Electroluminescent bifunctional electrode fiber and its use in the production of electroluminescent devices

Abstract

The application relates to an electrode fiber, in particular to an electroluminescent bifunctional electrode fiber and application of the electrode fiber in preparation of an electroluminescent device, and belongs to the technical field of electroluminescent electronic devices. The bifunctional electrode fiber is prepared by the following method: taking a zinc wire with a diameter of 0.3-2.0 mm as a core wire, adopting a spinning solution to electrostatically spin on the surface of the zinc wire to form a nanofiber layer, and preparing the bifunctional electrode fiber; the spinning solution contains 15-25% of thermoplastic polyurethane, 5-20% of zinc copper sulfide, 2-10% of PDMS, and the rest is a solvent composed of N-N dimethylformamide and tetrahydrofuran. The application integrates two functions on one electrode fiber, can easily prepare a fibrous zinc ion battery and a fibrous electroluminescent device by changing the formula of an electrolyte, and can also introduce a third fiber into the fibrous zinc ion battery to endow the battery with the electroluminescent capability.

Description

Technical Field

[0001] The present invention relates to an electrode fiber, in particular to an electroluminescent dual-function electrode fiber and application thereof in preparing an electroluminescent device, belonging to the technical field of electroluminescent electronic devices. Background Art

[0002] Flexible alternating current electroluminescence (ACEL) is attracting academic and commercial attention in emerging flexible electronics fields such as wearable health monitoring systems, electronic skin, and electronic textiles. Traditional sandwich-structured EL devices are usually attached to textiles in a rough manner. Since planar EL can easily peel off from textiles, the underlying substrate must be planarized. In contrast, yarn-like EL devices can be flexibly integrated with traditional yarns to form textile displays, which are not only more stable and flexible, but can also adapt to more stringent external influences.

[0003] However, because electroluminescence requires alternating current (AC), all EL devices currently on the market require a DC-to-AC driver. Due to the low mechanical deformation of current energy storage batteries, these drivers are typically large and inflexible, which limits the use of EL devices. Therefore, the most significant challenge in this field is developing wearable energy storage devices with excellent electrochemical properties, high deformation resistance, and flexibility. One-dimensional aqueous zinc-ion batteries, with their safety and high mechanical properties, are considered one of the most promising devices among one-dimensional structural batteries. Furthermore, zinc-ion batteries using gel electrolytes share a similar structure to fiber-shaped EL devices, making it possible to combine both functions on a single electrode.

[0004] Nanofibers prepared by electrospinning have high orientation, high porosity, and insulating properties. Electroluminescent materials, namely copper zinc sulfide and PDMS, are attached to the nanofiber layer through electrospinning. This effectively suppresses side reactions in zinc-ion battery systems, while improving the zinc ion transport pathway and the electrochemical performance of zinc-ion batteries. The nanofiber layer also serves as the light-emitting layer and dielectric layer in electroluminescent devices, effectively emitting light when connected to an alternating current. However, due to the insulation between the two electrodes required for electroluminescence, ions cannot be transported between the two electrodes, making energy storage impossible. Therefore, how to effectively control the device structure and selectively prepare zinc-ion batteries and electroluminescent devices has become a major systemic problem in this system. Summary of the Invention

[0005] The purpose of the present invention is to provide a bifunctional electrode fiber. The preparation method of the bifunctional electrode fiber has the advantages of being simple and convenient, low cost, continuous preparation, and green and environmentally friendly. The electrode fiber can be used to prepare fibrous zinc-manganese batteries and fibrous electroluminescent devices.

[0006] The technical solution adopted by the present invention to solve its technical problem is:

[0007] A bifunctional electrode fiber is prepared by the following method:

[0008] Using zinc wire with a diameter of 0.3-2.0 mm as the core wire, a spinning solution is used to electrospin the zinc wire surface to form a nanofiber layer to prepare a dual-functional electrode fiber;

[0009] The spinning solution contains, by weight percentage, 15-25% of thermoplastic polyurethane, 5-20% of zinc copper sulfide, 2-10% of PDMS, and the balance being a solvent consisting of N-N-dimethylformamide and tetrahydrofuran. The mass ratio of N-N-dimethylformamide to tetrahydrofuran in the solvent is 100:0-50:50, and the molecular weight of the thermoplastic polyurethane is 10,000-50,000.

[0010] The fibers attached to the zinc wire surface are controlled by adjusting the winding device speed, the funnel collector rotation speed, the injector flow rate and the positive and negative voltages.

[0011] Preferably, the electrospinning parameters are set as follows: the angle between the needle tip and the collector is 60°, the distance between the needle tip and the collector is 8 cm, the injection pump propels the spinning solution at a rate of 1.2 mL / h, 12-17 KV DC high voltage electricity is used during the spinning process, the funnel-shaped collector rotates at a speed of 120-240 rpm, and the winding device speed is 0.06 m / min.

[0012] Preferably, the spinning dope comprises, by weight, 18-20% thermoplastic polyurethane, 18-20% zinc copper sulfide, 7-8% PDMS, and the balance a solvent consisting of N-N-dimethylformamide and tetrahydrofuran, with the mass ratio of N-N-dimethylformamide to tetrahydrofuran being 50:50. The optimal spinning dope formulation is: 18.5% thermoplastic polyurethane, 18.5% zinc copper sulfide, 7.5% PDMS, 27.7% N-N-dimethylformamide, and 27.7% tetrahydrofuran.

[0013] The application point of the application is mainly in the preparation of the bifunctional electrode fiber, and secondly, the application can selectively construct a battery or an electroluminescent device by controlling the electrolyte preparation, and the difficulty lies in that the electroluminescent device requires no ion transmission, while the battery requires ion transmission, and how to selectively control the ion transmission in the nanofiber layer is the key point of the application. In the application, the hydrophobic PDMS is added, so that the nanofiber membrane will not be wetted when the gel precursor of the electroluminescent gel is used to construct the gel, and therefore there will be no ion transmission. After the photoinitiator is added in the electrolyte, the photoinitiator will penetrate into the nanofiber layer because the photoinitiator is an amphiphilic substance. At this time, the added luminescent powder zinc copper sulfide and PDMS in the nanofiber can provide more zinc ion transmission sites, and thus improve the battery performance.

[0014] In order to make the environment of the positive and negative electrodes of the battery different, and improve the performance of the battery, the application adopts neutral electrolyte and weakly acidic electrolyte to prepare the fibrous aqueous zinc ion battery.

[0015] By controlling the components in the electrolyte, whether the nanofiber layer will be wetted can be easily controlled, and therefore a single-function electrode fiber can be selectively prepared. When a third fiber is introduced into the system, the device can be given a second function, and a new idea is provided for the integrated application of flexible electronics.

[0016] A fibrous aqueous zinc ion battery prepared by using the bifunctional electrode fiber described in the application, the fibrous zinc ion battery is prepared by the following method:

[0017] S1 preparation of electrolyte

[0018] The acrylamide and zinc sulfate heptahydrate are sequentially added to water and mixed, and then the N-N methylene bisacrylamide and the photoinitiator are sequentially added and mixed to obtain a neutral electrolyte; the neutral electrolyte contains the following components in mass percentage: acrylamide 10-20%, zinc sulfate heptahydrate 45-55%, N-N methylene bisacrylamide 0.05-0.5%, photoinitiator 0.05-0.5%, and the balance is water;

[0019] The acrylamide, zinc sulfate heptahydrate and manganese sulfate are added to a weakly acidic solution with a pH value of 2-3 and mixed, and then the N-N methylene bisacrylamide and the photoinitiator are sequentially added and mixed to obtain a weakly acidic electrolyte; the weakly acidic electrolyte contains the following components in mass percentage: acrylamide 10-20%, zinc sulfate heptahydrate 40-50%, manganese sulfate 5-10%, N-N methylene bisacrylamide 0.05-0.5%, photoinitiator 0.05-0.5%, and the balance is a weakly acidic solution with a pH value of 3-5;

[0020] S2 preparation of fibrous aqueous zinc ion battery

[0021] The bifunctional electrode fiber is used as the negative electrode and inserted into a polytetrafluoroethylene tubular mold. The neutral electrolyte prepared in S1 is injected into the mold and photoinitiated to obtain a bifunctional electrode fiber / photoinitiator gel electrolyte yarn.

[0022] The bifunctional electrode fiber and the conductive carbon filament are used as positive electrode current collectors, and two bifunctional electrode fiber / photoinitiator gel electrolyte yarns are inserted into a heat shrink tube in parallel. The weak acid electrolyte prepared in S1 is injected into the heat shrink tube using a syringe, and photoinitiated to obtain a yarn-shaped aqueous zinc ion battery without a positive electrode;

[0023] S3 active material loading

[0024] A yarn-shaped aqueous zinc ion battery without a positive electrode prepared with S2 was used as a device. The manganese ions in the electrolyte were oxidized into manganese oxides and deposited on the surface of the positive electrode current collector by chronoamperometry or constant voltage charging for several minutes under constant voltage conditions using an electrochemical workstation or a blue-electric workstation.

[0025] Preferably, the photoinitiator is one or more of 2-hydroxy-2-methylpropiophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, and 1-hydroxycyclohexylphenyl ketone;

[0026] The weak acid solution is a weak acid solution with a pH value of 2-3 obtained by dissolving an appropriate amount of acid in water and stirring for 1-5 hours; the acid is selected from one or more of citric acid, concentrated sulfuric acid, carbonic acid, hydrochloric acid, malic acid, oxalic acid or nitric acid.

[0027] Preferably, the photoinitiator uses UV light with a wavelength of 250-400nm, and the initiation time is 2-30min; the specifications of the conductive carbon filament are one or more of 1K, 3K, 12K, and 24K;

[0028] The diameter of the PTFE tubular mold is 0.5-3 mm;

[0029] The diameter of the heat shrink tubing is 1-10mm.

[0030] Preferably, the constant voltage charging voltage in S3 is 1.6-2.4V, and the charging time is 1-120min.

[0031] A fiber-shaped electroluminescent device made using the bifunctional electrode fiber of the present invention is made by the following method:

[0032] acrylamide, zinc sulfate heptahydrate, and water are mixed, and NN methylenebisacrylamide is added and mixed to obtain an electroluminescent electrolyte; the electroluminescent electrolyte comprises the following components in percentage by weight: 10-20% acrylamide, 45-55% zinc sulfate heptahydrate, 0.05-0.5% NN methylenebisacrylamide, and the balance water;

[0033] Mixing a thermal initiator and water to obtain a thermal initiator solution with a mass percentage of 5-10%; the thermal initiator is one or both of potassium persulfate and ammonium persulfate;

[0034] Take two of the bifunctional electrode fibers, insert them into a heat shrink tube, quickly mix the electroluminescent electrolyte and the thermal initiator solution, and then fill the heat shrink tube to make the weight ratio of the electroluminescent electrolyte to the thermal initiator be 400:1-200:1. Initiate gelation at room temperature to obtain a fiber-shaped electroluminescent device.

[0035] An application of the bifunctional electrode fiber of the present invention in the preparation of an electroluminescent device.

[0036] The method of the present invention has simple preparation steps. The nanofiber layer prepared by electrospinning can not only serve as a diaphragm in the battery field to inhibit side reactions, but also serve as a light-emitting layer and dielectric layer in the electroluminescence field, integrating the two functions on one electrode fiber. By changing the formula in the electrolyte, fiber-shaped zinc ion batteries and fiber-shaped electroluminescent devices can be easily prepared. At the same time, a third fiber can be introduced into the fiber zinc ion battery to give it electroluminescence ability.

[0037] The present invention uses zinc wire as a substrate and prepares a nanofiber layer on the surface of the zinc wire by electrospinning to construct a dual-functional electrode fiber. The added PDMS is hydrophobic, and the photoinitiator usually has an oleophilic group. Therefore, the configured electrolyte can wet the nanofiber layer to provide the ion transmission channel required by the zinc ion battery. When an electroluminescent electrolyte is used, since a thermal initiator without an oleophilic group is used, the solution cannot wet the nanofiber layer. At this time, the nanofiber layer can act as the light-emitting layer and dielectric layer in the electroluminescent device. After connecting to an alternating current, electroluminescence can be performed through the liquid corresponding mechanism. It is worth mentioning that It is worth noting that when the zinc sulfate concentration is sufficient, the precursor solution can be quickly triggered at room temperature after the heated initiator solution is dripped, which reduces the possibility of the nanofiber layer being wetted and optimizes the process of the fiber electroluminescent device; and adding a third dual-functional electrode fiber to the constructed zinc ion battery system will not only not affect the energy storage function, but the positive and negative fibers of the zinc ion battery can now charge the other electrode of the electroluminescent device, realizing the application of three electrode fibers in one device to meet two functions; the device prepared by this preparation method belongs to the field of one-dimensional semi-solid-state batteries and electroluminescence, making it promising for application in the field of flexible electronics.

[0038] Compared with the prior art, the present invention has the following characteristics:

[0039] 1. The present invention uses an electrospinning method to prepare a nanofiber layer on the surface of a zinc wire, and adds an electroluminescent material to the spinning solution to construct a dual-function electrode fiber;

[0040] 2. The present invention uses different electrolytes and realizes different functional applications of bifunctional electrode fibers by controlling the components in the solution. When the electrolyte is used for photoinitiation, the lipophilic molecules can wet the nanofiber layer. The special structure of the nanofiber can provide an electrolyte transmission channel for the battery. At the same time, the zinc copper sulfide can provide more zinc-philic sites, and the dynamic BO bond in PDMS can reduce the hydrogen evolution reaction and inhibit the growth of zinc dendrites. Therefore, the fiber zinc ion battery has more excellent electrochemical performance. When the electroluminescent electrolyte is used, it cannot wet the nanofiber layer. At this time, the device is similar to a capacitor structure. The nanofiber layer acts as a light-emitting layer and a dielectric layer in the system, which can effectively meet the electroluminescence function.

[0041] 3. The present invention uses active material current collectors to directly assemble batteries, which can reduce the time required to prepare active material paste. It can also reduce the uneven coating of active material on the yarn surface and the loss of active material due to scratches during subsequent operations, greatly accelerating the preparation speed and stability, and laying the foundation for subsequent large-scale production.

[0042] 4. The present invention adds zinc sulfate in a sufficient concentration to the acrylamide solution, which can be initiated at room temperature under the premise of using a thermal initiator, and has the advantages of fast speed and low energy consumption;

[0043] 5. The present invention can impart energy storage and electroluminescence functions to the same device through three electrode fibers, realizing energy storage-application integration and providing new ideas for the development of flexible electronics. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 The brightness curves of electroluminescent devices with different masses of zinc copper sulfide in Example 2;

[0045] Figure 2 The EIS spectra of zinc ion batteries with different masses of zinc copper sulfide in Example 2;

[0046] Figure 3 The SEM images and mapping images of the dual-functional electrode fibers of Supplementary Example 1, wherein Figure a is the SEM image, Figures bf are mapping images, (b) Si element (c) B element (d) O element (e) Zn element (f) Cu element;

[0047] Figure 4 This is the infrared spectrum analysis diagram of Supplementary Example 1;

[0048] Figure 5 To supplement the contact angle test in Example 2, Figure a shows the contact angle between the electrolyte for zinc ion batteries and the nanofiber membrane, and Figure b shows the contact angle between the electroluminescent electrolyte and the nanofiber membrane;

[0049] Figure 6 To supplement the actual pictures of different gels in Example 3, the left one is the electrolyte for zinc ion batteries, and the right one is the electroluminescent electrolyte;

[0050] Figure 7 To supplement the polarization performance test of Example 4, Figures ac are Nyquist plots before and after the chronoamperometry test, and Figures df are chronoamperometry test curves, where Figures a and d are Zn-Zn symmetric batteries, Figures b and e are TPU / PAM-based control batteries, and Figures c and f are PAM-based control batteries;

[0051] Figure 8 To supplement the Arrhenius curve and EIS spectra at different temperatures of Example 4, Figure a is the Arrhenius curve, Figures b and d are EIS spectra at different temperatures, Figure b is a Zn-Zn symmetric battery, Figure c is a TPU / PAM-based control battery, and Figure d is a PAM-based control battery;

[0052] Figure 9 The linear sweep voltammetry curve of Supplementary Example 4 is shown;

[0053] Figure 10 To supplement the Tafel curve of Example 4;

[0054] Figure 11 To supplement the rate performance test of the zinc-zinc symmetrical battery in Example 4;

[0055] Figure 12 To supplement the long cycle performance test of the zinc-zinc symmetric battery in Example 4;

[0056] Figure 13 To supplement the long cycle performance test of the fiber zinc-manganese full battery in Example 5;

[0057] Figure 14 This is a photo of the fiber electroluminescent device of Example 6 being lit up;

[0058] Figure 15 This is a graph showing the variation of the brightness of the fiber electroluminescent device with voltage and frequency in Supplementary Example 6;

[0059] Figure 16 This is a graph showing how the luminous color of the fiber electroluminescent device in Supplementary Example 6 changes with frequency. DETAILED DESCRIPTION

[0060] The technical solution of the present invention is further described in detail below through specific examples. It should be understood that the implementation of the present invention is not limited to the following examples, and any form of modification and / or change made to the present invention will fall within the scope of protection of the present invention.

[0061] In the present invention, unless otherwise specified, all parts and percentages are by weight, and the equipment and raw materials used are commercially available or commonly used in the art. The methods in the following examples are all conventional methods in the art unless otherwise specified.

[0062] Unless otherwise specified, the reagents used in the following examples can be purchased from conventional biochemical reagent stores.

[0063] The UV lamp model is WFH-204B, with wavelengths of 254nm and 365nm.

[0064] The present invention uses zinc wire as the main body, adds traditional electroluminescent materials, namely zinc copper sulfide and PDMS, into the spinning solution, and performs electrostatic spinning to obtain bifunctional electrode fibers; when the bifunctional electrode fibers are used as the negative electrode, the conductive carbon fibers are used as the positive electrode current collector and are inserted into a heat shrink tube in parallel, and the heat shrink tube is filled with a weak acid gel electrolyte to construct a fiber zinc ion battery, and the manganese ions in the electrolyte are oxidized and deposited on the surface of the positive electrode current collector through constant voltage charging or chronoamperometry to form the final device; when two bifunctional electrode fibers are used and inserted into a heat shrink tube in parallel and filled with an electroluminescent gel electrolyte, a fiber electroluminescent device is constructed.

[0065] Among them, the construction of the nanofiber layer gives the electrode fiber dual functions. By controlling the formula of the electrolyte precursor solution, the wetting of the nanofiber layer can be effectively controlled. When the nanofiber layer is wetted, it can provide an ion transmission channel. At the same time, the polymer body in the nanofiber and the added zinc copper sulfide, PDMS can further protect the zinc negative electrode, thereby constructing a fiber battery. When the nanofiber layer is not wetted, the nanofiber layer acts as a light-emitting layer and a dielectric layer, effectively constructing a fiber electroluminescent device. Since the two devices are in similar environments, it is entirely possible to introduce a third electrode fiber into the fiber-shaped zinc ion battery system and give it an electroluminescent function, combining the electroluminescent function with energy storage into one device, and using a zinc ion battery to power the electroluminescent device, providing a new idea for the inheritance of fiber-shaped flexible electronic devices.

[0066] Example 1 Investigation of zinc sulfate concentration in electroluminescent electrolyte

[0067] Preparation of electroluminescent electrolyte

[0068] 3g of acrylamide was taken in several portions, and 7.5g of deionized water was added to each portion. Then, 2.8g, 4.2g, 5.6g, 7g, 8.4g, 9.8g, 11.2g, 12.6g, and 14g of zinc sulfate heptahydrate were added in sequence, and the mixture was stirred on a stirrer at room temperature for 5 minutes. Then, 20μg of NN methylenebisacrylamide was added, and the mixture was stirred on a stirrer for 5 minutes to obtain electroluminescent electrolytes with different zinc sulfate heptahydrate contents.

[0069] 0.5 g of potassium persulfate was added to 10 g of deionized water, and the mixture was placed on a stirrer and stirred at room temperature for 10 min to obtain a thermal initiator solution.

[0070] Several 200mg portions of the electroluminescent electrolyte were added, followed by the addition of 10mg of thermal initiator, and the initiation process was observed. The initiation times of the electroluminescent electrolytes containing different amounts of zinc sulfate heptahydrate are shown in Table 1.

[0071] Table 1

[0072]

[0073] Typically, thermal initiators require temperatures above 80°C to initiate gelation. However, when the electrolyte is in a high zinc sulfate concentration system, initiation can occur at room temperature. As shown in Table 1, when the zinc sulfate heptahydrate addition amount is less than 5.6g, the electrolyte is completely uninitiated and cannot form a gel. However, as the zinc sulfate heptahydrate mass increases, initiation can be achieved in less than two minutes at room temperature. When the zinc sulfate heptahydrate mass exceeds 9.8g, the initiation time is maintained at approximately 30 seconds. Rapid gelation helps to immobilize water molecules and prevent the nanofiber layer from being penetrated, meeting the requirements of electroluminescent devices. However, when the zinc sulfate heptahydrate mass exceeds 14g, it is close to saturation and cannot be completely dissolved.

[0074] Taking the cost and the priming effect into consideration, the optimal concentration was finally considered to be 45-55%.

[0075] Example 2 Investigation of the amount of zinc copper sulfide in the spinning solution for electrospinning

[0076] 1. Preparation of spinning solution for electrospinning

[0077] 2 g, 3 g, 4 g, 5 g, 6 g, and 7 g of zinc copper sulfide were added to 5 g of thermoplastic polyurethane in sequence, and dissolved in 7.5 g of N-N-dimethylformamide and 7.5 g of tetrahydrofuran solvent. The mixture was magnetically stirred at room temperature for 12 h. 2 g of PDMS was then added to the solution, and magnetically stirred at room temperature for another 1 h to form a uniform spinning solution.

[0078] 2. Preparation of bifunctional electrode fibers

[0079] Using 0.5 mm zinc wire as the core wire, the spinning solution prepared in step (1) was used to perform electrostatic spinning using an electrospinning device. The angle between the needle tip and the collector was 60°, the distance between the needle tip and the collector was 8 cm, and the spinning solution was pushed forward by the injection pump at a speed of 1.2 mL / h. During the spinning process, 16 kV DC high voltage electricity was used, the funnel-shaped collector speed was 80 rpm, and the winding device speed was 0.06 m / min to prepare bifunctional electrode fibers with different zinc copper sulfide concentrations.

[0080] 3. Preparation of neutral electrolyte

[0081] 3 g of acrylamide and 8.4 g of zinc sulfate heptahydrate were added to 7.5 g of deionized water in sequence, and the mixture was stirred on a stirrer at room temperature for 5 min. 20 μg of NN methylenebisacrylamide and 20 μL of 2-hydroxy-2-methylpropiophenone were then added in sequence, and the mixture was stirred on a stirrer for 5 min to obtain a neutral electrolyte.

[0082] 4. Preparation of electroluminescent electrolyte

[0083] 3 g of acrylamide and 8.4 g of zinc sulfate heptahydrate were added to 7.5 g of deionized water in sequence, and the mixture was stirred on a stirrer at room temperature for 5 min. 20 μg of N-N methylenebisacrylamide was then added and the mixture was stirred on a stirrer for 5 min to obtain an electroluminescent electrolyte.

[0084] 0.5 g of potassium persulfate was added to 10 g of deionized water, and the mixture was placed on a stirrer and stirred at room temperature for 10 min to obtain a thermal initiator solution.

[0085] 5. Yarn-shaped stainless steel symmetrical battery test group

[0086] Taking the bifunctional electrode fiber as the substrate, two 5cm bifunctional electrode fibers were sequentially stuffed into a polytetrafluoroethylene tubular mold with a diameter of 0.8mm. A neutral electrolyte was injected into the mold using a syringe, and photoinduced for 2 minutes by a UV lamp with a wavelength of 254nm. After taking out, the two fibers were again stuffed into a heat shrink tube with a diameter of 2mm in parallel, and a neutral electrolyte was injected into the heat shrink tube using a syringe. Photoinduced for 10 minutes by a UV lamp with a wavelength of 254nm to obtain a yarn-shaped zinc-zinc symmetrical battery.

[0087] 6. Preparation of yarn-shaped electroluminescent devices

[0088] Take 20 cm of the bifunctional electrode fiber prepared in Example 1 and a 0.5 mm zinc wire and insert them in parallel into a 1 mm diameter heat shrink tube. Take 1 g of electroluminescent electrolyte and 0.05 g of thermal initiator solution, stir them quickly, and inject them into the tube through a syringe to initiate gelation at room temperature, thereby constructing a yarn-shaped electroluminescent device.

[0089] Table 2 shows the activation energy of zinc ion batteries with different zinc copper sulfide contents in Example 2.

[0090] Table 2

[0091] Copper zinc sulfide mass (g) 2 3 4 5 6 7 <![CDATA[活化能(kJmol -1 )]]> 7.968 8.015 8.023 8.034 8.044 8.058

[0092] The concentration of zinc copper sulfide is one of the determining factors of the brightness of electroluminescent devices. At the same time, zinc copper sulfide can provide more zinc-affinity sites in zinc ion batteries, accelerate the transfer of zinc ions, and thus improve the cycle life of zinc ion batteries. Figure 1 As shown in the figure, under the condition of 300V 3kHz, the brightness of the electroluminescent device increases with the increase of the concentration of zinc copper sulfide. However, when the mass of zinc copper sulfide exceeds 5g, the brightness of the electroluminescent device basically does not remain unchanged. The EIS spectrum of the prepared stainless steel symmetrical battery test is shown in the attached figure. Figure 2 As shown in Table 2, the calculated activation energy shows that as the quality of zinc copper sulfide increases, the resistance and activation energy further decrease, which shows that zinc copper sulfide helps to improve the transport of zinc ions. Combined with the performance of electroluminescent devices and zinc ion batteries, the optimal zinc copper sulfide concentration is finally considered to be 18.5%.

[0093] Example 3 Preparation method of dual-function electrode fiber

[0094] 1. Preparation of spinning solution for electrospinning

[0095] 5 g of thermoplastic polyurethane and 5 g of zinc copper sulfide powder were dissolved in 7.5 g of N-N-dimethylformamide and 7.5 g of tetrahydrofuran solvent, and magnetically stirred at room temperature for 12 h. 2 g of PDMS was then added to the solution, and magnetically stirred at room temperature for another 1 h to form a uniform spinning solution.

[0096] 2. Preparation of bifunctional electrode fibers

[0097] Using 0.5 mm zinc wire as the core wire, the spinning solution prepared in step (1) was used to perform electrostatic spinning using an electrospinning device. The angle between the needle tip and the collector was 60°, the distance between the needle tip and the collector was 8 cm, and the spinning solution was pushed forward by the injection pump at a speed of 1.2 mL / h. During the spinning process, 16 kV DC high voltage electricity was used, the funnel-shaped collector speed was 80 rpm, and the winding device speed was 0.06 m / min to prepare bifunctional electrode fibers.

[0098] Supplementary Example 1: Analysis of the morphology of bifunctional electrode fibers

[0099] 1. Morphology analysis: The actual image of the dual-function electrode fiber prepared in Example 1 under UV light is shown in the attached figure. It can be seen that zinc copper sulfide is evenly attached to the yarn surface; the SEM image and mapping image of the dual-function electrode fiber are shown in the attached figure. Figure 3As described above, it can be seen that the size and structure of the nanofiber layer prepared by electrospinning are uniform and flat, and the fibers as a whole present a uniformly arranged structure. The element distribution of Zn, Cu, Si, and B shows that zinc copper sulfide and PDMS are relatively evenly dispersed without a granular structure. The uniform distribution of zinc copper sulfide plays an important role in subsequently accelerating zinc ion migration and uniform luminescence, while the uniform distribution of PDMS plays an important role in subsequently stabilizing hydrophobicity and inhibiting side reactions.

[0100] 2. Infrared spectrum analysis: as attached Figure 4 As shown, 794cm -1 Si-C stretching vibration peak, 1014 cm -1 The stretching vibration peaks of Si-O are 1058 cm-1 and 1225 cm-1. -1 They are the bending vibration and stretching vibration peaks of BO, 1411 cm -1 and 1531cm -1 They are the characteristic peaks of amide I and amide II, 1731 cm -1 is the carbonyl vibration peak, 2964 cm -1 is the stretching vibration peak of -CH3, 3347cm -1 It is the NH stretching peak of the amide bond, which further illustrates the uniform distribution of PDMS.

[0101] Example 4 Preparation method of nanofiber membrane

[0102] 1. Preparation of spinning solution for electrospinning: same as in Example 1.

[0103] 2. Preparation of nanofiber membrane

[0104] The spinning solution prepared in step (1) was used for electrospinning. The distance between the needle tip and the collector was 8 cm. The injection pump pushed the spinning solution at a speed of 1.5 mL / h. During the spinning process, a 9 KV DC high voltage point was used and the collector speed was 150 rpm to prepare a nanofiber membrane.

[0105] 3. Preparation of neutral electrolyte

[0106] 3 g of acrylamide and 8.4 g of zinc sulfate heptahydrate were added to 7.5 g of deionized water in sequence, and the mixture was stirred on a stirrer at room temperature for 5 min. 20 μg of NN methylenebisacrylamide and 20 μL of 2-hydroxy-2-methylpropiophenone were then added in sequence, and the mixture was stirred on a stirrer for 5 min to obtain a neutral electrolyte.

[0107] 4. Preparation of electroluminescent electrolyte

[0108] 3 g of acrylamide and 8.4 g of zinc sulfate heptahydrate were added to 7.5 g of deionized water in sequence, and the mixture was stirred on a stirrer at room temperature for 5 min. 20 μg of N-N methylenebisacrylamide was then added and the mixture was stirred on a stirrer for 5 min to obtain an electroluminescent electrolyte.

[0109] 0.5 g of potassium persulfate was added to 10 g of deionized water, and the mixture was placed on a stirrer and stirred at room temperature for 10 min to obtain a thermal initiator solution.

[0110] Supplementary Example 2 Wetting Performance Test

[0111] Due to the difference in structure between electroluminescent devices and zinc ion batteries, in zinc ion battery systems, it is necessary to promote the transmission of zinc ions between electrodes, while in electroluminescent devices, the electrodes need to be relatively insulated to construct a capacitor structure. Therefore, controlling the wetting of the nanofiber layer by the electrolyte becomes the key to selectively constructing different devices. The nanofiber membrane prepared in step (2) of Example 2 was used as a test sample, and the precursor solution of steps (3) and (4) was used as the liquid. The contact angle was measured using a video contact angle tensiometer. 5 μL of liquid was dropped on the surface of the fiber membrane. The water contact angle was as shown in the attached figure. Figure 5 As shown in the figure. Due to the hydrophobicity of PDMS, the prepared nanofiber membrane has a certain degree of hydrophobicity. Therefore, when using an electroluminescent electrolyte, the nanofiber membrane presents a large contact angle. This results in the nanofiber layer isolating the ion transmission between the two electrodes, thus meeting the requirements of the electroluminescent device. However, since the 2-hydroxy-2-methylpropiophenone added to the neutral electrolyte is an amphiphilic molecule, the neutral electrolyte can effectively wet the nanofiber membrane. At this time, the nanofiber layer can form a double network structure with the gel, which can increase the transmission speed of zinc ions and thus improve the performance of the zinc ion battery.

[0112] Supplementary Example 3 Gel Properties

[0113] 200 mg of the electroluminescent electrolyte of step (4) of Example 2 was mixed with 10 mg of the thermal initiator solution at room temperature. Within one minute of the mixing of the solutions, the solutions reacted rapidly and polymerized to form a gel. 200 μL of the neutral electrolyte of step (3) was photo-initiated by a UV lamp with a wavelength of 254 nm for 10 minutes to form a gel. Figure 6 As shown, the electroluminescent electrolyte has a more transparent transparency than the electrolyte used in zinc ion batteries.

[0114] Example 5 Preparation of yarn-shaped zinc-zinc symmetric battery

[0115] Preparation of control group electrode fibers: 5g of thermoplastic polyurethane was weighed and dissolved in 7.5g of N-N dimethylformamide and 7.5g of tetrahydrofuran solvent. The solution was stirred magnetically at room temperature for 12h to form a uniform control group spinning solution. Using a 0.5mm zinc wire as the core wire, the prepared spinning solution was used to perform electrospinning using an electrospinning device. The angle between the needle tip and the collector was 60°, the distance between the needle tip and the collector was 8cm, and the syringe pump pushed the spinning solution at a rate of 1.2mL / h. During the spinning process, 16kV DC high voltage electricity was applied, the funnel-shaped collector rotated at 80rpm, and the winding device speed was 0.06m / min to prepare the control group electrode fibers. Compared with the bifunctional electrode fiber spinning solution described in the present invention, the control group spinning solution did not contain 5g of zinc copper sulfide and 2g of PDMS.

[0116] Preparation of neutral electrolyte: same as in Example 2.

[0117] Yarn-shaped zinc-zinc symmetrical batteries were prepared using the bifunctional electrode fibers prepared in Example 1 and the electrode fibers prepared in the control group.

[0118] 1. Yarn-shaped zinc-zinc symmetric battery test group

[0119] Taking the bifunctional electrode fiber as the substrate, two 5cm bifunctional electrode fibers were sequentially stuffed into a polytetrafluoroethylene tubular mold with a diameter of 0.8mm. A neutral electrolyte was injected into the mold using a syringe, and photoinduced for 2 minutes by a UV lamp with a wavelength of 254nm. After taking out, the two fibers were again stuffed into a heat shrink tube with a diameter of 2mm in parallel, and a neutral electrolyte was injected into the heat shrink tube using a syringe. Photoinduced for 10 minutes by a UV lamp with a wavelength of 254nm to obtain a yarn-shaped zinc-zinc symmetrical battery.

[0120] 2. Yarn-shaped zinc-zinc symmetric battery control group

[0121] The yarn-shaped Zn-Zn symmetric TPU / PAM-based control battery was prepared in the same way, except that the control group electrode fiber was used as the substrate, and two 5-cm control group electrode fibers were sequentially stuffed into a polytetrafluoroethylene tubular mold.

[0122] The yarn-like Zn-Zn symmetric PAM-based control cells were prepared in the same way, except that 0.5 mm zinc wire was used as the substrate, and two 5 cm zinc wires were sequentially stuffed into a polytetrafluoroethylene tubular mold.

[0123] Supplementary Example 4: Testing of zinc protection performance of yarn-shaped zinc-zinc symmetric battery

[0124] 1. Polarization test: The prepared zinc-zinc symmetrical battery was used for testing. The EIS spectrum at 10m-100K was first tested by electrochemical workstation. The chronoamperometry test was carried out for 2h at a constant polarization potential of 10mV. The polarized symmetrical battery was tested again for EIS spectrum at 10m-100K. The prepared PAM-based control battery and TPU / PAM-based control battery were used as control groups. The test results are shown in the attached figure. Figure 7 As shown in the figure, the zinc ion migration number (t Zn 2+ ) is 0.732, while the TPU / PAM-based control battery and the PAM-based control battery are only 0.603 and 0.463, respectively. Zn 2+ The value will lead to the Zn 2+ Ion concentration polarization exacerbates the problems of zinc dendrites and parasitic side reactions, t Zn 2+ The improvement is due to the fact that copper zinc sulfide can provide more zinc-philic sites and accelerate the transfer of zinc ions, thus achieving stable and continuous 3D spatial zinc accumulation on the zinc metal surface.

[0125] 2. Arrhenius curve: The prepared zinc-zinc symmetrical battery was used for testing. The EIS spectrum at 10m-100K was measured on an electrochemical workstation at 30-80℃. The Arrhenius curve was prepared by fitting. At the same time, the prepared PAM-based control battery and TPU / PAM-based control battery were used as control groups. Figure 8 As shown in Figure 2, according to the Arrhenius equation, the activation energy (Ea) values ​​of the yarn-shaped Zn-Zn symmetric battery, TPU / PAM-based control battery, and PAM-based control battery are 10.98, 20.03, and 23.86 kJ mol, respectively. -1 The lowest Ea of yarn-shaped Zn-Zn symmetric battery indicates that the nanofiber layer of doped Zn-CuS and PDMS is beneficial to the Zn 2+ The desolvation process has a positive effect on the deposition / dissolution kinetics of Zn on the anode surface. This is also due to the strong interaction between ZnS and Zn ions, which significantly reduces the dissolution energy barrier, prevents water from entering the solvation sheath, and promotes the deposition / dissolution of Zn. 2+ Dissolves faster with less energy expenditure.

[0126] 3. Linear sweep voltammetry curve and Tafel curve: The prepared Zn-Zn symmetrical battery was used for testing. The electrochemical workstation was used to measure the linear sweep voltammetry curve at 0.1 mV s -1 Linear sweep voltammetry was performed, and the prepared PAM-based control battery and TPU / PAM-based control battery were used as control groups, as shown in the attached figure. Figure 9As shown in the figure, after negative scanning, the current of the Zn-Zn symmetric battery is less than that of the PAM-based control battery and the TPU / PAM-based control battery, which indicates that the kinetics of hydrogen evolution at the Zn-PTP interface is suppressed, and the hydrogen evolution voltage between -0.14 and -0.03 is significantly reduced, and a lower slope is shown during the current increase, which indicates that the zinc anode provides excellent inhibition of hydrogen absorption reaction and corrosion reaction; Tafel curve is shown in the attached figure. Figure 10 As shown, the corrosion voltage of the yarn-shaped Zn-Zn symmetric cell is -0.010 V and the corrosion current is 3.247 mA cm -2 , which is much lower than the TPU / PAM-based control battery (-0.021V / 8.144mAcm -2 ) and PAM-based control cells (-0.028V / 10.56mAcm -2 ), indicating a slow corrosion rate, which is due to the dynamic BO bonds in PDMS that can effectively lighten the hydrogen evolution reaction and inhibit the growth of zinc dendrites;

[0127] 4. Rate performance test: The prepared zinc-zinc symmetrical battery was used for testing, and the rate performance was tested at 1-8 mA cm by the Blue Power workstation. -2 The current density and 1 mAh cm -2 The capacity of the battery was tested for rate performance, and the prepared PAM-based control battery and TPU / PAM-based control battery were used as the control group. Figure 11 As shown in the figure, it can be seen that when the current density is from 1mAcm -2 Up to 10mAcm -2 When the current density returns to 1 mA cm -2 , the battery overpotential can also return to 0.1V. In contrast, the TPU / PAM-based control battery has a high current density of 10mA cm -2 Under the condition of , the battery overpotential is increased to 0.3V, while the PAM-based control battery reaches 5mAcm -2 A short circuit occurs when the Zn-Zn symmetric battery is charged.

[0128] 5. Long cycle performance test: The prepared zinc-zinc symmetrical battery was used for testing, and the battery was tested at 1 mA cm -2 The current density is 1 mAh cm -2 The capacity of the long cycle performance test is carried out, as shown in the attached Figure 12 As shown, the battery operated normally for more than 400 hours, and the voltage hysteresis only increased slightly to 120mV after 400 hours of operation, indicating its ultra-long life.

[0129] Example 6 Preparation of Yarn-Shaped Aqueous Zinc Ion Battery

[0130] Neutral electrolyte: same as in Example 2;

[0131] Weakly acidic electrolyte: 3 g acrylamide, 8.4 g zinc sulfate heptahydrate, 1.7 g manganese sulfate monohydrate, and 0.05 g citric acid were added to 7.2 g deionized water in sequence, placed on a stirrer and stirred at room temperature for 5 min, then 20 μg NN methylenebisacrylamide and 20 μL 2-hydroxy-2-methylpropiophenone were added in sequence and placed on a stirrer and stirred for 5 min to obtain a weakly acidic electrolyte.

[0132] Preparation of yarn-shaped aqueous zinc ion battery: 5 cm of the bifunctional electrode fiber prepared in Example 1 was stuffed into a polytetrafluoroethylene tubular mold with a diameter of 0.8 mm, and a neutral electrolyte was injected into the mold using a syringe. The mold was photoinduced for 2 minutes by a UV lamp with a wavelength of 254 nm. After being taken out, the fiber was stuffed into a heat shrink tube with a diameter of 2 mm in parallel with a 5 cm long 3K conductive carbon filament. A weak acid electrolyte was injected into the heat shrink tube using a syringe, and the fiber was photoinduced for 10 minutes by a UV lamp with a wavelength of 254 nm to obtain a yarn-shaped zinc ion battery.

[0133] Supplementary Example 5 Electrochemical Performance Test of Yarn-like Aqueous Zinc Ion Battery

[0134] Long cycle test: the battery was charged at 2.2V constant voltage for 5 minutes and at 0.5mAcm -2 The current density is constant current discharge, as shown in the attached Figure 13 As shown in the figure, the number of cycles of the battery can reach more than 700 cycles, which shows that it has a good cycle life. The capacity of the battery gradually increases in the first 100 cycles, and the capacity remains basically stable after 100 cycles. After 700 cycles, the capacity retention rate can still be maintained at 100%. At the same time, the efficiency is basically maintained at 95%-100%, which shows that the battery has good charge and discharge capabilities.

[0135] Example 7 Preparation of yarn-shaped electroluminescent device

[0136] Preparation of electroluminescent electrolyte: same as in Example 2;

[0137] Take 20 cm of the bifunctional electrode fiber prepared in Example 1 and a 0.5 mm zinc wire and insert them in parallel into a 1 mm diameter heat shrink tube. Take 1 g of electroluminescent electrolyte and 0.05 g of thermal initiator solution, stir them quickly, and inject them into the tube through a syringe to initiate gelation at room temperature, thereby constructing a yarn-shaped electroluminescent device.

[0138] By connecting the electrodes at both ends of the yarn-shaped electroluminescent device through the EL driver, the device can be lit. Figure 14As shown, since the luminescent powder is evenly dispersed, the prepared yarn-shaped electroluminescent device emits light evenly. At the same time, due to the insulating properties of PDMS, the wetting of the nanofiber layer is effectively prevented. When the precursor solution is triggered, most of the water molecules are fixed by the gel to become bound water, and the probability of the nanofiber layer being wetting is further reduced, which allows the device to emit light stably for a long time.

[0139] Supplementary Example 6: Luminescence Performance Test of Yarn-Shaped Electroluminescent Device

[0140] The electroluminescent device prepared in Example 5 was tested. Figure 15 As shown in the figure, as the load voltage increases, the brightness of the yarn-shaped electroluminescent device increases accordingly. In addition, since the frequency has a positive effect on the generation of electron holes and the excitation of luminescent centers, the brightness will be further improved when the frequency increases from 1 kHz to 6 kHz. At the same time, the frequency will also cause the electroluminescent color to change, as shown in the figure. Figure 16 As shown in the figure, as the frequency increases, the electroluminescence color can obviously change from green to blue, which provides a possibility for the preparation of tunable light-emitting fibers.

[0141] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on its differences from the other embodiments. Reference can be made to the descriptions of the identical or similar parts between the various embodiments. For the devices disclosed in the embodiments, since they correspond to the methods disclosed in the embodiments, the descriptions are relatively simple, and the relevant parts can be referred to the descriptions of the methods.

[0142] The above is a detailed introduction to the electroluminescent bifunctional electrode fiber provided by the present invention and its application in the preparation of electroluminescent devices. Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above examples is only intended to help understand the method and core concept of the present invention. It should be noted that for ordinary technicians in this technical field, various improvements and modifications can be made to the present invention without departing from the principles of the present invention, and such improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A dual-function electrode fiber, characterized in that The dual-function electrode fiber is prepared by the following method: Using zinc wire with a diameter of 0.3-2.0 mm as the core wire, a spinning solution is used to electrospin the zinc wire surface to form a nanofiber layer to prepare a dual-functional electrode fiber; The spinning solution contains, by weight percentage, 15-25% of thermoplastic polyurethane, 5-20% of zinc copper sulfide, 2-10% of PDMS, and the balance being a solvent consisting of N-N-dimethylformamide and tetrahydrofuran. The mass ratio of N-N-dimethylformamide to tetrahydrofuran in the solvent is 100:0-50:50, and the molecular weight of the thermoplastic polyurethane is 10,000-50,000. The fibers attached to the zinc wire surface are controlled by adjusting the winding device speed, the funnel collector rotation speed, the injector flow rate and the positive and negative voltages.

2. The dual-function electrode fiber according to claim 1, characterized in that: The electrospinning parameters were set as follows: the angle between the needle tip and the collector was 60°, the distance between the needle tip and the collector was 8 cm, the syringe pump pushed the spinning solution at a rate of 1.2 mL / h, 12-17 kV DC high voltage electricity was used during the spinning process, the funnel-shaped collector rotated at a speed of 120-240 rpm, and the winding device speed was 0.06 m / min.

3. The dual-function electrode fiber according to claim 1, characterized in that: The spinning solution contains, by weight percentage, 18-20% of thermoplastic polyurethane, 18-20% of zinc copper sulfide, 7-8% of PDMS, and the balance being a solvent consisting of N-N-dimethylformamide and tetrahydrofuran, wherein the mass ratio of N-N-dimethylformamide to tetrahydrofuran in the solvent is 50:

50.

4. A fibrous aqueous zinc ion battery made using the bifunctional electrode fiber according to claim 1, characterized in that The fiber-shaped zinc ion battery is prepared by the following method: S1 Preparation of electrolyte Acrylamide and zinc sulfate heptahydrate are sequentially added to water and mixed, and then NN methylene bisacrylamide and a photoinitiator are sequentially added and mixed to obtain a neutral electrolyte; the neutral electrolyte contains the following components in percentage by weight: 10-20% acrylamide, 45-55% zinc sulfate heptahydrate, 0.05-0.5% NN methylene bisacrylamide, 0.05-0.5% photoinitiator, and the balance is water; acrylamide, zinc sulfate heptahydrate, and manganese sulfate are added to a weakly acidic solution having a pH of 2-3 and mixed uniformly; then, NN methylenebisacrylamide and a photoinitiator are added in sequence and mixed uniformly to obtain a weakly acidic electrolyte; the weakly acidic electrolyte comprises the following components in percentage by weight: 10-20% acrylamide, 40-50% zinc sulfate heptahydrate, 5-10% manganese sulfate, 0.05-0.5% NN methylenebisacrylamide, 0.05-0.5% photoinitiator, and the balance being weakly acidic solution; and the pH of the solution is 3-5; Preparation of S2 fibrous aqueous zinc ion batteries The bifunctional electrode fiber is used as the negative electrode and inserted into a polytetrafluoroethylene tubular mold. The neutral electrolyte prepared in S1 is injected into the mold and photoinitiated to obtain a bifunctional electrode fiber / photoinitiator gel electrolyte yarn. The bifunctional electrode fiber and the conductive carbon filament are used as positive electrode current collectors, and two bifunctional electrode fiber / photoinitiator gel electrolyte yarns are inserted into a heat shrink tube in parallel. The weak acid electrolyte prepared in S1 is injected into the heat shrink tube using a syringe, and photoinitiated to obtain a yarn-shaped aqueous zinc ion battery without a positive electrode; S3 active material loading A yarn-shaped aqueous zinc ion battery without a positive electrode prepared with S2 was used as a device. The manganese ions in the electrolyte were oxidized into manganese oxides and deposited on the surface of the positive electrode current collector by chronoamperometry or constant voltage charging for several minutes under constant voltage conditions using an electrochemical workstation or a blue-electric workstation.

5. The fibrous aqueous zinc ion battery according to claim 4, wherein: The photoinitiator is one or more of 2-hydroxy-2-methylpropiophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, and 1-hydroxycyclohexylphenyl ketone; The weak acid solution is a weak acid solution with a pH value of 2-3 obtained by dissolving an appropriate amount of acid in water and stirring for 1-5 hours; the acid is selected from one or more of citric acid, concentrated sulfuric acid, carbonic acid, hydrochloric acid, malic acid, oxalic acid or nitric acid.

6. The fibrous aqueous zinc ion battery according to claim 4, wherein: Photoinitiation uses UV light with a wavelength of 250-400nm and an initiation time of 2-30min; The specifications of the conductive carbon filament are one or more of 1K, 3K, 12K and 24K; The diameter of the PTFE tubular mold is 0.5-3 mm; The diameter of the heat shrink tubing is 1-10mm.

7. The fibrous aqueous zinc ion battery according to claim 4, wherein: The constant voltage charging voltage in S3 is 1.6-2.4V, and the charging time is 1-120min.

8. A fiber-shaped electroluminescent device made using the bifunctional electrode fiber according to claim 1, characterized in that The fiber-shaped electroluminescent device is prepared by the following method: acrylamide, zinc sulfate heptahydrate, and water are mixed, and NN methylenebisacrylamide is added and mixed to obtain an electroluminescent electrolyte; the electroluminescent electrolyte comprises the following components in percentage by weight: 10-20% acrylamide, 45-55% zinc sulfate heptahydrate, 0.05-0.5% NN methylenebisacrylamide, and the balance water; Mix the thermal initiator and water to obtain a thermal initiator solution with a mass percentage of 5-10%; The thermal initiator is one or both of potassium persulfate and ammonium persulfate; Take two of the bifunctional electrode fibers, insert them into a heat shrink tube, quickly mix the electroluminescent electrolyte and the thermal initiator solution, and then fill the heat shrink tube to make the weight ratio of the electroluminescent electrolyte to the thermal initiator be 400:1-200:

1. Initiate gelation at room temperature to obtain a fiber-shaped electroluminescent device.

9. Use of the bifunctional electrode fiber according to claim 1 in preparing an electroluminescent device.

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