Integrated zinc ion battery based on curled nanofiber-based gel electrolyte

Abstract

The invention discloses an integrated zinc ion battery based on a curled nanofiber-based gel electrolyte. The integrated zinc ion battery is structurally characterized by being composed of a curled nanofiber-based gel electrolyte layer, a positive electrode layer, a negative electrode layer, an upper packaging layer and a lower packaging layer, wherein the positive electrode layer is composed of a positive electrode material with zinc ion intercalation / deintercalation activity; the negative electrode layer is composed of metal zinc and a carbon nanomaterial; the preparation method mainly comprises the following steps: preparation of a polyisophthaloyl metaphenylene diamine coated polyurethane curled nanofiber membrane, preparation of a polyvinyl alcohol hydrogel electrolyte, compounding of a curled nanofiber based gel electrolyte, loading of a positive electrode material, loading of a negative electrode material, and packaging of the integrated zinc ion battery. According to the design, the mechanical property of the gel electrolyte is remarkably enhanced through the curled nanofibers, the impedance can be effectively reduced and the ionic conductivity can be effectively improved through better interface contact, the relative displacement or separation between adjacent assemblies can be prevented through the unique integrated structure, and even if the surface of the battery is deformed, the continuous and effective ion transfer capacity in the battery can be ensured; therefore, the device has excellent structural design and stable electrochemical performance, and is expected to provide a new direction for the development of next-generation wearable energy storage devices.

Description

Technical Field

[0001] The present invention belongs to the field of zinc ion battery materials and technologies, and in particular relates to an integrated zinc ion battery based on a curled nanofiber-based gel electrolyte and a preparation method thereof. Background Art

[0002] The development of portable and multifunctional wearable and implantable electronic devices has become a key trend in the pursuit of a versatile and lightweight future smart lifestyle. This requires lightweight, safe, and high-performance power sources. Zinc-ion batteries have attracted considerable attention due to their safety, ease of processing, and cost-effectiveness, offering a wide range of electrolyte and separator options. However, conventional energy storage devices employ a sandwich structure consisting of a cathode, separator, and anode, which exhibits poor mechanical properties and a significant performance degradation upon deformation. Furthermore, electrolyte leakage can affect the cycling performance of zinc-ion batteries with liquid electrolytes when subjected to various mechanical deformations. Developing energy storage devices with optimal performance and optimal configurations is a significant challenge. Currently, the solid-liquid interface is gradually transforming into a solid-solid interface, which not only addresses these challenges but also provides innovative approaches for flexible integrated batteries. This novel integrated structure integrates all battery components together, ensuring integrity under various bending conditions by preventing relative slippage and separation between the integrated layers. Therefore, integrated energy storage devices have the potential to meet the requirements of wearable devices and related applications.

[0003] In recent years, more and more scholars have begun to study integrated structures and have shown great potential in wearable and stretchable electronic products. For example, Zhang et al. formed an integrated zinc ion battery by fully freezing-casting a reduced graphene oxide / polyaniline cathode, a cellulose nanofiber separator, and an exfoliated graphene / Zn anode to accelerate the transmission of zinc ions (Y Zhang, Q. Wang, S. Bi, NANOSCALE 11 (2019) 17630-17636). In addition, it has been found that the use of an excellent self-supporting flexible membrane structure based on electrospinning nanofibers provides another effective method for constructing flexible integrated batteries (MHTai, P. Gao, BYLTan, ACS Appl. Mater. Interfaces 6 (2014) 9393-9401). For example: Shao et al. designed a “paper-like” zinc ion battery with an integrated structure, which prepares polyacrylonitrile nanofiber membrane as a battery separator by electrospinning technology, and performs in situ deposition of negative electrode Zn nanosheets and positive electrode manganese dioxide nanosheets on the separator, avoiding the relative sliding and separation of the integrated layer, ensuring the formation of monomers in different bending states (Z.Shao, S.Cheng, YZhang, H.Guo, ACS Appl.Mater.Inter 13 (2021) 34349-34356). Although the electrolytes prepared by the above method all show a certain degree of flexibility, in practical applications, there are more prominent problems at the interface between the electrode and the solid electrolyte. Specifically manifested in that the reaction kinetics at the interface are slow, and the interfacial compatibility of the two is poor. The combined effect of these factors makes the conduction of zinc ions therein hindered, and the conductivity is at a low level. In addition, the mechanical strength of the above-mentioned electrolyte itself is insufficient, and a series of problems such as the cumbersome and complicated assembly process have seriously restricted the process of realizing large-scale industrial production of integrated zinc ion batteries.

[0004] Based on this, the present invention provides an integrated zinc-ion battery based on curled nanofiber-based gel electrolyte. The uniform pore size and high porosity of the curled nanofibers can better combine with the gel electrolyte to enhance the overall mechanical properties. The integrated structure can effectively alleviate the interface contact problem and improve the battery ion transmission rate, providing a direction for the development of high-performance wearable flexible integrated zinc-ion batteries. Summary of the Invention

[0005] The purpose of the present invention is to solve the problems of poor interface contact and low ionic conductivity in traditional zinc-ion batteries, and to provide an integrated preparation method for a flexible gel-state zinc-ion battery reinforced with curled nanofibers. This method uses a specially made rough plate as a receiving substrate to prepare a polyisophthalamide@polyurethane curled nanofiber membrane, the pores of which can promote the infiltration of gel electrolytes and thus improve ionic conductivity; the combination of nanofibers and hydrogel electrolytes can significantly enhance mechanical strength; and the curled structure can alleviate the mechanical stress generated by the battery during the reaction process. The positive and negative electrodes are located on both sides of the gel electrolyte by in-situ coating. Due to the strong viscosity of the gel electrolyte, the electrolyte and electrodes can be bonded together to form an integrated structure. This unique integrated structure prevents relative displacement or separation between adjacent components, and ensures continuous and effective ion transfer capabilities inside even if the battery surface is deformed, so that the device has excellent structural design and stable electrochemical performance.

[0006] The purpose of the present invention can be achieved by the following solutions:

[0007] A method for preparing an integrated zinc ion battery based on a curled nanofiber-based gel electrolyte, characterized by comprising the following steps:

[0008] (1) Preparation of poly(m-phenylene isophthalamide)@polyurethane curly nanofiber membrane: Poly(m-phenylene isophthalamide) and polyurethane were dissolved in a solvent at a certain mass ratio and blended to prepare a spinning solution. Curly nanofiber membranes were prepared on a specially prepared roughened plate by a one-step electrospinning technique under the following parameters: voltage 10-40 kV, receiving distance 10-30 cm, temperature 15°C-30°C, and humidity 10-40%;

[0009] (2) Preparation of polyvinyl alcohol hydrogel electrolyte: polyvinyl alcohol, zinc salt and crosslinking agent were added to deionized water, heated and stirred at 60-95°C in a water bath to obtain a colorless and transparent solution;

[0010] (3) Composite of curly nanofiber-based gel electrolyte: PVA hydrogel electrolyte was poured into the curly nanofiber membrane to ensure complete infiltration for 10-30 min, and cross-linked and cured at room temperature;

[0011] (4) Loading of positive electrode material: positive electrode active material, conductive carbon black, and binder in a mass ratio of 1 to 10:1 to 4:1 are mixed and stirred into a uniform slurry, and the slurry is in situ coated on one side of the curled nanofiber-based gel electrolyte layer using a doctor blade method, and then dried as the positive electrode material;

[0012] (5) Loading of negative electrode materials: Zinc powder with a particle size of 3-5 μm and carbon nanotubes were ultrasonically dispersed in N-methyl-2-pyrrolidone at a mass ratio of 10-20:1. The dispersion was concentrated by solvent evaporation to obtain a slurry. The slurry was in situ coated on the other side of the curled nanofiber-based gel electrolyte layer using a doctor blade method and dried as the negative electrode material;

[0013] (6) Packaging: Attach polyethylene terephthalate film, polyimide film or aluminum foil to both sides of the positive and negative electrodes and package them by hot pressing. The heat sealing temperature is 110-130°C, the pressure is 0.3-0.8 MPa, and the time is 10-30 seconds to obtain an integrated zinc ion battery with a curled nanofiber-based gel electrolyte.

[0014] Furthermore, in step (1), the mass fraction of the blended spinning solution is 10-25%, wherein the mass ratio of polyisophthalamide and thermoplastic polyurethane solute is 1-5:1-4; the specially made rough plate is a conductive receiving plate with a roughness of 10-400 μm, and a groove structure with a depth of 20-500 μm is provided on the surface, and the cross-sectional shape of the groove is polygonal or circular.

[0015] Furthermore, in step (2), the zinc salt is any one or more combinations of zinc chloride, zinc nitrate, zinc acetate, zinc sulfate, zinc perchlorate, zinc trifluoromethanesulfonate, and zinc bis(trifluoromethylsulfonyl)imide; the cross-linking agent is one or more combinations of NN′-methylenebis(acrylamide), divinylbenzene, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 1,4-butanediol diacrylate, and ethylene glycol dimethacrylate.

[0016] Furthermore, in step (4), the positive electrode active material is one or more combinations of manganese-based oxides, vanadium-based oxides, polyaniline, and Prussian blue analogs; and the binder is one or more combinations of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethyl cellulose, sodium alginate, and polydopamine.

[0017] Compared with the prior art, the present invention has the following advantages and benefits:

[0018] The present invention successfully completes the preparation of the curled fiber membrane by using only a specially made rough plate as an auxiliary tool. This simple and efficient preparation method opens up a new path for the controllable, large-scale preparation of curled fiber membranes. The combination of the curled nanofiber membrane and the gel electrolyte significantly improves the mechanical strength and ion transfer rate of the electrolyte, increasing the possibility of high-performance zinc-ion batteries. Both the fiber membrane and the gel have good stretchability and elasticity, which can effectively alleviate the mechanical stress generated during the battery reaction and improve the cycle life of the zinc-ion battery. The unique integrated structure prevents relative displacement or separation between adjacent components, ensuring continuous and effective ion transfer capacity within the battery even if the battery surface is deformed, thus giving the device an excellent structural design and stable electrochemical performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 Schematic diagram of the preparation process of an integrated zinc-ion battery with curled nanofiber-based gel electrolyte.

[0020] Figure 2 Schematic diagram of electron microscopy of curled nanofiber reinforced gel electrolyte.

[0021] Figure 3 Schematic diagram of the tensile stress-strain curve of curled nanofiber reinforced gel electrolyte.

[0022] Figure 4 Schematic diagram of the ionic conductivity of an integrated zinc-ion battery with a curled nanofiber-based gel electrolyte.

[0023] Figure 5 Schematic diagram of the impedance of an integrated zinc-ion battery with curled nanofiber-based gel electrolyte. DETAILED DESCRIPTION

[0024] The present invention will be further described below with reference to specific embodiments.

[0025] Example 1

[0026] (1) Preparation of poly(m-phenylene isophthalamide)@polyurethane curly nanofiber membrane: Poly(m-phenylene isophthalamide) and polyurethane were dissolved in N,N-dimethylformamide at a mass ratio of 2:1 and blended to prepare a spinning solution. The solution was allowed to stand to remove bubbles before use. Curly nanofiber membranes were prepared on a specially prepared roughened plate using a one-step electrospinning technique under the spinning parameters of 30 kV voltage, 18 cm receiving distance, 25°C temperature, and 15% humidity. The collected nanofiber membranes were then dried in a vacuum oven for 24 h to remove any residual solvent.

[0027] (2) Preparation of polyvinyl alcohol hydrogel electrolyte: 25 wt% polyvinyl alcohol and 1.5 mol / L zinc trifluoromethanesulfonate were added to a mixed solvent of deionized water. The mixture was magnetically stirred at room temperature for 3 h to allow the polyvinyl alcohol to fully swell. The mixture was then placed in a water bath and heated and stirred at 90°C for 6 h to completely dissolve the polyvinyl alcohol. 5 μL of a 4 wt% boric acid solution was added dropwise to the polyvinyl alcohol solution, and stirring was continued for 0.5 h. Stirring was then turned off and heating was continued for 0.5 h to eliminate small bubbles generated during stirring, resulting in a colorless and transparent polyvinyl alcohol mixed solution.

[0028] (3) Composite preparation of curly nanofiber-based gel electrolyte: The polyvinyl alcohol hydrogel electrolyte solution was poured into the poly(m-phenylene isophthalamide)@polyurethane curly nanofiber membrane, and the mixture was allowed to soak for 30 min and then cross-linked and cured at room temperature.

[0029] (4) Loading of positive electrode material: Manganese dioxide, conductive carbon black, and binder polyvinylidene fluoride in a mass ratio of 7:3:1 were mixed and stirred into a uniform slurry. The slurry was in situ coated on one side of the curled nanofiber-based gel electrolyte layer using a scraper method and used as the positive electrode material after drying.

[0030] (5) Loading of negative electrode material: Zinc powder with a particle size of 3 μm and carbon nanotubes were ultrasonically dispersed in N-methyl-2-pyrrolidone at a mass ratio of 15:1. The dispersion was concentrated by solvent evaporation to obtain a slurry. The slurry was in situ coated on the other side of the curled nanofiber-based gel electrolyte layer using a doctor blade method and dried as the negative electrode material.

[0031] (6) Packaging: A polyethylene terephthalate film was attached to both sides of the positive and negative electrodes and packaged by hot pressing at a heat sealing temperature of 130°C, a pressure of 0.5 MPa, and a time of 20 s to obtain an integrated zinc ion battery with a curled nanofiber-based gel electrolyte.

[0032] The preparation process of the integrated zinc ion battery with curled nanofiber-based gel electrolyte is shown in the figure. Figure 1 shown.

[0033] Electron microscopy images of curled nanofiber reinforced gel electrolytes Figure 2 shown.

[0034] Example 2

[0035] (1) Preparation of poly(m-phenylene isophthalamide)@polyurethane nanofiber membrane: Poly(m-phenylene isophthalamide) and polyurethane were dissolved in N,N-dimethylformamide at a mass ratio of 2:1 and mixed to prepare a spinning solution. The solution was allowed to stand to remove bubbles before use. Nanofiber membranes were prepared on ordinary receiving paper using a one-step electrospinning technique under the spinning parameters of 30 kV voltage, 18 cm receiving distance, 25°C temperature, and 15% humidity. The collected nanofiber membranes were then dried in a vacuum oven for 24 h to remove any residual solvent.

[0036] (2) Preparation of polyvinyl alcohol hydrogel electrolyte: 25 wt% polyvinyl alcohol and 1.5 mol / L zinc trifluoromethanesulfonate were added to a mixed solvent of deionized water and magnetically stirred at room temperature for 3 h to allow the polyvinyl alcohol to fully swell. The mixture was then placed in a water bath and heated and stirred at 90°C for 6 h to completely dissolve the polyvinyl alcohol. 5 μL of a 4 wt% boric acid solution was added dropwise to the polyvinyl alcohol solution, and stirring was continued for 0.5 h. Stirring was then turned off and heating was continued for 0.5 h to eliminate small bubbles generated during stirring, resulting in a colorless and transparent polyvinyl alcohol mixed solution.

[0037] (3) Composite preparation of nanofiber-based gel electrolyte: The polyvinyl alcohol hydrogel electrolyte solution was poured into the poly(m-phenylene isophthalamide)@polyurethane nanofiber membrane, and the membrane was completely infiltrated for 30 min, and then cross-linked and cured at room temperature.

[0038] (4) Loading of positive electrode materials: Manganese dioxide, conductive carbon black, and binder polyvinylidene fluoride in a mass ratio of 7:3:1 were mixed and stirred into a uniform slurry. The slurry was in situ coated on one side of the nanofiber-based gel electrolyte layer using a scraper method and used as the positive electrode material after drying.

[0039] (5) Loading of negative electrode material: Zinc powder with a particle size of 3 μm and carbon nanotubes were ultrasonically dispersed in N-methyl-2-pyrrolidone at a mass ratio of 15:1. The dispersion was concentrated by solvent evaporation to obtain a slurry. The slurry was in situ coated on the other side of the nanofiber-based gel electrolyte layer using a doctor blade method and dried as the negative electrode material.

[0040] (6) Packaging: A polyethylene terephthalate film was attached to both sides of the positive and negative electrodes and packaged by hot pressing at a heat sealing temperature of 130°C, a pressure of 0.5 MPa, and a time of 20 s to obtain an integrated zinc ion battery with a nanofiber-based gel electrolyte.

[0041] Example 3

[0042] (1) Preparation of polyvinyl alcohol hydrogel electrolyte: 25 wt% polyvinyl alcohol and 1.5 mol / L zinc trifluoromethanesulfonate were added to a mixed solvent of deionized water and magnetically stirred at room temperature for 3 h to allow the polyvinyl alcohol to fully swell. The mixture was then placed in a water bath and heated and stirred at 90°C for 6 h to completely dissolve the polyvinyl alcohol. 5 μL of a 4 wt% boric acid solution was added dropwise to the polyvinyl alcohol solution, and stirring was continued for 0.5 h. Stirring was then turned off and heating was continued for 0.5 h to eliminate small bubbles generated during stirring, resulting in a colorless and transparent polyvinyl alcohol mixed solution.

[0043] (2) Loading of positive electrode material: Manganese dioxide, conductive carbon black, and binder polyvinylidene fluoride in a mass ratio of 7:3:1 were mixed and stirred into a uniform slurry. The slurry was in situ coated on one side of the gel electrolyte layer using a scraper method and used as the positive electrode material after drying.

[0044] (3) Loading of negative electrode material: Zinc powder with a particle size of 3 μm and carbon nanotubes were ultrasonically dispersed in N-methyl-2-pyrrolidone at a mass ratio of 15:1. The dispersion was concentrated by solvent evaporation to obtain a slurry. The slurry was in situ coated on the other side of the gel electrolyte layer using a doctor blade method and dried as the negative electrode material.

[0045] (4) Packaging: A polyethylene terephthalate film was attached to both sides of the positive and negative electrodes and packaged by hot pressing at a heat sealing temperature of 130°C, a pressure of 0.5 MPa, and a time of 20 seconds to obtain a gel electrolyte integrated zinc ion battery.

[0046] Comparative Example 1

[0047] (1) Preparation of poly(m-phenylene isophthalamide)@polyurethane nanofiber membrane: Poly(m-phenylene isophthalamide) and polyurethane were dissolved in N,N-dimethylformamide at a mass ratio of 2:1 and mixed to prepare a spinning solution. The solution was allowed to stand to remove bubbles before use. Nanofiber membranes were prepared on ordinary receiving paper using a one-step electrospinning technique under the spinning parameters of 30 kV voltage, 18 cm receiving distance, 25°C temperature, and 15% humidity. The collected nanofiber membranes were then dried in a vacuum oven for 24 h to remove any residual solvent.

[0048] (2) Preparation of polyvinyl alcohol hydrogel electrolyte: 25 wt% polyvinyl alcohol and 1.5 mol / L zinc trifluoromethanesulfonate were added to a mixed solvent of deionized water and magnetically stirred at room temperature for 3 h to allow the polyvinyl alcohol to fully swell. The mixture was then placed in a water bath and heated and stirred at 90°C for 6 h to completely dissolve the polyvinyl alcohol. 5 μL of a 4 wt% boric acid solution was added dropwise to the polyvinyl alcohol solution, and stirring was continued for 0.5 h. Stirring was then turned off and heating was continued for 0.5 h to eliminate small bubbles generated during stirring, resulting in a colorless and transparent polyvinyl alcohol mixed solution.

[0049] (3) Composite preparation of nanofiber-based gel electrolyte: The polyvinyl alcohol hydrogel electrolyte solution was poured into the poly(m-phenylene isophthalamide)@polyurethane nanofiber membrane, and the membrane was allowed to soak for 30 min to ensure complete soaking. The membrane was then cross-linked and cured at room temperature to obtain a composite gel electrolyte.

[0050] (4) Loading of positive electrode material: Manganese dioxide, conductive carbon black, and binder polyvinylidene fluoride in a mass ratio of 7:3:1 were mixed and stirred into a uniform slurry, and the slurry was coated on a stainless steel foil using a scraper method and dried as a positive electrode material.

[0051] (5) Packaging: The composite gel electrolyte, zinc foil negative electrode and positive electrode materials of the same size are combined and packaged by hot pressing at a heat sealing temperature of 130°C, a pressure of 0.5 MPa and a time of 20 seconds to obtain a composite gel zinc ion battery.

[0052] The mechanical properties of the integrated gel electrolytes constructed in Examples 1 to 3 were tested. Figure 3 As shown in the figure, it can be seen that compared with pure gel electrolyte, the nanofiber membrane-based reinforced gel electrolyte has better mechanical strength, and the curled nanofiber-reinforced gel electrolyte has better tensile properties than the conventional nanofiber-reinforced gel electrolyte, thereby improving the overall flexibility of the integrated battery.

[0053] The zinc ion batteries constructed in Examples 1 to 3 and Comparative Example 1 were tested for ionic conductivity and impedance. Figures 4-5 As shown. It can be seen that long-range continuous nanofibers can provide additional ion transport channels, playing an important role in improving the ionic conductivity of polymer electrolyte batteries. At the same time, compared with ordinary nanofibers, curly fibers have a uniform pore structure and a larger porosity, which is conducive to the uniform compounding of the gel and accelerates the transmission rate of zinc ions, thereby significantly improving the ionic conductivity. In addition, the integrated structure has better interface contact than conventional assembled batteries, which can effectively increase the charge transfer channel, reduce impedance, and ultimately show better cycle stability.

Claims

1. An integrated zinc ion battery based on a curled nanofiber-based gel electrolyte, characterized in that: It consists of a curled nanofiber-based gel electrolyte layer, a positive electrode layer composed of a positive electrode material with zinc ion insertion / deinsertion activity, a negative electrode layer composed of metallic zinc and carbon nanomaterials, and two upper and lower encapsulation layers, with a thickness of 180-650μm; The curled nanofiber-based gel electrolyte has a thickness of 50-300 μm and comprises a curled nanofiber support prepared by composite electrospinning of poly(m-phenylene isophthalamide) and polyurethane, a zinc salt, and a polyvinyl alcohol hydrogel electrolyte, wherein the diameter of the curled nanofiber is 50-1200 nm, the number of curls is 3-7 / 25 μm, the curl height is 3-10 μm, the thickness of the curled nanofiber membrane is 30-100 μm, the porosity is 70-95%, and the pore size is 1-10 μm; The positive electrode layer is composed of a positive electrode material containing zinc ion intercalation / deintercalation activity and is directly constructed on one side of the curled nanofiber-based gel electrolyte layer by in-situ coating. The thickness is 10-50 μm. The negative electrode layer is composed of zinc powder and carbon nanotubes and is constructed on the other side of the curled nanofiber-based gel electrolyte layer by in-situ coating. The thickness is 20-100 μm. The encapsulation layer is encapsulated as a whole by a thin film, and the thickness of a single layer is 50-100 μm.

2. The method for preparing an integrated zinc ion battery based on a curled nanofiber-based gel electrolyte according to claim 1, characterized in that: The following steps are involved: (1) Preparation of poly(m-phenylene isophthalamide)@polyurethane curly nanofiber membrane: Poly(m-phenylene isophthalamide) and polyurethane were dissolved in a solvent at a certain mass ratio and blended to prepare a spinning solution. Curly nanofiber membranes were prepared on a specially prepared roughened plate by a one-step electrospinning technique under the following parameters: voltage 10-40 kV, receiving distance 10-30 cm, temperature 15°C-30°C, and humidity 10-40%; (2) Preparation of polyvinyl alcohol hydrogel electrolyte: polyvinyl alcohol, zinc salt and crosslinking agent were added to deionized water, heated and stirred at 60-95°C in a water bath to obtain a colorless and transparent solution; (3) Composite of curly nanofiber-based gel electrolyte: PVA hydrogel electrolyte was poured into the curly nanofiber membrane to ensure complete infiltration for 10-30 min, and cross-linked and cured at room temperature; (4) Loading of positive electrode material: positive electrode active material, conductive carbon black, and binder in a mass ratio of 1 to 10:1 to 4:1 are mixed and stirred into a uniform slurry, and the slurry is in situ coated on one side of the curled nanofiber-based gel electrolyte layer using a doctor blade method, and then dried as the positive electrode material; (5) Loading of negative electrode materials: Zinc powder with a particle size of 3-5 μm and carbon nanotubes were ultrasonically dispersed in N-methyl-2-pyrrolidone at a mass ratio of 10-20:

1. The dispersion was concentrated by solvent evaporation to obtain a slurry. The slurry was in situ coated on the other side of the curled nanofiber-based gel electrolyte layer using a doctor blade method and dried as the negative electrode material; (6) Packaging: Attach polyethylene terephthalate film, polyimide film or aluminum foil to both sides of the positive and negative electrodes and package them by hot pressing. The heat sealing temperature is 110-130°C, the pressure is 0.3-0.8 MPa, and the time is 10-30 seconds to obtain an integrated zinc ion battery with a curled nanofiber-based gel electrolyte.

3. The preparation method according to claim 2, characterized in that In step (1), the mass fraction of the blended spinning solution is 10-25%, wherein the mass ratio of polyisophthalamide (m-phenylenediamine) and thermoplastic polyurethane solute is 1-5:1-4; the specially made rough plate is a conductive receiving plate with a roughness of 10-400 μm, and a groove structure with a depth of 20-500 μm is provided on the surface, and the cross-sectional shape of the groove is polygonal or circular.

4. The preparation method according to claim 2, wherein In step (2), the zinc salt is any one or more combinations of zinc chloride, zinc nitrate, zinc acetate, zinc sulfate, zinc perchlorate, zinc trifluoromethanesulfonate, and zinc bis(trifluoromethylsulfonyl)imide; the cross-linking agent is one or more combinations of NN′-methylenebis(acrylamide), divinylbenzene, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 1,4-butanediol diacrylate, and ethylene glycol dimethacrylate.

5. The preparation method according to claim 2, characterized in that In step (4), the positive electrode active material is one or more combinations of manganese-based oxides, vanadium-based oxides, polyaniline, and Prussian blue analogs; the binder is one or more combinations of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethyl cellulose, sodium alginate, and polydopamine.

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