A fluorescent display fibrous aqueous zinc ion battery and a preparation method and application thereof

Abstract

The application provides a fluorescent display fibrous aqueous zinc ion battery, which comprises a zinc wire as an inner anode, a nickel Prussian blue / carbon nanotube fiber current collector as an outer cathode, and a carbon dot modified hydrogel electrolyte as an electrolyte, and is assembled to obtain the fluorescent display fibrous aqueous zinc ion battery; the fluorescent display fibrous aqueous zinc ion battery can be used for weaving smart textiles with multicolor display and energy storage. Through the technical scheme of the application, a quantum-sized carbon dot with abundant zincophilic groups and bright fluorescence is prepared as an additive for modifying a hydrogel electrolyte, so that the dual functions of zinc anode protection and fluorescence are realized; the abundant zincophilic groups on the surface of the carbon dot are used to inhibit the growth of zinc anode dendrites, meanwhile, the current collector obtained by in-situ growth of nickel Prussian blue on the surface of the carbon nanofiber is used as the inner anode, and the high active sites of nickel provide the zinc ion battery with cycle stability and capacity retention rate.

Description

Technical Field

[0001] This invention relates to the field of functional nanomaterials technology, specifically to a fluorescent display fibrous aqueous zinc-ion battery, its preparation method and application, and in particular, to the ability to use it to weave textiles with dual functions of multi-color display and energy storage. Background Technology

[0002] Wearable smart textiles are a natural carrier that can be integrated with various functional fibers, enabling highly sensitive and pervasive environmental sensing and response. However, the numerous interfaces between existing fibers with different functions significantly increase the complexity of smart textiles and reduce their durability and comfort. Therefore, the multifunctional integration of fibers is both significant and challenging for achieving miniaturized, lightweight, and highly reliable smart textiles. Color rendering and energy storage are indispensable components of information visualization and energy supply in smart textiles, and their compatibility is a priority factor in forming integrated fluorescent display fiber-like batteries.

[0003] In recent years, aqueous zinc-ion batteries have been considered a promising alternative to mainstream lithium-ion batteries due to their good safety, low cost, and fast charging capability. However, the tip effect of the non-uniform electric field and the contact between the zinc electrode and the aqueous electrolyte lead to dendrite growth and unavoidable corrosion, resulting in poor reversibility of Zn anode cycling. Existing technologies often address the Zn dendrite problem by adding additives to the electrolyte, which is simple and economical. Examples include Chinese invention patents CN114039109A and CN112635860A.

[0004] On the other hand, Chinese invention patent CN113488706A discloses a hydrogel electrolyte that can be used in flexible energy storage devices to address issues such as electrolyte leakage, maintaining physical integrity and flexibility under mechanical deformation, and suppressing dendrite growth in metal electrodes, thereby improving electrochemical stability. The hydrogel electrolyte provides a quasi-solid-state electrolyte solution, and as a flexible material, it can be fully integrated into fiber battery applications. However, inevitably, a simple hydrogel electrolyte still corrodes the zinc anode in aqueous zinc-ion batteries and cannot effectively suppress dendrite growth. Therefore, the dendrite growth problem still needs to be addressed when using hydrogel electrolytes as aqueous zinc-ion batteries to prepare wearable textiles.

[0005] Clearly, the goal is to provide a multifunctional, integrated fibrous aqueous zinc-ion battery that can be directly applied to wearable smart textiles, solve the problem of the reversibility of the zinc ion anode cycle, and also consider the feasibility of the product's preparation method, making it suitable for widespread use. Summary of the Invention

[0006] The purpose of this invention is to disclose a fluorescent display fibrous aqueous zinc-ion battery, its preparation method, and its application. It provides a functional fibrous aqueous zinc-ion battery that integrates multi-color display and energy storage, providing technical support for information visualization and energy supply in modern smart textile processes. It can effectively suppress dendrite growth in the zinc anode and has good electrochemical stability, making it suitable for large-scale production.

[0007] To achieve the above objectives, the present invention provides the following technical solution: a fluorescent display fibrous aqueous zinc-ion battery, comprising a zinc wire as the inner anode, a nickel Prussian blue / carbon nanotube fiber current collector as the outer cathode, and a carbon dot-modified hydrogel electrolyte, assembled to obtain the fluorescent display fibrous aqueous zinc-ion battery; the fluorescent display fibrous aqueous zinc-ion battery can be used to weave smart textiles with multi-color display and energy storage; preferably, the carbon dots in the carbon dot-modified hydrogel electrolyte have abundant zinc-loving groups on their surface.

[0008] Preferably, the surfaces of both the zinc wire and the nickel Prussian blue / carbon nanotube fiber current collector are coated with the carbon-dot modified hydrogel electrolyte. The nickel Prussian blue / carbon nanotube fiber current collector is wound onto the zinc wire by coaxial winding, and then encapsulated with the hydrogel electrolyte to obtain the fluorescent display fiber-shaped aqueous zinc-ion battery. The hydrogel electrolyte ensures that the two electrodes of the inner and outer anodes are tightly attached and fully immersed in the electrolyte environment.

[0009] Preferably, the carbon dot-modified hydrogel electrolyte is prepared by adding carbon dots to a polyvinyl alcohol solution and then performing a cyclic freezing method.

[0010] Preferably, in the carbon dot-modified hydrogel electrolyte, the carbon dots are prepared by reacting citric acid with an organic compound containing two or more -NH2 groups using a microwave method. After dialysis-freezing, nitrogen-doped carbon dots are obtained. The surface of the prepared carbon dots is rich in zinc-loving groups, such as -COOH, -OH, and -NH2. The zinc-loving groups on the surface of the carbon dots can enhance their solubility in the hydrogel and enhance their binding energy with zinc ions, thus inhibiting the growth of zinc anode dendrites.

[0011] Preferably, the nickel Prussian blue on the nickel Prussian blue / carbon nanotube fiber current collector is a nanocubic material; wherein, the nickel Prussian blue is uniformly distributed on the carbon nanotube fiber through in-situ growth.

[0012] Preferably, the preparation of the nickel Prussian blue / carbon nanotube fiber current collector includes:

[0013] (1) Solution A: Carbon nanotube fibers are immersed in a mixed solution of nickel salt and citrate to obtain solution A;

[0014] (2) Solution B: Dissolve potassium ferrocyanide in water to obtain solution B;

[0015] (3) Preparation of nickel Prussian blue / carbon nanotube fiber current collector: Solution B is slowly added dropwise to solution A, and after stirring slowly overnight, the carbon nanotube fiber is taken out and dried to obtain the nickel Prussian blue / carbon nanotube fiber current collector.

[0016] To achieve another technical objective, the present invention also provides a method for preparing the above-mentioned fluorescent display fibrous aqueous zinc-ion battery, comprising the following steps:

[0017] S1. Synthesis of carbon dots: Citric acid is ultrasonically dispersed in deionized water, and an organic compound containing at least two or more -NH2 is added as a precursor solution; the precursor solution is subjected to microwave reaction in a microwave reactor, and the reaction product is purified by dialysis and freeze-dried to obtain powdered carbon dots;

[0018] S2. Preparation of carbon dot-modified hydrogel electrolyte; The carbon dots prepared in S1 are added to a polyvinyl alcohol solution to form a carbon dot / polyvinyl alcohol solution; Zinc sulfate solution is added to the carbon dot / polyvinyl alcohol solution, and the carbon dot-modified hydrogel electrolyte is obtained by cyclic freezing.

[0019] S3. Preparation of nickel Prussian blue / carbon nanotube fiber current collector: Carbon nanotube fibers are soaked in a mixed solution of nickel salt and citrate, potassium ferrocyanide solution is added, and the mixture is slowly stirred overnight and then dried to obtain the nickel Prussian blue / carbon nanotube fiber current collector.

[0020] S4. Assembly of the fluorescent display fibrous aqueous zinc-ion battery: Zinc wire and the nickel Prussian blue / carbon nanotube fiber current collector prepared in S3 are respectively immersed in the carbon-dot modified hydrogel electrolyte, ensuring that the surfaces of both the zinc wire and the nickel Prussian blue / carbon nanotube fiber current collector are coated with the carbon-dot modified hydrogel electrolyte. After removal, washing and drying, the nickel Prussian blue / carbon nanotube fiber current collector is wound onto the zinc wire using a coaxial winding method. The battery is then encapsulated with the hydrogel electrolyte to obtain the fluorescent display fibrous aqueous zinc-ion battery. The hydrogel electrolyte ensures tight adhesion between the two electrodes and full immersion in the electrolyte environment. Finally, encapsulation with the carbon-dot modified hydrogel electrolyte yields the fluorescent fibrous aqueous zinc-ion battery with multi-color display and energy storage functions.

[0021] Preferably, in S1, the dialysis purification-freeze-drying method includes centrifuging the reaction product obtained by the microwave reaction, taking the supernatant, transferring the supernatant to a 1000 Da dialysis bag, dialyzing for 2 days, and changing the deionized water every 6 hours during the period; after the dialysis is completed, the solution is frozen at -20°C and then transferred to a freeze dryer, and vacuum-frozen until it is completely formed into powder, thus obtaining the carbon dots.

[0022] Preferably, in S2, the cyclic freezing method includes freezing the carbon dot / polyvinyl alcohol solution with the zinc sulfate solution at -20°C for 6 hours after the reaction is completed, cooling to room temperature, and repeating the freeze-thaw process 3 times.

[0023] Preferably, in step S3, the Prussian blue solution and the nickel salt solution are prepared in an equimolar ratio.

[0024] Carbon quantum dots (CQDs or Cdots), also known as carbon quantum dots or carbon nanodots, are a class of zero-dimensional carbon nanomaterials with significant fluorescence properties. They consist of ultrafine, dispersed, quasi-spherical particles. This invention uses carbon dot materials as electrolyte additives to modify hydrogel electrolytes, thereby providing the electrolyte with a conversion-luminescence function and further realizing fluorescence display. This provides a feasible approach to realizing integrated fluorescent display fibers in aqueous zinc-ion batteries.

[0025] Specifically, carbon dots not only possess ultra-small dimensions but also contain abundant zinc-loving functional groups containing oxygen, nitrogen, and sulfur. On one hand, thanks to the stronger binding energy between the zinc-loving functional groups and zinc ions, carbon dots can reduce nucleation overpotential and interfacial impedance, improve reaction kinetics, and continuously regulate zinc ion flow, guiding the uniform deposition of zinc ions on the composite negative electrode surface. This effectively suppresses the formation of zinc dendrites or dendrites, thereby significantly improving the rate performance and cycle performance of aqueous zinc-ion batteries, making them a promising electrolyte additive for suppressing Zn dendrites. On the other hand, the excellent photoluminescence properties derived from the functional groups of carbon dots make them excellent candidate materials for color filter modules. Furthermore, carbon dots synthesized using different carbon precursors can be used to prepare aqueous zinc-ion batteries with fluorescent fiber shapes possessing different fluorescence properties. These fibers can also be woven into multi-color in-cell display textiles, applicable to wearable energy supply and rescue scenarios in dark environments. Therefore, by adopting the technical solution of this invention, carbon dots are introduced into the hydrogel electrolyte to modify it. Carbon dots with zinc-loving functional groups and photoluminescence properties are introduced into the electrolyte, which simultaneously satisfies the dual functions of zinc anode protection and fluorescence. This allows the quasi-solid-state electrolyte modified with carbon dots to be combined with carbon nanofibers and zinc wires as positive and negative electrodes, respectively, to assemble an integrated fluorescent fiber-like aqueous zinc-ion battery. This battery can then be used to weave fluorescent display fibers into smart wearable textiles, which is a simple and feasible technical solution.

[0026] Technical effects of the present invention:

[0027] 1. By adopting the technical solution of the present invention, a quantum-sized carbon dot with abundant zinc-loving groups and bright fluorescence is prepared as an additive to modify the hydrogel electrolyte, realizing the dual functions of zinc anode protection and fluorescence; the abundant zinc-loving groups on the surface of the carbon dot are used to inhibit the growth of zinc anode dendrites, and the current collector obtained by in-situ growth of nickel Prussian blue on the surface of carbon nanofibers is used as the inner anode. Based on the high active sites of nickel, the zinc-ion battery is provided with cycle stability and capacity retention.

[0028] 2. By adopting the technical solution of the present invention, using Zn wire as the inner anode, a self-supporting nickel Prussian blue / carbon nanofiber composite as the outer cathode, and a hydrogel electrolyte modified with fluorescent carbon dots in the middle, a fluorescent fiber aqueous zinc-ion battery with a high voltage platform and stable operation was successfully assembled, achieving a cycle performance of at least 2500 hours.

[0029] 3. By adopting the technical solution of the present invention, fluorescent fiber-shaped aqueous zinc-ion batteries are woven into wearable smart textiles to form dual-function multi-color display / energy storage textiles, enabling wearable battery display systems to drive electronic devices. Attached Figure Description

[0030] Figure 1a The image shows a single fiber of the fluorescent fibrous aqueous zinc-ion battery prepared in Example 1 of this invention under sunlight and ultraviolet light.

[0031] Figure 1b The image shows a physical photograph of a multicolor fluorescent fibrous aqueous zinc-ion battery mass-produced using the preparation methods provided in Examples 1 and 2.

[0032] Figure 1c The image shows a physical photograph of a multicolor fluorescent fibrous aqueous zinc-ion battery, mass-produced using the methods provided in Examples 1 and 2, woven into a textile under a UV lamp.

[0033] Figure 1d shows the fluorescence spectra of fibrous aqueous zinc-ion batteries prepared by the preparation methods provided in Examples 1 and 2, with different fluorescent carbon dots.

[0034] Figure 2a and Figure 2e The images are transmission electron microscope images of blue carbon dots in the fluorescent fibrous aqueous zinc-ion battery prepared in Example 1, at different magnifications.

[0035] Figure 2b The Fourier transform infrared spectrum of the blue carbon dots in the fluorescent fibrous aqueous zinc-ion battery prepared in Example 1 is shown.

[0036] Figure 2c This is a transmission electron microscope image of green carbon dots in the fluorescent fibrous aqueous zinc-ion battery prepared in Example 2.

[0037] Figure 2d The Fourier transform infrared spectrum of the green carbon dots in the fluorescent fibrous aqueous zinc-ion battery prepared in Example 2 is shown.

[0038] Figure 3a (a) Scanning electron microscope images of the zinc anode (ab) with and without carbon dots in the fluorescent fibrous aqueous zinc-ion battery prepared in Example 1; (b) X-ray diffraction spectra of the Zn anode with and without carbon dots.

[0039] Figure 4a and Figure 4c The images shown are scanning electron microscope images of nickel Prussian blue grown in situ on carbon nanotube fibers in Example 1.

[0040] Figure 4b This is a wide-angle X-ray scattering image of nickel Prussian blue grown in situ on carbon nanotube fibers in Example 1.

[0041] Figure 4d The X-ray photoelectron spectrum of nickel Prussian blue grown in situ on carbon nanotube fibers in Example 1.

[0042] Figure 5a Linear cyclic voltammetry curves of the fluorescent fibrous aqueous zinc-ion batteries prepared in Examples 1-2 and Comparative Example 1.

[0043] Figure 5b The constant current charge-discharge curves are for the fluorescent fibrous aqueous zinc-ion batteries prepared in Examples 1-2 and Comparative Example 1.

[0044] Figure 5c The cycling stability and coulombic efficiency curves of the fluorescent fibrous aqueous zinc-ion batteries prepared in Examples 1-2 and Comparative Example 1 are shown. Detailed Implementation

[0045] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the protection scope of the present invention.

[0046] This invention provides a fluorescent display fibrous aqueous zinc-ion battery, which uses a zinc wire as the inner anode, a nickel Prussian blue / carbon nanotube fiber current collector as the outer cathode, and a carbon dot-modified hydrogel electrolyte to assemble the fluorescent display fibrous aqueous zinc-ion battery. The fluorescent display fibrous aqueous zinc-ion battery can be used to weave smart textiles with multi-color display and energy storage.

[0047] The technical solution of this invention utilizes nitrogen-doped carbon dots to modify hydrogels, which are then used as electrolytes to encapsulate the inner anode and outer cathode. On the one hand, the photoluminescence properties of carbon dots can be used for multicolor display; on the other hand, the zinc-loving groups on the surface of carbon dots are used to suppress the growth of zinc anode dendrites. Simultaneously, a current collector obtained by in-situ growth of nickel Prussian blue on the surface of carbon nanofibers is used as the inner anode. The high active sites of nickel provide cycle stability and capacity retention for the zinc-ion battery.

[0048] The technical solution of the present invention will be further described in detail below through specific embodiments.

[0049] Example 1

[0050] This embodiment provides a fluorescent fiber-like aqueous zinc-ion battery for dual-functional multi-color display and energy storage textiles, the preparation method of which includes the following steps:

[0051] (1) Synthesis of carbon dots:

[0052] Dissolve 0.48 g of citric acid in 5 mL of deionized water, slowly add 345 μL of ethylenediamine, and then sonicate to uniformly disperse the solution. Transfer the uniformly dispersed precursor solution to a microwave reactor and react at 800 W for 2 min. After the reaction product cools, centrifuge the mixture at 6500 rad / min and collect the supernatant. Transfer the supernatant to a 1000 Da dialysis bag and dialyze for 2 days, changing the deionized water every 6 h. After dialysis, freeze the solution at -20 °C and then transfer it to a freeze dryer for vacuum freezing until carbon dot powder is completely formed.

[0053] (2) Preparation of carbon dot modified hydrogel electrolytes

[0054] Add 10g of polyvinyl alcohol to 50mL of deionized water and stir at 95℃ until completely dissolved. Add 25mg of carbon dot powder to the polyvinyl alcohol solution and stir evenly so that the carbon dots are fully coated with polyvinyl alcohol to form a carbon dot / polyvinyl alcohol hydrogel.

[0055] Add 28.76 g of zinc sulfate heptahydrate to 50 mL of water and stir until completely dissolved. Slowly add the solution dropwise to the carbon dot / polyvinyl alcohol solution at 60 °C. After stirring thoroughly, cool to room temperature and freeze at -20 °C for 6 h. Cool to room temperature and repeat the freeze-thaw process 3 times until zinc ions are fully in contact with the carbon dot / polyvinyl alcohol hydrogel, thereby forming a carbon dot modified hydrogel electrolyte.

[0056] (3) Preparation of nickel Prussian blue / carbon nanotube fiber composite current collector

[0057] Dissolve 0.263 g of nickel sulfate hexahydrate and 4.60 g of potassium citrate in 50 mL of deionized water to obtain a precursor solution; immerse a 20 cm long carbon nanotube fiber in the precursor solution and stir slowly, denoted as solution A.

[0058] Dissolve 0.422 g of potassium ferrocyanide trihydrate in 50 mL of deionized water to form a potassium ferrocyanide solution, denoted as solution B.

[0059] Solution B was added dropwise to solution A, and after slow stirring overnight, nickel Prussian blue grew in situ on the surface of carbon nanotube fibers. The dropwise addition rate of solution B should not be too fast, otherwise the nickel Prussian blue particles grown in situ may be too large.

[0060] The carbon nanotube fibers were removed, washed with deionized water and ethanol, and dried at 110℃ for 12 hours to obtain an in-situ grown nickel Prussian blue / carbon nanotube fiber composite current collector. Solution B should be added dropwise to solution A. If the addition is too fast, solution B will cause the nickel Prussian blue grains to be too large and will not be able to grow successfully on the carbon nanotube fibers.

[0061] (4) Preparation of fluorescent fiber zinc-ion batteries

[0062] Zinc wire and nickel Prussian blue / carbon nanotube fiber were respectively immersed in carbon dot-modified hydrogel electrolyte for 30 min, so that the zinc wire and nickel Prussian blue / carbon nanotube fiber were respectively wrapped by the gel electrolyte. The zinc wire and nickel Prussian blue / carbon nanotube fiber composite current collector was taken out and dried at 60℃ for 30 min.

[0063] The dried zinc wire and nickel Prussian blue / carbon nanotube fiber composite current collector were coaxially wound with the zinc wire and carbon dot modified hydrogel electrolyte to form a fibrous zinc-ion battery with blue fluorescence.

[0064] Among them, the blue fluorescent fibrous zinc-ion battery uses Zn wire as the inner anode, a self-supporting nickel Prussian blue / carbon nanotube fiber composite as the outer cathode, and a carbon dot-modified hydrogel electrolyte with fluorescent properties, thus assembling a fluorescent fibrous aqueous zinc-ion battery.

[0065] Example 2

[0066] This embodiment provides a method for preparing a fluorescent fiber-like aqueous zinc-ion battery for dual-function multicolor display and energy storage textiles, specifically including the following steps:

[0067] (1) Synthesis of carbon dots

[0068] Dissolve 0.48 g of citric acid and 1 g of urea in 5 mL of deionized water and sonicate to ensure uniform dispersion. Transfer the uniformly dispersed precursor solution to a microwave reactor and react at 800 W for 2 min. After the reaction product cools, centrifuge the mixture at 6500 rad / min and collect the supernatant. Transfer the supernatant to a 1000 Da dialysis bag and dialyze for 2 days, changing the deionized water every 6 hours. After dialysis, freeze the solution at -20°C and then transfer it to a freeze dryer for vacuum freezing until carbon dot powder is completely formed.

[0069] (2) Preparation of carbon dot modified hydrogel electrolytes

[0070] Add 10g of polyvinyl alcohol to 50mL of deionized water and stir at 95℃ until completely dissolved. Add 25mg of carbon dot powder to the polyvinyl alcohol solution and stir until homogeneous. Add 28.76g of zinc sulfate heptahydrate to 50mL of water and stir until completely dissolved. Slowly add the solution dropwise to the carbon dot polyvinyl alcohol solution at 60℃, stir thoroughly, cool to room temperature, freeze at -20℃ for 6 hours, cool to room temperature, and repeat the freeze-thaw process three times to form a carbon dot-modified hydrogel electrolyte.

[0071] (3) Preparation of nickel Prussian blue / carbon nanotube fiber composite

[0072] Dissolve 0.263 g of nickel sulfate hexahydrate and 4.60 g of potassium citrate in 50 mL of deionized water to obtain a precursor solution; immerse carbon nanotube fibers in the precursor solution and stir slowly to form solution A.

[0073] Dissolve 0.422 g of potassium ferrocyanide trihydrate in 50 mL of deionized water to form solution B.

[0074] Solution B was slowly added dropwise to solution A, and the mixture was stirred slowly overnight. The carbon nanotube fibers were then removed, washed with deionized water and ethanol, and dried at 110°C for 12 hours to obtain a nickel Prussian blue / carbon nanotube fiber composite current collector, which is the positive electrode of the battery.

[0075] (4) Preparation of fluorescent fiber zinc-ion batteries

[0076] The zinc wire and the nickel Prussian blue / carbon nanotube fiber composite current collector were respectively immersed in carbon dot-modified hydrogel electrolyte, so that the surface of the zinc wire and the nickel Prussian blue / carbon nanotube fiber composite current collector were both coated with hydrogel electrolyte. The zinc wire and the nickel Prussian blue / carbon nanotube fiber composite current collector were then removed and dried at 60°C for 30 min.

[0077] The dried zinc wire and carbon nanotube fiber were assembled into a green fluorescent fiber-shaped zinc-ion battery by coaxial winding.

[0078] Among them, the green fluorescent fibrous zinc-ion battery uses Zn wire as the inner anode, a self-supporting nickel Prussian blue / carbon nanotube fiber composite as the outer cathode, and a carbon dot-modified hydrogel electrolyte with fluorescent properties, thus assembling a fluorescent fibrous aqueous zinc-ion battery.

[0079] Comparative Example 1

[0080] This comparative example presents an aqueous zinc-ion battery without the addition of carbon dots, the specific steps of which include:

[0081] (1) Preparation of hydrogel electrolytes

[0082] Add 10g of polyvinyl alcohol to 50mL of deionized water and stir at 95℃ until completely dissolved.

[0083] Add 28.76g of zinc sulfate heptahydrate to 50mL of water and stir until completely dissolved. Slowly add the solution dropwise to polyvinyl alcohol at 60℃, stir thoroughly, cool to room temperature, freeze at -20℃ for 6 hours, cool to room temperature, and repeat the freeze-thaw process 3 times to form a hydrogel electrolyte.

[0084] (2) Preparation of the positive electrode for nickel-Prussian blue / carbon nanotube fiber batteries

[0085] Dissolve 0.263 g of nickel sulfate hexahydrate and 4.60 g of potassium citrate in 50 mL of deionized water. Soak carbon nanotube fibers in the precursor solution and stir slowly to form solution A.

[0086] Dissolve 0.422 g of potassium ferrocyanide trihydrate in 50 mL of deionized water to form solution B.

[0087] Solution B was slowly added dropwise to solution A, and the mixture was stirred slowly overnight. The fibers were then removed, washed with deionized water and ethanol, and dried at 110°C for 12 hours to obtain the positive electrode of the nickel Prussian blue / carbon nanotube fiber battery.

[0088] (3) Preparation of fibrous zinc-ion batteries

[0089] Zinc wire and nickel Prussian blue / carbon nanotube fiber were respectively immersed in bifunctional electrolyte to encapsulate the gel electrolyte. The zinc wire and carbon nanotube fiber were then removed and dried at 60°C for 30 min.

[0090] The dried zinc wire and nickel Prussian blue / carbon nanotube fibers are coaxially wound together to form a fibrous zinc-ion battery.

[0091] The fluorescent fiber-shaped aqueous zinc-ion batteries prepared in Examples 1 and 2 were woven together and their performance was characterized.

[0092] Performance characterization and results analysis:

[0093] See Figure 1a The images show the fluorescent fiber aqueous zinc-ion battery prepared in Example 1 under fluorescent light and ultraviolet light, respectively. It is clear that the sample from Example 1 exhibits fluorescent blue under ultraviolet light.

[0094] Figure 1b and Figure 1c The images show fluorescent fiber-shaped aqueous zinc-ion batteries prepared in Examples 1 and 2, respectively; they exhibit fluorescent blue and fluorescent green fluorescence under ultraviolet light, respectively. In particular, through... Figure 1a Figure 1b illustrates the uniformity of the prepared fluorescent fibrous battery and shows that it can be mass-produced. Figure 1c The fact that fibers can be woven into textiles to power LEDs demonstrates the practicality of fluorescent fiber batteries.

[0095] Figure 1d The spectra of the fluorescent fiber aqueous zinc-ion batteries prepared in Examples 1 and 2 accurately characterize the emission wavelengths of the fluorescent fiber batteries as 450 nm and 520 nm, further demonstrating that the fibers of different colors have high visual resolution.

[0096] Figures 2a-2d Characterization of carbon dots in the fluorescent fibrous aqueous zinc-ion batteries prepared in Examples 1 and 2.

[0097] Depend on Figure 2a and Figure 2c It is evident that the carbon dots, which are quantum-sized nanomaterials with a size of less than 5 nm, can be fully encapsulated by polyvinyl alcohol during the crosslinking polymerization process.

[0098] Depend on Figure 2b and Figure 2d This demonstrates that the carbon dot surface has abundant zinc-loving groups such as -OH, -COOH, and -NH2, which can improve the solubility of the carbon dot and the hydrogel, and also facilitate the function of zinc anode protection.

[0099] Figures 3a-3cThe dendrite suppression is compared between the fluorescent fibrous aqueous zinc-ion batteries prepared in Example 1 and Comparative Example 1. Figure 3a It is evident that the presence of carbon dots prevents dendrite formation in the Zn anode, which is beneficial for improving battery life. Figure 3b It is evident that without carbon dots, a large number of disordered dendrites appear, severely hindering battery life. Figure 3c This further illustrates that in the presence of carbon dots, no dendrites are formed in the Zn anode, which is beneficial to improving battery life; however, in the absence of carbon dots, X-ray diffraction peaks of dendrites appear on the surface of the Zn anode, indicating that the lack of carbon dot protection will cause a large number of dendrites to form in the Zn anode, thereby reducing battery life.

[0100] The principle is analyzed by combining the infrared spectrum of carbon dots: the surface of carbon dots is rich in a large number of zinc-loving groups, which enables carbon dots to have a stronger binding energy with zinc ions, reduce nucleation overpotential and interfacial impedance, improve reaction kinetics, and can continuously regulate zinc ion flow, guide zinc ions to be uniformly deposited on the surface of composite negative electrode, thereby effectively suppressing the generation of zinc dendrites or dendrites.

[0101] See Figures 4a-4c , of which Figure 4a and Figure 4c Scanning electron microscope images of nickel Prussian blue on carbon nanotube fibers at different magnifications show that the nickel Prussian blue is a cubic material with nanoscale dimensions. The nickel Prussian blue is grown in situ on the carbon nanotube fibers and is evenly distributed.

[0102] Figure 4b The image shows a wide-angle X-ray scattering image of nickel Prussian blue on carbon nanotube fibers. As can be seen from the image, it matches the crystal form of nickel Prussian blue.

[0103] Figure 4d The figure shows the X-ray photoelectron spectrum of nickel Prussian blue on carbon nanotube fibers. As can be seen from the figure, nickel was successfully introduced into Prussian blue.

[0104] Figures 5a-5c Electrochemical performance of the fluorescent fibrous aqueous zinc-ion batteries prepared in Examples 1-3. Figure 5a The linear cyclic voltammetry curves of the fiber-optic aqueous zinc-ion battery demonstrate that the high active sites of nickel provide a high voltage plateau of 1.55V. Figure 5b The constant current charge-discharge curve of the fluorescent fiber aqueous zinc-ion battery demonstrates the battery's excellent rate performance, maintaining 60% of its original capacity even at 40 times the current density. Figure 5cThe cycle stability and coulombic efficiency curves of the fluorescent fiber aqueous zinc-ion battery clearly show that the battery still retains 90% of its capacity after 1500 cycles. This demonstrates that the bifunctional electrolyte and the highly active nickel Prussian blue ensure the battery's stability, further illustrating the excellent application prospects of this battery.

[0105] In summary, by employing the technical solution of this invention, a carbon dot with abundant zinc-loving groups on its surface is prepared to enhance the binding energy with zinc ions, thereby inhibiting dendrite growth of the zinc anode and enhancing the cycle stability of the zinc-ion battery.

[0106] Using the technical solution of this invention, a carbon-dot-modified hydrogel is prepared as the electrolyte. A zinc wire is used as the inner anode, and a nickel Prussian blue / carbon nanotube fiber current collector is used as the outer cathode. On the one hand, by utilizing the zinc-philic groups of carbon dots, the inner anode and outer cathode are encapsulated by the carbon-dot-modified hydrogel, ensuring that the two electrodes are in close contact and fully immersed in the electrolyte environment, thus preparing an aqueous zinc-ion battery with stable cycle performance. On the other hand, by utilizing the fluorescence properties of carbon dots for multicolor display, a fibrous battery integrating fluorescence display and energy storage is prepared. This battery can be applied to the weaving field of wearable smart textiles, providing technical support for information visualization and energy supply in modern smart textile processes.

[0107] Obviously, the technical solution of this invention utilizes the abundant zinc-loving groups on the surface of carbon dots to suppress the growth of zinc anode dendrites, and at the same time uses the current collector obtained by in-situ growth of nickel Prussian blue on the surface of carbon nanofibers as the inner anode. Based on the high active sites of nickel, it provides the zinc-ion battery with cycle stability and capacity retention.

[0108] In particular, the fluorescent fiber-shaped aqueous zinc-ion battery with a high voltage platform and stable operation prepared using the technical solution of this invention provides technical support for information visualization and energy supply in the field of wearable smart textiles, enabling integrated wearable smart textile processes.

[0109] The above are merely preferred embodiments of the present invention and do not limit the scope of protection of the present invention. For those skilled in the art, the present invention can have various modifications and variations. Any changes, modifications, substitutions, integrations, and parameter alterations to these embodiments within the spirit and principles of the present invention, achieved through conventional substitutions or by achieving the same function without departing from the principles and spirit of the present invention, fall within the scope of protection of the present invention.

Claims

1. A fluorescent display fibrous aqueous zinc-ion battery, characterized in that, Using zinc wire as the inner anode, nickel Prussian blue / carbon nanotube fiber current collector as the outer cathode, and carbon dot-modified hydrogel electrolyte, the fluorescent display fiber-like aqueous zinc-ion battery is assembled; the fluorescent display fiber-like aqueous zinc-ion battery can be used to weave smart textiles with multi-color display and energy storage. The surfaces of both the zinc wire and the nickel Prussian blue / carbon nanotube fiber current collector are coated with the carbon-dot-modified hydrogel electrolyte. The nickel Prussian blue / carbon nanotube fiber current collector is wound onto the zinc wire by coaxial winding, and the fluorescent display fiber-like aqueous zinc-ion battery is encapsulated with the carbon-dot-modified hydrogel electrolyte. The hydrogel electrolyte ensures that the two electrodes of the inner anode and the outer cathode are tightly attached and fully wetted in the electrolyte environment. The carbon dot-modified hydrogel electrolyte is prepared by adding carbon dots to a polyvinyl alcohol solution and then performing a cyclic freezing method; the carbon dots are prepared by reacting citric acid with an organic compound containing -NH2 using a microwave method, followed by dialysis-freezing to obtain nitrogen-doped carbon dots; the surface of the carbon dots contains abundant zinc-loving groups. In the nickel Prussian blue / carbon nanotube fiber current collector, nickel Prussian blue is uniformly distributed on the carbon nanotube fibers through in-situ growth.

2. The fluorescent display fibrous aqueous zinc-ion battery according to claim 1, characterized in that, In the carbon dot-modified hydrogel electrolyte, the carbon dots are added in the range of 0.1 g / L to 0.5 g / L.

3. The fluorescent display fibrous aqueous zinc-ion battery according to claim 1, characterized in that, In the nickel Prussian blue / carbon nanotube fiber current collector, the nickel Prussian blue is a cubic nanostructure.

4. The fluorescent display fibrous aqueous zinc-ion battery according to any one of claims 1-3, characterized in that, The preparation of the nickel Prussian blue / carbon nanotube fiber current collector includes: (1) Solution A: Carbon nanotube fibers are immersed in a mixed solution of nickel salt and citrate to obtain solution A; (2) Solution B: Dissolve potassium ferrocyanide in water to obtain solution B; (3) Preparation of nickel Prussian blue / carbon nanotube fiber current collector: Solution B is slowly added dropwise to solution A, and after stirring slowly overnight, the carbon nanotube fiber is taken out and dried to obtain the nickel Prussian blue / carbon nanotube fiber current collector.

5. A method for preparing a fluorescent display fibrous aqueous zinc-ion battery as described in any one of claims 1-4, characterized in that, Includes the following steps: S1. Synthesis of carbon dots: Citric acid was ultrasonically dispersed in deionized water, and an organic compound containing -NH2 was added as a precursor solution; The precursor solution was subjected to a microwave reaction in a microwave reactor, and the reaction product was purified by dialysis and freeze-dried to obtain powdered carbon dots. S2. Preparation of carbon dot modified hydrogel electrolyte: The carbon dots obtained in S1 are added to a polyvinyl alcohol solution to form a carbon dot / polyvinyl alcohol solution; Zinc sulfate solution was added to the carbon dot / polyvinyl alcohol solution, and the carbon dot-modified hydrogel electrolyte was obtained by cyclic freezing. S3. Preparation of nickel Prussian blue / carbon nanotube fiber current collector: Carbon nanotube fibers are soaked in a mixed solution of nickel salt and citrate, potassium ferrocyanide solution is added, and the mixture is slowly stirred overnight and then dried to obtain the nickel Prussian blue / carbon nanotube fiber current collector. S4. Assembly of the fluorescent display fibrous aqueous zinc-ion battery: The zinc wire and the nickel Prussian blue / carbon nanotube fiber current collector prepared in S3 are respectively immersed in the carbon dot-modified hydrogel electrolyte, so that the surfaces of the zinc wire and the nickel Prussian blue / carbon nanotube fiber current collector are both coated with the carbon dot-modified hydrogel electrolyte. After being removed, washed and dried, the nickel Prussian blue / carbon nanotube fiber current collector is wound onto the zinc wire by coaxial winding. After encapsulation with the carbon dot-modified hydrogel electrolyte, the fluorescent display fibrous aqueous zinc-ion battery is obtained. The carbon dot-modified hydrogel electrolyte can ensure that the two electrodes are tightly attached and fully immersed in the electrolyte environment.

6. The method for preparing a fluorescent display fibrous aqueous zinc-ion battery according to claim 5, characterized in that, In S1, the dialysis purification-freeze-drying method includes centrifuging the reaction product obtained by the microwave reaction, taking the supernatant, transferring the supernatant to a 1000 Da dialysis bag, dialyzing for 2 days, and changing the deionized water every 6 hours during the period; after the dialysis is completed, the solution is frozen at -20°C and then transferred to a freeze dryer, and vacuum-frozen until it is completely formed into powder, thus obtaining the carbon dots.

7. The method for preparing a fluorescent display fibrous aqueous zinc-ion battery according to claim 5, characterized in that, In S2, the cyclic freezing method includes freezing the carbon dot / polyvinyl alcohol solution with the zinc sulfate solution at -20°C for 6 hours after the reaction is completed, cooling it to room temperature, and repeating the freeze-thaw process 3 times.

8. The method for preparing a fluorescent display fibrous aqueous zinc-ion battery according to claim 5, characterized in that, In S3, the potassium ferrocyanide solution and the nickel salt solution are prepared in an equimolar ratio.

9. An electrochemical energy storage device, characterized in that, Including the fluorescent fiber aqueous zinc-ion battery as described in any one of claims 1-4.

10. A wearable smart textile fabric woven from a fluorescent fiber aqueous zinc-ion battery as described in any one of claims 1-4, having the functions of multi-color display and energy storage.

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