elastic film in the fields of man-machine interaction, electronic skin, energy, sensing, display or national defense and military industry.
Preferably, the application in the field of man-machine interaction comprises an electronic touch screen or information interaction equipment.
Preferably, the application of the electronic skin comprises a mechanical or robotic skin device.
Preferably, the application of the energy field comprises an energy harvesting or energy management device.
Preferably, the application of the display field includes application of night writing visualization and force visualization.
Preferably, the national defense and military field application comprises an application of information encryption.
The invention obtains the stretchable and self-healable polymer by blending the polymer with the self-healing function and the polymer with high elasticity. The dielectric elastic polymer is used as a matrix to prepare the packaging layer. The mechanoluminescence-generating layer and the conductive layer were prepared by incorporating a mechanoluminescence powder and a conductive material into a polymer solution, respectively. By a layer-by-layer preparation method, the elastic film which can emit light to generate electricity and can be self-healed is prepared. The luminescence is caused by the mechanoluminescence material property in the luminescence-generation layer, and the generation of electricity is caused by the triboelectric property of the dielectric elastomer in the luminescence-generation layer.
Advantageous effects
The invention can realize stress luminescence and friction power generation, and realize overall high stretchability (1000%) and self-healing property (self-healing efficiency is 90%), namely the stretchability of the self-healed film is 90% of the original stretchability, and can be applied to the fields of man-machine interaction, electronic skin, energy, sensing, display or national defense and military industry.
Drawings
FIG. 1 is a schematic view of the self-healing luminescent-power generating elastic film of the present invention.
FIG. 2 shows the tensile stress-strain curve (a) and the current output (b) after self-healing after cutting and self-healing of the self-healing luminescent-power generating elastic film of example 1.
FIG. 3 is a cross-sectional scanning electron microscope image of a self-healing luminescent-power generating elastic film of example 2.
FIG. 4 shows the voltage (a), current (b), and charge output (c) of the self-healing luminescent-generating elastic film of example 2 at 20N,2 Hz.
FIG. 5 is a cyclic tensile stress-strain curve of the self-healing luminescent-power generating elastic film of example 3 at 100% strain.
FIG. 6 is a graph showing the self-healing rate of the self-healing luminescent-generating elastic film of example 3 at various self-healing times.
FIG. 7 is a cross-sectional scanning electron microscope image of the mechanoluminescence-generation layer in the self-healing luminescence-generation elastic film of example 4.
FIG. 8 shows the voltage (a), current (b), and charge output (c) of the self-healing luminescent-generating elastic film of example 4 at 20N, 2 Hz.
FIG. 9 is a tensile stress-strain curve (a) and a voltage output (b) after self-healing after cutting and self-healing of the self-healing luminescent-power generating elastic film of example 5.
FIG. 10 is the voltage output of the self-healing luminescent-power generating elastic film of example 5 at different stretching conditions under 20N,2Hz slapping.
Detailed Description
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Example 1
In this embodiment, a self-healing luminescent-generating elastic film is provided, and the preparation method of the elastic film is as follows: 0.35g of the styrene-isoprene-styrene block copolymer and 0.35g of the ethylene-vinyl acetate copolymer were poured into 2.1g of a solvent, and mixed and stirred for 24 hours at 800rpm, with toluene as the solvent. A polymer A solution having self-healing and stretchability was obtained at a concentration of 25% by weight. To the obtained polymer A solution, 0.5g of a mechanoluminescence powder ZnS/CaZnOS: mn 2+ was added, and the mixture was stirred at 800rpm for 1 hour to obtain a polymer B solution having mechanoluminescence properties. Pouring the polymer B solution into a mold and drying to obtain a semi-cured power-induced luminescence-power generation elastic film; to the resulting polymer A solution, 1.5g of an ultrasonically dispersed gallium indium alloy was added and stirred for 20 minutes. Then, 0.8g of silver powder was added thereto and stirred for 40 minutes. And (3) defoaming to obtain a conductive polymer solution C, placing the polymer solution C on the semi-cured power-induced luminescence-power generation elastic film in a die, and performing heat treatment at 45 ℃ for 120min to obtain the semi-cured conductive elastic film with tightly-adhered interfaces. Finally, 1.4g of polymer solution A is cast on the semi-solidified conductive elastic film, and the self-healing luminous-generating elastic film is obtained after heat treatment is carried out at 45 ℃ for 480min until the solvent in the three layers of films is completely volatilized. FIG. 1 shows a schematic structure of the self-healing luminescent-power generation elastic film. As shown in FIG. 2, the self-healing luminous-power generation elastic film can keep the original 92% elongation at break after self-healing, and can still keep the current output above 0.4 mu A after self-healing.
Example 2
In this embodiment, a self-healing luminescent-generating elastic film is provided, and the preparation method of the elastic film is as follows: 0.3g of the styrene-isoprene-styrene block copolymer and 0.4g of the ethylene-vinyl acetate copolymer were poured into 2.2g of a solvent, and mixed and stirred for 12 hours, the stirrer rotation speed was 600rpm, and the solvent was toluene. A polymer A solution having self-healing and stretchability was obtained at a concentration of 25% by weight. To the obtained polymer A solution, 0.5g of a mechanoluminescence powder ZnS/CaZnOS: mn 2+ was added and stirred at 600rpm for 1.5 hours to obtain a polymer B solution having mechanoluminescence properties. Pouring the polymer B solution into a mold and drying to obtain a semi-cured power-induced luminescence-power generation elastic film; to the resulting polymer A solution, 1.5g of an ultrasonically dispersed gallium indium alloy was added and stirred for 15 minutes. Then, 0.5g of silver powder was added thereto and stirred for 30 minutes. And (3) defoaming to obtain a conductive polymer solution C, placing the polymer solution C on the semi-cured power-induced luminescence-power generation elastic film in a die, and performing heat treatment at 45 ℃ for 120min to obtain the semi-cured conductive elastic film with tightly-adhered interfaces. Finally, 1.5g of polymer solution A is cast on the semi-solidified conductive elastic film, and the self-healing luminous-generating elastic film is obtained after heat treatment is carried out at 45 ℃ for 480min until the solvent in the three layers of films is completely volatilized. FIG. 3 is a cross-sectional scanning electron microscope image of the self-healing luminescent-generating elastic membrane that can generate 66V voltage, 2.2 μA current and 25nC charge at a fixed frequency of 20N,2Hz (FIG. 4).
Example 3
In this embodiment, a self-healing luminescent-generating elastic film is provided, and the preparation method of the elastic film is as follows: 0.4g of the styrene-isoprene-styrene block copolymer and 0.6g of the ethylene-vinyl acetate copolymer were poured into 2g of a solvent, and mixed and stirred for 24 hours, the stirrer rotation speed was 600rpm, and the solvent was toluene. A polymer A solution having self-healing and stretchability was obtained at a concentration of 33.3% by weight. And adding 1g of mechanoluminescence powder MgF 2:Mn2+ into the obtained polymer A solution, and stirring at 600rpm for 2h to obtain a polymer B solution with mechanoluminescence performance. Pouring the polymer B solution into a mold and drying to obtain a semi-cured power-induced luminescence-power generation elastic film; to the resulting polymer A solution, 1g of an ultrasonically dispersed gallium indium alloy was added and stirred for 300 minutes. Then, 1g of silver powder was added thereto and stirred for 60 minutes. And (3) defoaming to obtain a conductive polymer solution C, placing the polymer solution C on the semi-cured power-induced luminescence-power generation elastic film in a die, and performing heat treatment at 50 ℃ for 60min to obtain the semi-cured conductive elastic film with tightly-adhered interfaces. Finally, 2g of polymer solution A is cast on the semi-solidified conductive elastic film, and the self-healing luminous-generating elastic film is obtained after heat treatment is carried out at 50 ℃ for 360min until the solvent in the three layers of films is completely volatilized. The self-healing luminous-power generation elastic film can still maintain certain mechanical properties after being circularly stretched for 10 times under 100% strain, as shown in figure 5. Further, as shown in fig. 6, the self-healing luminescent-generating elastic film was subjected to self-healing test at various temperatures, which was recovered to 90% of the original state after heating at 85 ℃ for 240 minutes.
Example 4
In this embodiment, a self-healing luminescent-generating elastic film is provided, and the preparation method of the elastic film is as follows: 0.25g of the styrene-isoprene-styrene block copolymer and 0.75g of the ethylene-vinyl acetate copolymer were poured into 3g of a solvent, and mixed and stirred for 12 hours, the stirrer rotation speed was 600rpm, and the solvent was toluene. A polymer A solution having self-healing and stretchability was obtained at a concentration of 25% by weight. And adding 1.2g of mechanoluminescence powder MgF 2:Mn2+ into the obtained polymer A solution, and stirring at 800rpm for 2h to obtain polymer B solution with mechanoluminescence performance. Pouring the polymer B solution into a mold and drying to obtain a semi-cured power-induced luminescence-power generation elastic film; fig. 7 shows that the mechanoluminescence powder particles were uniformly dispersed in the polymer matrix. To the resulting polymer A solution, 1.5g of an ultrasonically dispersed gallium indium alloy was added and stirred for 20 minutes. Then, 1.5g of silver powder was added thereto and stirred for 60 minutes. And (3) defoaming to obtain a conductive polymer solution C, placing the polymer solution C on the semi-cured power-induced luminescence-power generation elastic film in a die, and performing heat treatment at 50 ℃ for 120min to obtain the semi-cured conductive elastic film with tightly-adhered interfaces. Finally, casting 6g of polymer solution A on the semi-solidified conductive elastic film, and carrying out heat treatment at 45 ℃ for 480min until the solvent in the three layers of films is completely volatilized, thus obtaining the self-healing luminous-power generation elastic film. FIG. 8 shows the 55V voltage, 0.6 μA current and 19nC charge output generated by the self-healing luminescent-generating elastic membrane at a fixed frequency of 20N,2 Hz.
Example 5
In this embodiment, a self-healing luminescent-generating elastic film is provided, and the preparation method of the elastic film is as follows: 0.27g of the styrene-isoprene-styrene block copolymer and 0.47g of the ethylene-vinyl acetate copolymer were poured into 2.22g of a solvent, and mixed and stirred for 12 hours at 600rpm, with toluene as the solvent. A polymer A solution having self-healing and stretchability was obtained at a concentration of 25% by weight. To the obtained polymer A solution, 1.2g of a mechanoluminescence powder ZnS/CaZnOS: mn 2+ was added and stirred at 600rpm for 0.5 hours to obtain a polymer B solution having mechanoluminescence properties. Pouring the polymer B solution into a mold and drying to obtain a semi-cured power-induced luminescence-power generation elastic film; and adding 1g gallium indium alloy subjected to ultrasonic dispersion into the obtained polymer A solution, and stirring for 20min. Then, 0.6g of silver powder was added thereto and stirred for 60 minutes. And (3) defoaming to obtain a conductive polymer solution C, placing the polymer solution C on the semi-cured power-induced luminescence-power generation elastic film in a die, and performing heat treatment at 45 ℃ for 180min to obtain the semi-cured conductive elastic film with tightly-adhered interfaces. Finally, 2.94g of polymer solution A is cast on the semi-solidified conductive elastic film, and the self-healing luminous-generating elastic film is obtained after heat treatment is carried out at 45 ℃ for 480min until the solvent in the three layers of films is completely volatilized. As shown in fig. 9, the finally obtained self-healing luminescent-power generation elastic film can be circularly stretched under 100% strain and bear more than 1000% strain, and can bear more than 900% strain (90% of initial performance) after being cut off and self-healed. And has almost the same 71V voltage output as before self-healing. As shown in FIG. 10, the self-healing luminescent-generating elastic film can still generate a triboelectric output of 60V at a fixed slapping frequency of 20N,1Hz under a tensile state of 400%.
Comparative example 1
Zhang et al prepared a luminescent power generation film, which was prepared as follows: the ZnS: cu 2+ particles were mixed with polydimethylsiloxane in a mass ratio of 7:3 to form a homogeneous dispersion, and then the curing agent was added in a ratio of polydimethylsiloxane to curing agent of 10:1. Subsequently, the mixture was poured into a polytetrafluoroethylene mold equipped with a layer of sandpaper and cured at 80℃for 2 hours to prepare a PDMS/ZnS: cu 2+ composite elastomer. Then, the gallium/indium (mass ratio of 3:1) mixture was heated in a nitrogen atmosphere at 120 ℃ for 2 hours to prepare a liquid metal. The liquid metal is dripped on the PDMS/ZnS: cu 2+ composite elastomer to construct an electrode, and then a copper foil is adhered to the surface of the electrode. Finally, uniformly coating polydimethylsiloxane on the electrode, and encapsulating the electrode formed by liquid metal after curing. The prepared luminous power generation film can emit light under mechanical stimulation and simultaneously generate triboelectricity, but the strain is less than 100%, and the film has no self-healing property.

Claims (6)

1. A self-healing luminous-generating elastic film is characterized in that: the elastic film comprises a force-induced luminescence-power generation layer, a conductive layer and a packaging layer from top to bottom; the mechanoluminescence-generating layer is composed of mechanoluminescence powder and dielectric elastic polymer; the conductive layer consists of solid conductive filler, conductive liquid and dielectric elastic polymer; the encapsulation layer is composed of a dielectric elastic polymer; the solid conductive filler is combined with the dielectric elastic polymer to form a stretchable polymer conductive matrix, the conductive liquid is combined with the dielectric elastic polymer to form a stretchable polymer conductive conductor, the conductive liquid deforms along with the dielectric elastic polymer in the stretching process of the dielectric elastic polymer, and the autonomous repair and dynamic compensation of a conductive path are realized through active deformation and permeation;
The dielectric elastic polymer is a blend of an ethylene-vinyl acetate copolymer and a styrene-isoprene-styrene block copolymer, and the mass ratio of the blend is 1:10-10:1;
the solid conductive filler is silver micro-nano particles, and the conductive liquid is gallium-indium alloy; the mass ratio of the conductive liquid to the solid conductive filler is 1:50-10:1.
2. An elastic film according to claim 1, wherein: the mechanoluminescence powder includes one or more of ZnS/CaZnOS:Mn2+、MgF2:Mn2+、ZnS:Cu2+、SrAl2O4:Dy3+:Eu2+、LiGa5O8、CaF2:Er3+、Al2O3:Tb3+、Li2BaP2O7:Eu3+、CaAl2SiO8:Eu2+、ZnAl2O4:Mn2+、ZnGa2O4:Mn2+、ZrO2:Ti4+.
3. A method for preparing the self-healing luminescent-generating elastic film according to claim 1, comprising the steps of:
(1) Adding the dielectric elastic polymer into a solvent, and uniformly stirring to obtain a polymer solution A; mixing the polymer solution A with the mechanoluminescence powder, stirring, performing ultrasonic dispersion and defoaming to obtain a polymer solution B; pouring the polymer solution B into a mould for heat treatment to obtain a semi-cured mechanoluminescence-power generation elastic film;
(2) Mixing solid conductive filler, conductive liquid and polymer solution A, stirring and defoaming to obtain polymer solution C, placing the polymer solution C on a semi-cured power-induced luminescence-power generation elastic film in a mold, and performing heat treatment to obtain a semi-cured conductive elastic film;
(3) And casting the polymer solution A on the semi-solidified conductive elastic film, and performing heat treatment until the solvent in the three layers of films is completely volatilized, thereby obtaining the self-healing luminous-power generation elastic film.
4. A method of preparation according to claim 3, characterized in that: the solvent is toluene.
5. A method of preparation according to claim 3, characterized in that: the heat treatment temperature in the steps (1) - (3) is 10-150 ℃ and the heat treatment time is 1-720 min.
6. Use of the self-healing luminescent-power generating elastic film according to claim 1 in man-machine interaction, electronic skin, energy, sensing, display, or defense and military fields.
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