CN109659447B - Fibrous self-powered light-emitting device and preparation method thereof - Google Patents

Fibrous self-powered light-emitting device and preparation method thereof Download PDF

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CN109659447B
CN109659447B CN201811572273.8A CN201811572273A CN109659447B CN 109659447 B CN109659447 B CN 109659447B CN 201811572273 A CN201811572273 A CN 201811572273A CN 109659447 B CN109659447 B CN 109659447B
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anode
cathode
energy storage
light emitting
storage unit
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CN109659447A (en
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武青青
朱建军
胡少坚
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Shanghai IC R&D Center Co Ltd
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Shanghai IC R&D Center Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/182—OLED comprising a fiber structure
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a fibrous self-powered light-emitting device and a preparation method thereof. In the fibrous self-powered light-emitting device and the preparation method thereof provided by the invention, the energy storage unit is arranged on the fibrous substrate in a surrounding manner, the energy conversion unit is arranged on the energy storage unit in a surrounding manner, the fiber substrate is also provided with the electroluminescent unit, the connection between the electroluminescent unit and the energy storage unit is controlled by the light-operated switch, the connection and disconnection between the energy storage unit and the electroluminescent unit are realized by the light-operated switch, and sunlight can be absorbed and converted into electric energy to be stored in the energy storage unit when the light intensity is strong in the daytime.

Description

Fibrous self-powered light-emitting device and preparation method thereof
Technical Field
The invention relates to the technical field of electronic devices, in particular to a fibrous self-powered light-emitting device and a preparation method thereof.
Background
Electronic products have become an integral part of our lives. With the further development of science and technology, electronic products in the future not only have more and more powerful functions, but also become more and more flexible and convenient. The wearable technology is a new technology for directly wearing electronic products and other equipment on the body or integrating the electronic products and the other equipment into traditional fabrics, and has huge development space and application prospect. The various organisms in nature evolved their own specific functions gradually in the evolution of hundreds of millions of years, such as firefly flashing at night. Human beings are full of infinite longing for the peculiar functions in nature, inspired by nature, and by means of the power of scientific technology, the luminous power of fireflies is simulated, so that the electronic fabric capable of intelligently adjusting the brightness according to the ambient light is prepared, and the electronic fabric is applied to the environment with darker light, such as field mountaineering, diving exploration and mine operation, realizes the unique function of timely lighting, and has great application value.
Therefore, how to provide a wearable and environmentally responsive light emitting device is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a fibrous self-powered light-emitting device and a preparation method thereof, and provides a wearable light-emitting device capable of responding to the environment.
In order to solve the technical problems, the invention provides a fibrous self-powered light emitting device, which comprises an energy storage unit, an energy conversion unit, an electroluminescent unit and a photoswitch, wherein the energy storage unit is located on a fibrous substrate, the energy storage unit comprises an anode, a cathode, an electrolyte and an inner cylindrical tube, the inner cylindrical tube is sheathed on the fibrous substrate, the anode and the cathode are both arranged in the inner cylindrical tube, the electrolyte is filled between the fibrous substrate and the inner cylindrical tube, the energy conversion unit comprises a counter electrode and a photoelectric anode, the counter electrode and the photoelectric anode are located on the inner cylindrical tube, the counter electrode is connected with the cathode, the photoelectric anode is connected with the anode, the electroluminescent unit is located on the fibrous substrate, and the electroluminescent unit comprises a bottom electrode and a bottom electrode which are sequentially formed, The bottom electrode is connected with the anode, the transparent electrode is connected with the cathode, and the light-operated switch controls the connection between the electroluminescent unit and the energy storage unit.
Optionally, in the fibrous self-energized light emitting device, the anode and the cathode each comprise aligned carbon nanotubes and active nanoparticles.
Optionally, in the fibrous self-powered light emitting device, the bottom electrode includes aligned carbon nanotubes and conductive nanoparticles.
Optionally, in the fibrous self-powered light emitting device, the number of the energy conversion units is two or more, and the two or more energy conversion units are connected in series.
Optionally, in the fibrous self-powered light emitting device, the electrolyte is a gel electrolyte.
Optionally, in the fibrous self-powered light emitting device, the photo-anode is wound on the counter electrode in a linear spiral shape.
Optionally, in the fibrous self-energized light emitting device, the anode and the cathode are both disposed circumferentially on the fibrous substrate.
Optionally, in the fibrous self-powered light emitting device, the bottom electrode and the transparent electrode both include aligned carbon nanotubes, and the light emitting layer is a light emitting polymer material.
Optionally, in the fibrous self-powered light emitting device, the photoswitch includes a substrate, a conductive layer, a paraffin layer and an oriented carbon nanotube film layer, the conductive layer is located on one side of the substrate, the paraffin layer is located on the other side of the substrate, and the oriented carbon nanotube film layer is located on the paraffin layer.
The invention also provides a preparation method of the fibrous self-powered light-emitting device, which comprises the following steps:
providing a fiber substrate, forming an anode and a cathode on one end of the fiber substrate, and forming a bottom electrode on the other end of the fiber substrate, wherein the bottom electrode is connected with the anode;
disposing an inner cylindrical tube on the fiber substrate, the anode and the cathode both being located within the inner cylindrical tube, filling an electrolyte between the inner cylindrical tube and the fiber substrate, the anode, the cathode and the electrolyte forming an energy storage unit, and forming a light emitting layer on the bottom electrode;
forming a counter electrode on the inner cylindrical tube, forming a photoelectric anode on the counter electrode, forming an energy conversion unit by the counter electrode and the photoelectric anode, connecting the counter electrode with the cathode, connecting the photoelectric anode with the anode, forming a transparent electrode on the light-emitting layer, forming an electroluminescent unit by the bottom electrode, the light-emitting layer and the transparent electrode, and arranging a photoswitch to control the connection of the electroluminescent unit and the energy storage unit.
In summary, in the fibrous self-powered light emitting device and the method for manufacturing the same provided by the present invention, the energy storage unit is disposed on the fibrous substrate in a surrounding manner, the energy conversion unit is disposed on the energy storage unit in a surrounding manner, the fiber substrate is further disposed with the electroluminescent unit, the connection between the electroluminescent unit and the energy storage unit is controlled by the light control switch, since the energy conversion unit is in a linear fibrous shape, the energy conversion unit can receive incident light beams of various angles and convert the incident light beams into electric energy, and is particularly applied to a space filled with diffused light, the prepared electroluminescent unit can emit light at 360 degrees, is similar to the planar light emitting unit in a radial direction, reduces contact resistance, has a high contact area due to coaxial light emission, is beneficial to rapid transmission and transfer of electrons, can sense the intensity of light by the light control switch, and realizes connection and disconnection between the energy storage unit and the electroluminescent unit, can make fibrous self-power luminescent device can be when daytime light intensity is stronger through absorbing the sunlight and turn into the electric energy with it and store in energy storage unit, when the light intensity in the environment weakens to certain degree, can communicate electroluminescent unit through photoswitch energy storage unit realizes giving out light, and whole device possesses certain pliability and bendability, can compile the fabric as the fibre in, provides the condition to wearable electronic equipment's development.
Drawings
FIG. 1 is a schematic structural view of a fibrous self-powered light emitting device according to an embodiment of the present invention;
fig. 2 a to E are schematic structural views from inside to outside of the method for manufacturing a fibrous self-powered light emitting device according to an embodiment of the present invention.
Detailed Description
To make the objects, features and advantages of the present invention comprehensible, reference is made to the accompanying drawings. It should be understood that the drawings and figures are only for the purpose of illustration and description, and are not intended to limit the scope of the invention, which is defined by the claims, but rather by the claims.
As shown in fig. 1, the present invention provides a fibrous self-powered light emitting device, which comprises an energy storage unit 100, an energy conversion unit 200, an electroluminescent unit 300 and a light control switch 400, wherein the energy storage unit 100 is located on a fibrous substrate 110, the fibrous substrate 110 should comprise linear or filamentous fibers, the energy storage unit 200 comprises an anode 121, a cathode 122, an electrolyte 130 and an inner cylindrical tube 140, the inner cylindrical tube 140 is sleeved on the fibrous substrate 110, the anode 121 and the cathode 122 are both located in the inner cylindrical tube 140, the electrolyte 130 is filled between the fibrous substrate 110 and the inner cylindrical tube 140, that is, the anode 121, the cathode 122 and the electrolyte 130 together form a battery structure, the energy conversion unit 200 comprises a counter electrode 210 and a photo-anode 220, the counter electrode 210 and the photo-anode 220 are located on the inner cylindrical tube 140 (outer surface), the counter electrode 210 is connected to the cathode 122, the photo-anode 220 is connected to the anode 121, that is, the photo-anode is connected to the energy conversion unit 200 to convert light energy into electric energy, so as to be stored in the energy storage unit 100, the electroluminescent unit 300 is disposed on the fiber substrate 110, the electroluminescent device 300 includes a bottom electrode 310, a light emitting layer 320 and a transparent electrode 330, which are sequentially formed, the bottom electrode 310 is connected to the anode 121, the transparent electrode 330 is connected to the cathode 122, the electroluminescent unit 300 emits light after being powered on, the photoswitch 400 controls the connection between the electroluminescent unit 300 and the energy storage unit 100, and the photoswitch 400 realizes the connection or disconnection of the circuit through the influence of sunlight.
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Continuing to refer to fig. 1, the environmentally-responsive, fibrous, self-powered light emitting device includes a fibrous substrate 110, an energy storage cell 100 disposed around one end of the fibrous substrate 110, an electroluminescent cell 300 disposed around the other end of the fibrous substrate 110, a photoswitch 400 connecting the energy conversion cell 200 and the electroluminescent cell 300, and the energy conversion cell 200 surrounding the periphery of the energy storage cell 100.
In material selection, the fiber substrate 110 may comprise any insulating flexible material, such as polydimethylsiloxane, rubber fiber, and the like.
The energy storage unit 100 may employ a lithium ion battery structure by being disposed on a fibrous substrate 110, including an anode 121 and a cathode 122 disposed on the substrate 110, an inner cylindrical tube 140 wrapping the anode 121, the cathode 122, and the substrate 110, and an electrolyte 130 filled between the substrate 110 and the inner cylindrical tube 140, the electrolyte infiltrating the anode and the cathode. Both the anode 121 and the cathode 122 may be fibrous and disposed around the substrate 110 without contacting each other. The anode 121 and cathode 122 may include Aligned Carbon nanotubes (Aligned Carbon nanotubes), which are typically Aligned multi-walled Carbon nanotubes, and active nanoparticles attached to the Aligned Carbon nanotubes, which may include LiMn for the anode 1212O4Nanoparticles, the active nanoparticles for the cathode 122 may include Li2Ti5O12And (3) nanoparticles.
The electroluminescent unit 300 is disposed on the fiber substrate 110, and may include a bottom electrode 310 disposed on the fiber substrate 110, a light emitting layer 320 disposed on the bottom electrode 310, and a transparent electrode 330 disposed on the light emitting layer 320, which may be surrounded based on the fiber substrate. The bottom electrode 310 may comprise an oriented multi-walled carbon nanotube film, the carrier transport of the electrode may be increased by adding conductive nanoparticles, metal nanoparticles such as zinc oxide nanoparticles, silver nanowires (particles), etc. may be used. The light emitting layer 320 may be a light emitting polymer material, such as polyfluorene, Superyellow, and other light emitting polymers of different colors. The transparent electrode 330 may be an oriented carbon nanotube film, and on the premise that the electrode has a certain light transmittance, the carrier transmission of the electrode may also be increased by adding a small amount of conductive nano-materials, such as silver nanowires.
The optical switch 400 is disposed between the energy storage unit 100 and the electroluminescent unit 300 for controlling the switching, and a corresponding switching circuit structure may be formed by a conductive element 410 formed between the anode 121 of the energy storage unit and the bottom electrode 310 of the electroluminescent unit, an insulating layer 420 coated outside the conductive element 410 to prevent electrical leakage, and a controllably bent conductive tab 430 connecting the cathode 122 of the energy storage unit and the transparent electrode 320 of the electroluminescent unit. The conductive element 410 is made of a conductive material, such as conductive silver paste. The insulating layer 420 covering the conductive element 410 may be a polymer insulating sleeve material, such as rubber, teflon, polydimethylsiloxane, or heat shrink tubing.
The conductive plectrum in the photoswitch comprises a substrate, a conductive layer, a paraffin layer and an oriented carbon nanotube film layer, the conductive layer is positioned on one side of the substrate, the paraffin layer is positioned on the other side of the substrate, the oriented carbon nanotube film layer is positioned on the paraffin layer, because of the obvious difference of the thermal expansion coefficients between the paraffin and the matrix material, when the light is irradiated, the expansion degrees of the paraffin and the matrix material are different, meanwhile, the expansion amount of the paraffin is limited by the orientation of the oriented carbon nanotube film layer, the carbon nanotube film can absorb part of visible light and infrared light and convert the visible light and the infrared light into heat energy, the thermal expansion is accelerated, therefore, the composite sheet has the response of controllable direction and high speed, and when the controllable bent conductive poking sheet is illuminated, the conductive paddle may flex, disconnecting the energy storage cell from the electroluminescent cell, in the absence of illumination, the conductive paddle will flatten, turning on the connection of the energy storage unit and the electroluminescent unit.
The energy conversion unit 200 may surround the energy storage unit 100, and the energy conversion unit 200 may be in a solar cell structure, and the solar cell structure may convert the absorbed sunlight into electric energy to be output and stored in the energy storage unit. For example, the solar cell structure may employ a perovskite solar cell, and the energy conversion unit 200 of the perovskite solar cell may include a counter electrode 210 disposed on the inner cylindrical tube 140, a photo anode 220 disposed to surround the counter electrode 210, and an outer cylindrical tube 230 wrapping the counter electrode 210, the photo anode 220, and the inner cylindrical tube 140. The counter electrode 210 may comprise an oriented multi-walled carbon nanotube film, which may cover the outer surface of the inner cylindrical tube 140. The photo-anode 220 may surround the counter electrode 210 by a spiral shapeAnd (3) the outer side. The photo-anode 200 may comprise a spiral titanium wire with titanium dioxide nanotubes vertically arranged on the surface and a photo-active layer coated on the periphery of the titanium dioxide nanotube3NH3PbI3-xClx and organic hole transport layer OMeTAD. The outer cylindrical tube 230 is spaced apart from the inner cylindrical tube 140 and wraps around the inner cylindrical tube 140 for shielding. The outer cylindrical tube 240 may be made of a transparent insulating material, such as a transparent heat-shrinkable tube.
In this embodiment, the number of the energy conversion units is two or more, and two or more energy conversion units are connected in series, that is, the photo-anode of a solar cell can be electrically connected to the counter electrode of an adjacent solar cell, so that the two solar cells are connected in series, and the output voltage can be increased.
A switching device (not shown) that is turned on or off may be disposed between the energy storage unit 100 and the energy conversion unit 200, and when the energy conversion unit 200 charges the energy storage unit 100, the anode 121 of the energy storage unit 100 is turned on with the photo-anode 220 of the energy conversion unit, and the cathode 122 of the energy storage unit 100 is turned on with the counter electrode 210 of the energy conversion unit 200.
Correspondingly, the invention also provides a preparation method of the fibrous self-powered light-emitting device, which comprises the following steps from inside to outside:
step S10, providing a fiber substrate, forming an anode and a cathode on one end of the fiber substrate, and forming a bottom electrode on the other end of the fiber substrate, wherein the bottom electrode is connected with the anode;
step S20, arranging an inner cylindrical tube on the fiber substrate, wherein the anode and the cathode are both positioned in the inner cylindrical tube, an electrolyte is filled between the inner cylindrical tube and the fiber substrate, the anode, the cathode and the electrolyte form an energy storage unit, and a light-emitting layer is formed on the bottom electrode;
step S30, forming a counter electrode on the inner cylindrical tube, forming a photoelectric anode on the counter electrode, forming an energy conversion unit by the counter electrode and the photoelectric anode, connecting the counter electrode with the cathode, connecting the photoelectric anode with the anode to realize the connection between the energy conversion unit and the energy storage unit, forming a transparent electrode on the light-emitting layer, forming an electroluminescent unit by the bottom electrode, the light-emitting layer and the transparent electrode, and arranging a photoswitch to control the connection between the electroluminescent unit and the energy storage unit.
The method of making the above-described environmentally responsive, fibrous self-energized light emitting device will now be described in detail with reference to figures 2-a through E of the accompanying drawings.
In fig. 2-a, a fiber substrate 110 forming a line, an anode 121 and a cathode 122 of an energy storage unit 100, a bottom electrode 310 and a light emitting layer 320 of an electroluminescent unit 300, and a connection anode 121 and a bottom electrode 310 are prepared. The fibrous substrate 110 may be an insulating flexible material such as, for example, polydimethoxysilane having a diameter of 20 to 2000 microns. Anode 121 can include oriented multi-walled carbon nanotubes and active nanoparticles, which can include lithium manganate (LiMn)2O4)。
For preparing the high-performance oriented carbon nano tube, the spinnable carbon nano tube array is prepared by a chemical vapor deposition method, and the catalyst for preparing the spinnable carbon nano tube array can be prepared by an electron beam evaporation coating system. LiMn2O4The preparation method comprises the steps of synthesizing by a hot water method, dissolving 0.3-0.6g of lithium hydroxide in 30-50ml of deionized water, adding 1-2g of manganese dioxide, stirring for 0.5h, and then adding 0.1-0.5g of glucose and 20-50ml of deionized water. Finally, the mixture is reacted for 20 hours in a reaction kettle at the temperature of 200 ℃. Drying to obtain spinel-shaped LiMn2O4And (3) nanoparticles. 7.5mg of LiMn2O4The nanoparticles and the randomly dispersed multi-walled carbon nanotube powder were mixed and dispersed in 15ml of N, N-dimethylformamide to obtain a suspension of active nanoparticles. Dripping the active nano-particle suspension on the oriented multi-wall carbon nano-tube film, twisting along the orientation direction of the carbon nano-tube to obtain the oriented multi-wall carbon nano-tube/LiMn2O4The composite fiber of (3) can be used to form the anode 121.
The cathode 122 mayTo include oriented multi-walled carbon nanotubes and active nanoparticles, which may include lithium titanate (Li)4Ti5O12). For Li4Ti5O12Synthesized by a solid-state method, titanium dioxide and lithium carbonate are mixed according to a molar ratio of 5:2, heated to 800 ℃, kept for 24 hours under the protection of nitrogen, and reacted to obtain Li with good crystallization4Ti5O12And (4) crystals. Putting the obtained product into a ball mill for ball milling for 20h to obtain Li4Ti5O12And (3) nanoparticles. 75mg of Li are taken4Ti5O12The nanoparticles were dispersed in 15ml of N, N-dimethylformamide solvent to give Li4Ti5O12A suspension of (a). Dripping the suspension on the oriented multi-wall carbon nanotube film, and twisting to obtain oriented multi-wall carbon nanotube/Li4Ti5O12The composite fibers of (a) may be used to form cathode 122.
The anode 121 and the cathode 122 may be respectively wound on the fiber substrate 110 by a spiral shape while ensuring that the two electrodes do not contact each other.
The bottom electrode 310 may include an oriented multi-walled carbon nanotube film, which may include zinc oxide nanoparticles, and a conductive nanomaterial, which is formed by pulling out the oriented multi-walled carbon nanotube film through a spinnable carbon nanotube array and winding it around the fiber substrate 110.
The conductive element 410 is electrically connected to the anode 121 of the energy storage unit 100 and the bottom electrode 310 of the electroluminescent unit 300, and may include conductive silver paste.
The light emitting layer 320 may be a light emitting polymer material, such as polyfluorene, Superyellow, and other light emitting polymers of different colors. For example, a polyfluorene derivative (PF-B), ethoxylated trimethylolpropane triacrylate and lithium trifluoromethanesulfonate were dissolved in a tetrahydrofuran solvent at a mass ratio (20:10:1) with the concentration of PFB being 20 to 50 mg/ml. And coating the mixed solution on the outer side of the bottom electrode 310, and forming the light-emitting layer 320 on the outer side of the bottom electrode 310 by vacuumizing for 0.5-2 h. The light emitting layer 320 is not in contact with the conductive element 410.
In fig. 2-B, the anode 121, cathode 122, and fiber substrate 110 surfaces may be coated with an electrolyte 130, coated with an electrical insulation layer 140 outside the energy storage cell 100, and coated with an electrical insulation layer 420 at the junction of the energy storage cell 100 and the electroluminescent cell 400.
The electrolyte 130 can comprise a liquid electrolyte or a gel electrolyte, wherein the gel electrolyte is not easy to leak and has high safety, the gel electrolyte can be prepared in a glove box filled with nitrogen atmosphere, 0.2-0.6g of ethylene oxide, 0.2-0.6g of succinonitrile and 0.2-0.5g of lithium bis (trifluoromethyl) sulfonyl imide are mixed, a mixed solvent of acetone and dichloromethane is added, and after stirring for 5 hours, the clear and transparent ethylene oxide/succinonitrile/lithium bis (trifluoromethyl) sulfonyl imide gel electrolyte is obtained. An inner cylindrical tube 140 is wrapped around the anode 121, cathode 122 and fiber substrate 110 coated with the electrolyte 130 to separate the lithium ion battery and the solar cell and prevent the electrolytes from permeating each other. The inner cylindrical tube may be an insulating flexible material, such as a heat shrink tube.
An electrically insulating layer 420 is coated on the outer side of the conductive element 410 and the bottom electrode 310 without the light emitting layer 320, and a polymer insulating sleeve material such as rubber, teflon, polydimethylsiloxane, and heat shrinkable tube may be used.
In fig. 2-C, a transparent electrode 330 is disposed outside the light emitting layer 320 and the electrically insulating layer 420, and the transparent electrode 330 may include an oriented multi-walled carbon nanotube film, graphene, or the like. Transparent electrode 330 is not in direct contact with cathode 122. And a light-operated switch is provided between the energy storage cell and the electroluminescent cell, wherein one end of the paddle is connected to the cathode 122 via a controllably conductive bend. When no light is emitted, the plectrum becomes straight, and the connection between the cathode 122 and the transparent electrode 330 is conducted, so that the energy storage unit supplies power to the electroluminescent unit, and the electroluminescent unit emits light; in the absence of illumination, the paddle bends, disconnecting cathode 122 from transparent electrode 330 and the electroluminescent cell does not emit light.
In fig. 2-D, a counter electrode 210 of an energy conversion unit 200 of a solar cell is wound around the outer circumference of an inner cylindrical tube 140, and a photo-anode 220 may be wound outside the counter electrode 210 by a spiral shape. Counter electrode 210 may comprise an oriented multi-walled carbon nanotube film. The oriented multi-walled carbon nanotube film is formed by pulling out and winding the spinnable carbon nanotube array around the inner cylindrical tube 140. The spinnable carbon nanotube array is prepared through chemical vapor deposition process, and the catalyst for preparing the spinnable carbon nanotube array may be prepared through electron beam evaporating and coating system.
The photoanode 220 may be prepared by first winding a 250 μm titanium wire around a 2 mm iron wire to form a helix, then forming vertically aligned titanium dioxide nanotubes on the surface of the titanium wire by an anodic oxidation process, annealing the anodized titanium wire at 500 ℃ for one hour, cooling to room temperature, further performing surface treatment in an aqueous solution of titanium tetrachloride, and annealing again at 450 ℃. Then placing the titanium wire into a perovskite solution to be soaked for 1min, drying the titanium wire at the temperature of 100 ℃, and then repeatedly soaking and drying the titanium wire to form a perovskite crystal layer on the surface of the titanium wire. And then soaking the substrate in chlorobenzene solution containing organic hole transport material OMeTAD, taking out after 1-2min, and forming an organic hole transport layer on the surface after the solvent is volatilized. The prepared composite fiber of the organic hole transport layer/the perovskite crystal layer/the titanium dioxide nanotube/titanium is wound around the outer side of the counter electrode 210, and a thin oriented carbon nanotube film is wound on the outer side of the composite fiber again, so that the photo-anode 220 consisting of the oriented carbon nanotube film/the organic hole transport layer/the perovskite crystal layer/the titanium dioxide/titanium is obtained. Because the thickness of the oriented carbon nanotube film wound on the outermost layer is very thin, most light rays can penetrate through the oriented carbon nanotube film, and meanwhile, because of good conductivity of the oriented carbon nanotube film, the oriented carbon nanotube film is beneficial to transmission of current carriers.
In fig. 2-E, the outer cylindrical tube 230 is disposed outside the photo-anode 220 while enclosing the inner cylindrical tube 140, the counter electrode 210 and the photo-anode 220. The outer cylindrical tube 230 may comprise a transparent insulating flexible material, such as a transparent heat shrink tube.
The invention provides an environment-responsive fibrous self-powered light emitting device and a manufacturing method thereof, wherein a lithium ion battery structure of an energy storage unit is arranged around one end of a substrate; a solar cell as an energy conversion unit is arranged around the lithium ion battery structure; an electroluminescent unit is arranged around the other end of the substrate; a light control switch is provided intermediate the energy storage unit and the electroluminescent unit. The energy storage unit is arranged inside the energy conversion unit, and the part can realize the photoelectric conversion receiving and energy storage functions at the same time. When the solar battery is illuminated, the light-operated switch is switched off, and the energy storage unit stores the electric energy converted by the solar battery structure for later use; when no light is emitted, the light-operated switch is switched on, so that the energy storage unit supplies power to the electroluminescent unit, and the luminous effect is realized. The electrode material of the lithium ion battery structure of the energy storage unit can adopt oriented multi-wall carbon nanotube fibers, has high conductivity and large specific surface area, is easy to be compounded with other active materials, and realizes high energy density. The electrolyte of the lithium ion battery structure can be gel electrolyte, so that the conventional electrolyte leakage risk is avoided. The solar cell structure of the energy conversion unit is fibrous, can receive incident light from all directions, increases the light utilization rate, and is particularly suitable for spaces filled with diffuse scattering light. The novel fibrous integrated device is made of flexible materials, has certain flexibility, flexibility and knittability, and the electrolyte is in a gel state or a solid state, so that the safety of the device is improved, and the device has unique and wide application prospects, such as being woven into electronic fabrics and being used as an independent light-emitting system and a portable micro electronic device and equipment.
The invention integrates a multifunctional electronic device, which comprises an energy conversion unit, an energy storage unit, a photoswitch and an electroluminescent unit, on the same fiber to form a fibrous self-powered luminescent device with environmental response. The device can absorb sunlight and convert the sunlight into electric energy when the light intensity is strong in the daytime, and the electric energy can be stored in an energy storage device inside the fiber; when the light intensity in the environment weakens to a certain degree, the light driving unit can be intelligently communicated with the light emitting unit at the other end of the fiber, so that the fiber at the other end is lightened by the electric energy stored in the energy storage unit. The self-powered light-emitting device can flash like a firefly at night with weak light or dark color, and can play a warning role besides a decorative role when worn on the body.
In summary, in the fibrous self-powered light emitting device and the method for manufacturing the same provided by the present invention, the energy storage unit is disposed on the fibrous substrate in a surrounding manner, the energy conversion unit is disposed on the energy storage unit in a surrounding manner, the fiber substrate is further disposed with the electroluminescent unit, the connection between the electroluminescent unit and the energy storage unit is controlled by the light control switch, since the energy conversion unit is in a linear fibrous shape, the energy conversion unit can receive incident light beams of various angles and convert the incident light beams into electric energy, and is particularly applied to a space filled with diffused light, the prepared electroluminescent unit can emit light at 360 degrees, is similar to the planar light emitting unit in a radial direction, reduces contact resistance, has a high contact area due to coaxial light emission, is beneficial to rapid transmission and transfer of electrons, can sense the intensity of light by the light control switch, and realizes connection and disconnection between the energy storage unit and the electroluminescent unit, can make fibrous self-power luminescent device can be when daytime light intensity is stronger through absorbing the sunlight and turn into the electric energy with it and store in energy storage unit, when the light intensity in the environment weakens to certain degree, can communicate electroluminescent unit through photoswitch energy storage unit realizes giving out light, and whole device possesses certain pliability and bendability, can compile the fabric as the fibre in, provides the condition to wearable electronic equipment's development.
It should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the scope of the present invention.

Claims (10)

1. A fibrous self-energized light emitting device, said fibrous self-energized light emitting device comprising:
the energy storage unit is positioned on a fiber substrate and comprises an anode, a cathode, an electrolyte and an inner cylindrical tube, wherein the inner cylindrical tube is sleeved on the fiber substrate, the anode and the cathode are positioned in the inner cylindrical tube, the anode and the cathode are both in fiber shapes, the anode and the cathode are both wound on the fiber substrate in a spiral shape, the electrolyte is filled between the fiber substrate and the inner cylindrical tube, the energy storage unit adopts a lithium ion battery, and the electrolyte is in a gel state or a solid state so as to ensure that the anode and the cathode are not in contact;
the energy conversion unit adopts a perovskite solar cell, the energy conversion unit of the perovskite solar cell comprises a counter electrode and a photoelectric anode, the counter electrode and the photoelectric anode are positioned on the inner cylindrical tube, the counter electrode is connected with the cathode, and the photoelectric anode is connected with the anode;
the electroluminescent unit is positioned on the fiber substrate and comprises a bottom electrode, a light-emitting layer and a transparent electrode which are sequentially formed, wherein the bottom electrode is connected with the anode, and the transparent electrode is connected with the cathode;
the light-operated switch controls the connection between the electroluminescent unit and the energy storage unit, the light-operated switch comprises a conductive element, an insulating layer and a controllably bent conductive shifting sheet, the conductive element is connected between the anode of the energy storage unit and the bottom electrode of the electroluminescent unit, and the conductive shifting sheet is connected with the cathode of the energy storage unit and the transparent electrode of the electroluminescent unit.
2. The fibrous self-energized light emitting device of claim 1, wherein the anode and the cathode each comprise aligned carbon nanotubes and active nanoparticles.
3. The fibrous self-energized light emitting device of claim 1, wherein the bottom electrode comprises aligned carbon nanotubes and conductive nanoparticles.
4. The fibrous self-powered light emitting device of claim 1, wherein the number of the energy conversion units is two or more, and the two or more energy conversion units are connected in series.
5. The fibrous self-energized light emitting device of claim 1, wherein the electrolyte is a gel electrolyte.
6. The fibrous self-energized light emitting device of claim 1, wherein the photo-anode is wound in a linear spiral on the counter electrode.
7. The fibrous self-energized light emitting device of claim 1, wherein the anode and the cathode are both circumferentially disposed on the fibrous substrate.
8. The fibrous self-energized light emitting device of claim 1, wherein the bottom electrode and the transparent electrode each comprise aligned carbon nanotubes and the light emitting layer is a light emitting polymer material.
9. The fibrous self-powered light emitting device of any of claims 1-8, wherein the conductive pick comprises a substrate, a conductive layer, a paraffin layer, and an aligned carbon nanotube film layer, the conductive layer being on one side of the substrate, the paraffin layer being on the other side of the substrate, the aligned carbon nanotube film layer being on the paraffin layer.
10. A method for preparing a fibrous self-energized light-emitting device, the method comprising:
providing a fiber substrate, forming an anode and a cathode on one end of the fiber substrate, and forming a bottom electrode on the other end of the fiber substrate, wherein the bottom electrode is connected with the anode;
disposing an inner cylindrical tube on the fiber substrate, wherein the anode and the cathode are both located in the inner cylindrical tube, and both the anode and the cathode are in fiber shapes, the anode and the cathode are both spirally wound on the fiber substrate, an electrolyte is filled between the inner cylindrical tube and the fiber substrate, the anode, the cathode and the electrolyte form an energy storage unit, and a light emitting layer is formed on the bottom electrode, wherein the energy storage unit adopts a lithium ion battery, and the electrolyte is in a gel state or a solid state to ensure that the anode and the cathode are not in contact with each other;
forming a counter electrode on the inner cylindrical tube, forming a photo-anode on the counter electrode, the counter electrode and the photo-anode forming an energy conversion unit, the counter electrode is connected with the cathode, the photoelectric anode is connected with the anode, a transparent electrode is formed on the luminous layer, the bottom electrode, the luminescent layer and the transparent electrode form an electroluminescent unit, a photoswitch is arranged to control the connection of the electroluminescent unit and the energy storage unit, the energy conversion unit adopts a perovskite solar cell, wherein the photoswitch comprises a conductive element, an insulating layer and a controllably bendable conductive paddle, the conductive element is connected between the anode of the energy storage cell and the bottom electrode of the electroluminescent cell, the conductive plectrum is connected with the cathode of the energy storage unit and the transparent electrode of the electroluminescent unit.
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