A gel-zinc powder-based negative electrode fiber aqueous zinc ion battery and a preparation method thereof

Abstract

The present application belongs to the technical field of flexible fiber battery, and specifically relates to a fiber aqueous zinc ion battery based on gel zinc powder negative electrode and a preparation method thereof. In the present application, nickel and copper wires are used as the positive and negative current collectors of the fiber battery, zinc powder slurry is coated on the current collectors and in-situ polymerized gel zinc powder is used as the fiber negative electrode, manganese dioxide slurry is coated on the current collectors as the fiber positive electrode, a cellulose diaphragm is wrapped around the surface of the fiber manganese dioxide positive electrode and twisted with the fiber gel zinc powder negative electrode to prepare a winding structure fiber aqueous zinc ion battery. The integrated organic gel zinc powder negative electrode and the aqueous electrolyte form a two-phase interface through phase separation, which avoids the occurrence of side reactions such as hydrogen evolution and corrosion caused by the intrinsic thermodynamic instability of zinc powder in the aqueous electrolyte, thereby effectively improving the stability of the fiber aqueous zinc ion battery negative electrode. The fiber aqueous zinc ion battery of the present application has a simple structure and can be continuously prepared, and has a wide application prospect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of flexible fiber batteries, and particularly relates to a fiber aqueous zinc ion battery and a preparation method thereof. BACKGROUND

[0002] In recent years, the rise of portable and wearable electronic devices has strongly promoted the development of green and high-safety flexible energy storage power sources. Among them, flexible fiber batteries have attracted particular attention due to their advantages such as miniaturization, flexibility and integration with traditional fabric weaving. Traditional fiber lithium ion batteries have safety hazards such as high toxicity and easy combustion and explosion due to the use of organic electrolyte. Fiber aqueous zinc ion batteries with zinc metal as the negative electrode are considered to be the next generation of flexible energy storage devices due to their lower redox reaction potential (-0.76V vs SHE), higher theoretical specific capacity (820mAh / g or 5855mAh / cm 3 ) and outstanding intrinsic safety. At present, the construction of fiber aqueous zinc ion batteries mainly uses zinc metal wires as the negative electrode to match fiber positive electrodes with low active material loading. However, the use of zinc metal wires as both the fiber current collector and the negative active material also brings a series of problems: on the one hand, the use of zinc metal wires reduces the flexibility of the fiber battery, and during repeated bending and cyclic charging and discharging processes, the zinc metal wires are prone to fatigue fracture, which leads to performance degradation or even failure of the battery; on the other hand, the zinc metal wire negative electrode leads to a high negative / positive capacity ratio (N / P ratio), which in turn reduces the energy density of the entire fiber full battery device.

[0003] Compared with the integrated fiber morphology of traditional zinc wire, zinc powder in the form of particles has the advantages of low cost, good processability and strong adjustability. It can be adjusted by the surface area to form electrode slurry, which is compatible with the continuous coating and preparation process of existing fiber batteries. However, the different failure mechanisms caused by the different appearances of zinc powder and zinc wire limit its practical application. The larger contact area between zinc powder and electrolyte increases the corrosion risk and worsens the inherent thermodynamic instability of zinc in aqueous electrolyte, which promotes the reduction of water to generate hydrogen and changes the local pH value near the electrode. The strong alkaline environment formed can further corrode the zinc surface and lead to the loss of zinc and the generation of zinc hydroxide / zinc oxide and other by-products, ultimately limiting the electrochemical performance and service life of fiber aqueous zinc ion battery. Limiting the direct contact between zinc anode and free water in the electrolyte can significantly improve the thermodynamic stability of the zinc anode. Although previous studies have improved the stability of zinc anode in aqueous electrolyte by constructing organic / inorganic coating on the surface of zinc metal foil, this simple coating strategy is prone to coating rupture during the volume expansion / contraction of fiber zinc anode during high-capacity deposition / detachment, ultimately leading to battery failure. However, there are few reports on the protection of fiber zinc powder anode and the construction strategy of fiber aqueous zinc ion full battery. Therefore, there is an urgent need to develop an effective protection strategy for high-stability zinc powder anode and a continuous construction method for fiber aqueous zinc ion battery. SUMMARY

[0004] In order to solve the problems of poor stability and difficulty in continuous construction of fiber aqueous zinc ion battery zinc anode, the purpose of the present application is to provide a fiber aqueous zinc ion battery based on gel zinc powder anode with high stability and continuous construction and a preparation method thereof.

[0005] The fiber aqueous zinc ion battery based on gel zinc powder anode provided by the present application uses nickel and copper wire as the positive and negative current collectors of the fiber battery, respectively. Zinc powder slurry is coated on the current collector and in-situ polymerized gel zinc powder electrode as the fiber negative electrode, and manganese dioxide slurry is coated on the current collector as the fiber positive electrode. The fiber cellulose separator is wrapped around the surface of the fiber manganese dioxide positive electrode and twisted with the fiber gel zinc powder negative electrode to prepare a winding structure fiber aqueous zinc ion battery. The integrated organic gel zinc powder negative electrode and the aqueous electrolyte form a two-phase interface through phase separation, avoiding the occurrence of side reactions such as hydrogen evolution and corrosion caused by the intrinsic thermodynamic instability of zinc powder in the aqueous electrolyte, thereby effectively improving the stability of the fiber aqueous zinc ion battery negative electrode. The specific preparation steps include preparation of organic gel precursor solution, preparation of electrode slurry, preparation of fiber gel zinc powder negative electrode, preparation of fiber manganese dioxide positive electrode and assembly of fiber zinc ion full battery.

[0006] The application provides a preparation method of a fiber aqueous zinc ion battery based on a gel zinc powder negative electrode.

[0007] (1) Preparation of an organic gel precursor solution: the organic gel precursor solution is prepared by ultrasonic dissolution. First, a certain amount of zinc bis(trifluoromethylsulfonyl) imide (Zn(TFSI)2) is added to an organic solvent of tris(2,2,2-trifluoroethyl) phosphate (TFEP), and the zinc salt is completely dissolved in an ultrasonic cleaner; then, polyethylene glycol dimethacrylate (PEGDMA) monomer is added to the obtained organic electrolyte solution and stirred until the solution is uniform and transparent; then, 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP) is added as a photoinitiator for ultraviolet polymerization, and finally the obtained organic gel precursor solution is wrapped with aluminum foil to block light and placed on a magnetic stirring table for uniform stirring;

[0008] (2) Preparation of an electrode slurry: for the zinc powder electrode slurry, first, a certain amount of polyvinylidene fluoride (PVDF) powder is added to N-methyl pyrrolidone (NMP) solvent and stirred to completely dissolve the same, to obtain a binder solution; then, a certain amount of zinc powder, multi-walled carbon nanotube powder and tin powder are respectively added to a mortar and mixed and ground, and then added to the above binder solution, and continuously stirred and uniformly mixed to prepare the zinc powder electrode slurry; for the manganese dioxide electrode slurry, first, a certain amount of polyvinylidene fluoride (PVDF) powder is added to N-methyl pyrrolidone (NMP) solvent and stirred to completely dissolve the same, to obtain a binder solution; then, a certain amount of manganese dioxide powder and conductive carbon black are respectively added to a mortar and ground and mixed, and then added to the above binder solution, and continuously stirred and uniformly mixed to obtain the manganese dioxide electrode slurry.

[0009] (3) Preparation of a fiber gel zinc powder negative electrode: the prepared zinc powder negative electrode slurry is loaded into a slurry cylinder, a motor is started to make the customized copper wire fiber current collector pass through the slurry cylinder loaded with the zinc powder negative electrode slurry at a constant speed, and then the fiber zinc powder negative electrode is obtained by winding and rolling after passing through a temperature gradient hot air drying tube; further, the obtained fiber zinc powder electrode is soaked in the organic gel precursor solution in a vacuum glove box, and then irradiated by an ultraviolet light irradiation device, and the fiber gel zinc powder negative electrode is obtained by winding after in-situ photoinitiated radical polymerization.

[0010] (4) Preparation of a fiber manganese dioxide positive electrode: the prepared manganese dioxide electrode slurry is loaded into a slurry cylinder, a motor is started to make the customized nickel wire fiber current collector pass through the slurry cylinder loaded with the manganese dioxide slurry at a constant speed, and then the fiber manganese dioxide positive electrode is obtained by winding and rolling after passing through a temperature gradient hot air drying tube.

[0011] (5) The assembly of fiber aqueous zinc ion battery: Firstly, the obtained fiber manganese dioxide positive electrode is wound on the cellulose separator by the separator winding device, and then the fiber gel zinc powder negative electrode is twisted by the twisting device to obtain the fiber zinc ion battery cell with a winding structure. The cell is packaged with a commercial FEP tube and injected with bis(trifluoromethylsulfonyl) imide zinc (Zn(TFSI)2) liquid electrolyte, the tab is drawn out and the fiber ends are sealed with hot melt adhesive to obtain the fiber aqueous zinc ion battery.

[0012] Further, the specific preparation process of the organic gel precursor solution in step (1) is as follows: first, 1.56-12.5 grams of bis(trifluoromethylsulfonyl) imide zinc (Zn(TFSI)2) electrolyte salt is added to 5-10 milliliters of phosphoric acid tris(2,2,2-trifluoroethyl) ester (TFEP) organic solvent, and ultrasonic cleaning is performed for 50-120 minutes until the zinc salt is completely dissolved to obtain an organic electrolyte solution of 0.5-2 moles per liter; then 1-5 grams of polyethylene glycol dimethacrylate (PEGDMA) monomer is added to the above solution and magnetically stirred for 10-30 minutes until the solution is uniform and transparent; then 3wt%-8wt% of 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP) is added as a photoinitiator for ultraviolet light polymerization, and finally the obtained organic gel precursor solution is wrapped with aluminum foil to block light and placed on a magnetic stirrer for uniform stirring for 30-60 minutes.

[0013] Further, the specific preparation process of the electrode slurry in step (2) is as follows: in order to prepare a zinc powder electrode slurry with a solid content of 40wt%-43wt%, first, 6wt%-10wt% of polyvinylidene fluoride (PVDF) powder by solid mass is added to 5-10 milliliters of N-methyl pyrrolidone (NMP) solvent and stirred for 5-10 hours to completely dissolve it, then 70wt%-80wt% of zinc powder, 8wt%-12wt% of multi-walled carbon nanotube powder and 5wt%-10wt% of tin powder by solid mass are weighed into a mortar and mixed and ground for 20-40 minutes, then added to the above binder solution, continuously stirred for 12-24 hours, and then the zinc powder electrode slurry is prepared after uniform mixing; for the manganese dioxide electrode slurry with a solid content of 16wt%-20wt%, first, 8wt%-12wt% of polyvinylidene fluoride (PVDF) powder by solid mass is added to 5-10 milliliters of N-methyl pyrrolidone (NMP) solvent and stirred for 5-10 hours to completely dissolve it, then 65wt%-75wt% of manganese dioxide powder and 15wt%-25wt% of conductive carbon black by solid mass are weighed into a mortar and mixed and ground for 20-40 minutes, then added to the above binder solution, continuously stirred for 12-24 hours, and then the manganese dioxide electrode slurry is prepared after uniform mixing.

[0014] Further, the specific preparation process of the fiber gel zinc powder negative electrode in step (3) is as follows: the prepared zinc powder slurry is loaded into a slurry cylinder, a motor is started to make the customized copper wire fiber current collector pass through the slurry cylinder containing the zinc powder slurry at a speed of 2-6 revolutions per minute, then the fiber zinc powder negative electrode is obtained after drying through a temperature gradient hot air drying tube (the drying temperatures of the front, middle and rear sections are 170-190 degrees Celsius, 130-150 degrees Celsius and 90-110 degrees Celsius respectively) and winding, then the obtained fiber zinc powder electrode is soaked in an organic gel precursor solution in a vacuum glove box and irradiated by a ultraviolet light irradiation device for 1-3 minutes, and the fiber gel zinc powder negative electrode is obtained after in-situ photoinitiated radical polymerization and winding.

[0015] Further, the specific preparation process of the fiber manganese dioxide positive electrode in step (4) is as follows: the prepared manganese dioxide electrode slurry is loaded into a slurry cylinder, a motor is started to make the customized nickel wire fiber current collector pass through the slurry cylinder containing the manganese dioxide slurry at a speed of 2-6 revolutions per minute, then the fiber manganese dioxide positive electrode is obtained after drying through a temperature gradient hot air drying tube (the drying temperatures of the front, middle and rear sections are 130-150 degrees Celsius, 90-110 degrees Celsius and 50-70 degrees Celsius respectively) and winding.

[0016] Further, the specific assembly process of the fiber aqueous zinc ion full battery in step (5) is as follows: first, the fiber manganese dioxide positive electrode is wound with a cellulose separator with a width of 2-4 millimeters through a separator winding device, then the fiber gel zinc powder negative electrode is twisted with the fiber manganese dioxide positive electrode through a twisting device to obtain a fiber zinc ion battery cell with a winding structure, a commercial FEP pipe is used for packaging and injecting a liquid electrolyte of zinc bis(trifluoromethanesulfonyl) imide (Zn(TFSI)2) with a concentration of 0.5-2 moles per liter, a tab is drawn out and the fiber ends are sealed with hot melt adhesive to obtain a fiber aqueous zinc ion full battery.

[0017] The fiber aqueous zinc ion battery based on the gel zinc powder negative electrode prepared by the above preparation method has the advantages of simple structure, convenient assembly, high stability and continuous preparation.

[0018] Compared with the prior art, the present application has the following advantages:

[0019] (1) The fiber gel zinc powder negative electrode prepared by the present application has the characteristics of high stability and long cycle life compared with the traditional zinc powder negative electrode, and can be stably cycled for more than 450 hours under a surface current density of 1 mA / cm 2 and a surface capacity of 1 mAh / cm 2 .

[0020] (2) This invention prepares fiber gel zinc powder anodes by developing confined coating method and in-situ polymerization strategy, and provides a universal strategy for continuous construction of high-stability fiber zinc powder anodes. It effectively overcomes the challenges faced by traditional fiber zinc metal wire and zinc powder anodes and has broad application prospects. Attached Figure Description

[0021] Figure 1 This is a schematic diagram of the process for preparing fiber gel zinc powder anodes using confined coating and in-situ polymerization strategies.

[0022] Figure 2 Optical and scanning electron microscope images of the continuously prepared fiber gel zinc powder anode.

[0023] Figure 3 The cyclic voltammetry curves and constant current charge-discharge curves at a current density of 0.2 A / g are shown for zinc / copper half-cells based on zinc gel powder anode.

[0024] Figure 4 A schematic diagram of the in-situ polymerization preparation of fiber gel zinc powder negative electrode and the change of contact angle of the electrode at different times when the precursor solution wets the electrode.

[0025] Figure 5 The voltage-time curves and constant current charge-discharge curves at a current density of 1 A / g are shown for zinc / / zinc symmetric batteries based on gel zinc powder anodes during long-term cycle testing.

[0026] Figure 6 This image shows a schematic diagram, a photograph of the battery cell, and a scanning electron microscope image of an aqueous zinc-ion battery based on gel zinc powder anode fiber.

[0027] Figure 7 The coulombic efficiency cycling curves of the zinc / copper half-cell based on the gel zinc powder negative electrode and the corresponding constant current charge-discharge curves of the aqueous zinc-ion full cell at a current density of 0.5 A / g are shown. Detailed Implementation

[0028] The present invention will now be described in detail with reference to the accompanying drawings and embodiments. It should be noted that those skilled in the art can make various changes and modifications without departing from the concept of the present invention. These all fall within the scope of protection of the present invention.

[0029] The reagents used in the following examples were all purchased reagents, such as zinc powder (≥99.9%), N-methylpyrrolidone (NMP, electronic grade, 99.99%), and polyethylene glycol dimethacrylate (PEGDMA, M w (≈1000) Purchased from Aladdin.

[0030] Multi-walled carbon nanotubes (MWCNT, ≥95%, particle size 8-15 nm, length ≈ 50 nm, specific surface area > 140 m 2 Tin powder (particle size 500 nm, purity 99.99%), bis(trifluoromethanesulfonyl) imide zinc (Zn(TFSI)2, purity 98%), 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP, purity 98%) were purchased from Adama.

[0031] Tris(2,2,2-trifluoroethyl) phosphate (TFEP) was purchased from Dodd Chemical Reagents.

[0032] Manganese dioxide nanorods (α phase) were purchased from Future Material Technology Co., Ltd.

[0033] Polyvinylidene fluoride (PVDF, HSV900) was purchased from Dongguan Zanyang Polymer Material Co., Ltd.

[0034] Example 1, a preparation method of a fiber aqueous zinc ion battery based on a gel zinc powder negative electrode, the specific steps are as follows:

[0035] (1) Preparation of organic gel precursor solution: first, 3.13 grams of bis(trifluoromethanesulfonyl) imide zinc (Zn(TFSI)2) electrolyte salt was added to 5 milliliters (7.82 grams) of tris(2,2,2-trifluoroethyl) phosphate (TFEP) organic solvent, and placed in an ultrasonic cleaner for ultrasonic treatment for 60 minutes until the zinc salt was completely dissolved to obtain a 1 molar per liter organic electrolyte solution; then 5 grams of polyethylene glycol dimethacrylate (PEGDMA) monomer was added to the above solution and magnetically stirred for 30 minutes until the solution was uniform and transparent; then 5wt% of 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP) was added as a photoinitiator for ultraviolet polymerization, and finally the obtained organic gel precursor solution was wrapped with aluminum foil to block light and placed on a magnetic stirring table for uniform stirring for 40 minutes.

[0036] (2) Preparation of electrode slurry: In order to prepare zinc powder electrode slurry with solid content of 41wt%, first, 8wt% (0.286g) of polyvinylidene fluoride (PVDF) powder in the solid was weighed into 5ml (5.14g) of N-methyl pyrrolidone (NMP) solvent, and stirred for 6 hours to completely dissolve; then 75wt% (2.68g) of zinc powder, 10wt% (0.36g) of multi-walled carbon nanotube powder and 7wt% (0.25g) of tin powder in the solid were weighed into a mortar and mixed and ground for 30 minutes, and then added to the above binder solution, continuously stirred for 24 hours, and then the zinc powder electrode slurry was prepared after uniform mixing; for the solid content of 18wt% of the manganese dioxide electrode slurry, first, 10wt% (0.113g) of polyvinylidene fluoride (PVDF) powder in the solid was weighed into 5ml (5.14g) of N-methyl pyrrolidone (NMP) solvent, and stirred for 6 hours to completely dissolve; then 70wt% (0.791g) of manganese dioxide powder and 20wt% (0.226g) of conductive carbon black in the solid were weighed into a mortar and mixed and ground for 30 minutes, and then added to the above binder solution, continuously stirred for 24 hours, and then the manganese dioxide electrode slurry was prepared after uniform mixing.

[0037] (3) Preparation of fiber gel zinc powder negative electrode: The prepared zinc powder slurry was loaded into a slurry cylinder, and the customized composite copper wire fiber current collector was made to pass through the slurry cylinder filled with zinc powder slurry at a speed of 4 revolutions per minute, and then dried through a temperature gradient hot air drying tube (the drying temperatures of the front, middle and rear three sections are 180 degrees Celsius, 140 degrees Celsius and 100 degrees Celsius respectively), and then wound and rolled to obtain a fiber zinc powder negative electrode, and then the obtained fiber zinc powder electrode was infiltrated with an organic gel precursor liquid in a vacuum glove box, and then irradiated for 1 minute through a ultraviolet light irradiation device, and then the fiber gel zinc powder negative electrode was prepared after in-situ photoinitiated radical polymerization and rolling.

[0038] (4) Preparation of fiber manganese dioxide positive electrode: The prepared manganese dioxide electrode slurry was loaded into a slurry cylinder, and the customized composite nickel wire fiber current collector was made to pass through the slurry cylinder filled with manganese dioxide slurry at a speed of 4 revolutions per minute, and then dried through a temperature gradient hot air drying tube (the drying temperatures of the front, middle and rear three sections are 140 degrees Celsius, 100 degrees Celsius and 60 degrees Celsius respectively), and then wound and rolled to obtain a fiber manganese dioxide positive electrode.

[0039] (5) The assembly of fiber aqueous zinc ion battery: Firstly, the fiber manganese dioxide positive electrode was wound on the cellulose separator with a width of 3 mm by a separator winding device, and then the fiber gel zinc powder negative electrode was twisted with the fiber gel zinc powder negative electrode by a twisting device to obtain a fiber zinc ion battery cell with a winding structure. The fiber aqueous zinc ion battery was obtained by using a commercial FEP pipe to package and inject a zinc bis(trifluoromethanesulfonyl) imide (Zn(TFSI)2) liquid electrolyte with a concentration of 1 mol / L, leading out the tab, and sealing the fiber ends with hot melt glue.

[0040] In this embodiment, the preparation process of the fiber gel zinc powder negative electrode prepared by coating zinc powder slurry and in-situ polymerization is shown in Figure 1 The optical and scanning electron microscope photos of the fiber gel zinc powder negative electrode prepared by continuous preparation are shown in Figure 2 As shown in Figure 3 The cyclic voltammetry curves of the zinc / copper half-cell based on the gel zinc powder negative electrode at a scan rate of 1 mV / s are highly overlapped in the first 7 cycles, showing excellent cycle stability. The fiber gel zinc powder / manganese dioxide full battery has a high discharge specific capacity of 254.8 mAh / g at a current density of 0.2 A / g.

[0041] Example 2, a preparation method of a fiber aqueous zinc ion battery based on a gel zinc powder negative electrode, the specific steps are:

[0042] (1) Preparation of organic gel precursor solution: first, 2.5 grams of zinc bis(trifluoromethanesulfonyl) imide (Zn(TFSI)2) electrolyte salt is added to 8 milliliters (12.5 grams) of phosphoric acid tris(2,2,2-trifluoroethyl) ester (TFEP) organic solvent, and placed in an ultrasonic cleaner for ultrasonic treatment for 50 minutes until the zinc salt is completely dissolved to obtain a 0.5 mol / L organic electrolyte solution; then 4 grams of polyethylene glycol dimethyl acrylate (PEGDMA) monomer is added to the above solution and magnetically stirred for 20 minutes until the solution is uniform and transparent; then 4wt% 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP) is added as a photoinitiator for ultraviolet polymerization, and finally the obtained organic gel precursor solution is wrapped with aluminum foil to block light and placed on a magnetic stirring table for uniform stirring for 50 minutes.

[0043] (2) Preparation of electrode slurry: In order to prepare zinc powder electrode slurry with solid content of 42wt%, first, 7wt% (0.52g) of polyvinylidene fluoride (PVDF) powder in solid content was weighed into 10ml (10.28g) of N-methyl pyrrolidone (NMP) solvent, stirred for 5 hours to make it completely dissolved, then 73wt% (5.43g) of zinc powder, 12wt% (0.89g) of multi-walled carbon nanotube powder and 8wt% (0.6g) of tin powder in solid content were weighed into a mortar respectively, mixed and ground for 20 minutes, then added to the above binder solution, continuously stirred for 18 hours, and the zinc powder electrode slurry was prepared after uniform mixing; for the solid content of 17wt% of the manganese dioxide electrode slurry, first, 8wt% (0.17g) of polyvinylidene fluoride (PVDF) powder in solid content was weighed into 10ml (10.28g) of N-methyl pyrrolidone (NMP) solvent, stirred for 5 hours to make it completely dissolved, then 75wt% (1.58g) of manganese dioxide powder and 7wt% (0.15g) of conductive carbon black in solid content were weighed into a mortar respectively, mixed and ground for 20 minutes, then added to the above binder solution, continuously stirred for 18 hours, and the manganese dioxide electrode slurry was prepared after uniform mixing.

[0044] (3) Preparation of fiber gel zinc powder negative electrode: The prepared zinc powder slurry was loaded into the slurry cylinder, the customized composite copper wire fiber current collector was made to pass through the zinc powder slurry cylinder at a speed of 3 revolutions per minute, then dried through a temperature gradient hot air drying tube (the drying temperatures of the front, middle and rear sections are 170 degrees Celsius, 130 degrees Celsius and 90 degrees Celsius respectively), and then wound and rolled to obtain the fiber zinc powder negative electrode, then the obtained fiber zinc powder electrode was infiltrated with an organic gel precursor solution in a vacuum glove box and irradiated by a ultraviolet light irradiation device for 2 minutes, and the fiber gel zinc powder negative electrode was prepared after in-situ photoinitiated radical polymerization and rolling.

[0045] (4) Preparation of fiber manganese dioxide positive electrode: The prepared manganese dioxide electrode slurry was loaded into the slurry cylinder, the customized composite nickel wire fiber current collector was made to pass through the manganese dioxide slurry cylinder at a speed of 3 revolutions per minute, then dried through a temperature gradient hot air drying tube (the drying temperatures of the front, middle and rear sections are 130 degrees Celsius, 90 degrees Celsius and 50 degrees Celsius respectively), and then wound and rolled to obtain the fiber manganese dioxide positive electrode.

[0046] (5) The assembly of fiber aqueous zinc-ion battery: Firstly, the fiber manganese dioxide positive electrode was wound on the cellulose separator with a width of 2 mm by a separator winding device, and then the fiber gel zinc powder negative electrode was twisted with the fiber gel zinc powder negative electrode by a twisting device to obtain a fiber zinc-ion battery cell with a winding structure. The fiber zinc-ion battery cell was packaged with a commercial FEP pipe and injected with a liquid electrolyte of bis(trifluoromethanesulfonyl) imide zinc (Zn(TFSI)2) with a concentration of 0.5 mol / L. The tab was drawn out and sealed at both ends of the fiber with hot melt glue to obtain the fiber aqueous zinc-ion battery.

[0047] In this embodiment, during the preparation of the fiber gel zinc powder negative electrode, the organic gel precursor solution can quickly infiltrate the zinc powder electrode and undergo in-situ radical polymerization and gelation under ultraviolet light irradiation. The mechanism diagram of in-situ polymerization and the contact angle change diagram of the precursor solution infiltrating the electrode at different times are shown in Figure 4 . The prepared gel zinc powder negative electrode has excellent electrochemical stability, as shown in Figure 5 . The zinc / / zinc symmetric battery based on the gel zinc powder negative electrode remains stable in overpotential even after 450 hours of deposition / stripping during long-term cycle testing at a surface current density of 1 mA / cm 2 and a surface capacity of 1 mAh / cm 2 . The discharge specific capacity of the fiber gel zinc powder / / manganese dioxide full battery assembled is 165.5 mAh / g at a current density of 1 A / g.

[0048] Example 3, a preparation method of a fiber aqueous zinc-ion battery based on a gel zinc powder negative electrode, the specific steps are:

[0049] (1) Preparation of organic gel precursor solution: first, 9.38 grams of bis(trifluoromethanesulfonyl) imide zinc (Zn(TFSI)2) electrolyte salt is added to 10 milliliters (15.64 grams) of phosphoric acid tris(2,2,2-trifluoroethyl) ester (TFEP) organic solvent, and placed in an ultrasonic cleaner for ultrasonic treatment for 120 minutes until the zinc salt is completely dissolved to obtain an organic electrolyte solution with a concentration of 1.5 mol / L. Then, 3 grams of polyethylene glycol dimethyl acrylate (PEGDMA) monomer is added to the above solution and magnetically stirred for 25 minutes until the solution is uniform and transparent. Then, 7wt% of 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP) is added as a photoinitiator for ultraviolet polymerization, and finally the obtained organic gel precursor solution is wrapped with aluminum foil to block light and placed on a magnetic stirring table for uniform stirring for 30 minutes.

[0050] (2) Preparation of electrode slurry: In order to prepare zinc powder electrode slurry with solid content of 40wt%, first, 6wt% (0.33g) of polyvinylidene fluoride (PVDF) powder in solid content was weighed into 8ml (8.22g) of N-methyl pyrrolidone (NMP) solvent, and stirred for 7 hours to completely dissolve, then 80wt% (4.38g) of zinc powder, 8wt% (0.44g) of multi-walled carbon nanotube powder and 6wt% (0.33g) of tin powder in solid content were weighed into a mortar respectively, mixed and ground for 25 minutes, then added to the above binder solution, continuously stirred for 12 hours, and the zinc powder electrode slurry was prepared after uniform mixing; for the solid content of 19wt% of the manganese dioxide electrode slurry, first, 8wt% (0.15g) of polyvinylidene fluoride (PVDF) powder in solid content was weighed into 8ml (8.22g) of N-methyl pyrrolidone (NMP) solvent, and stirred for 7 hours to completely dissolve, then 67wt% (1.29g) of manganese dioxide powder and 25wt% (0.48g) of conductive carbon black in solid content were weighed into a mortar respectively, mixed and ground for 25 minutes, then added to the above binder solution, continuously stirred for 12 hours, and the manganese dioxide electrode slurry was prepared after uniform mixing.

[0051] (3) Preparation of fiber gel zinc powder negative electrode: The prepared zinc powder slurry was loaded into a slurry cylinder, and the customized composite copper wire fiber current collector was made to pass through the slurry cylinder filled with zinc powder slurry at a speed of 5 revolutions per minute, then dried through a temperature gradient hot air drying tube (the drying temperatures of the front, middle and rear three sections are 190 degrees Celsius, 150 degrees Celsius and 110 degrees Celsius respectively), and then wound and rolled to obtain a fiber zinc powder negative electrode, then the obtained fiber zinc powder electrode was infiltrated with an organic gel precursor solution in a vacuum glove box, and irradiated for 3 minutes through a ultraviolet light irradiation device, and the fiber gel zinc powder negative electrode was prepared after in-situ photoinitiated radical polymerization and rolling.

[0052] (4) Preparation of fiber manganese dioxide positive electrode: The prepared manganese dioxide electrode slurry was loaded into a slurry cylinder, and the customized composite nickel wire fiber current collector was made to pass through the slurry cylinder filled with manganese dioxide slurry at a speed of 5 revolutions per minute, then dried through a temperature gradient hot air drying tube (the drying temperatures of the front, middle and rear three sections are 150 degrees Celsius, 110 degrees Celsius and 70 degrees Celsius respectively), and then wound and rolled to obtain a fiber manganese dioxide positive electrode.

[0053] (5) Assembly of fiber aqueous zinc ion battery: firstly, the fiber manganese dioxide positive electrode is wound on the cellulose separator with a width of 4 mm by a separator winding device, then the fiber gel zinc powder negative electrode is twisted with the fiber manganese dioxide positive electrode by a twisting device to obtain a fiber zinc ion battery with a twisted structure, a commercial FEP pipe is used for packaging and injecting a liquid electrolyte of zinc bis(trifluoromethanesulfonyl) imide (Zn(TFSI)2) with a concentration of 1.5 mol / L, a tab is drawn and the fiber ends are sealed with hot melt adhesive to obtain a fiber aqueous zinc ion battery.

[0054] In this embodiment, the fiber aqueous zinc ion battery based on the gel zinc powder negative electrode has a twisted winding structure, and the corresponding structural diagram, physical diagram of the battery cell and scanning electron microscope diagram are as shown in Figure 6 The fiber aqueous zinc ion battery based on the gel zinc powder negative electrode can be stably cycled for 300 cycles under the test conditions of 1 mA / cm 2 and 1 mAh / cm 2 The discharge specific capacity of the assembled fiber gel zinc powder / / manganese dioxide battery at a current density of 0.5 A / g is 207.3 mAh / g, and the corresponding coulombic efficiency cycle curve and constant current charge-discharge curve are as shown in Figure 7 ​

Claims

1. A fiber-based aqueous zinc-ion battery based on a gel zinc powder negative electrode, characterized in that, Nickel and copper wires are used as the positive and negative current collectors of the fiber battery, respectively. A zinc powder slurry is coated onto the negative current collector, and an organic gel precursor solution is polymerized in situ to form the fiber gel zinc powder negative electrode. A manganese dioxide slurry is coated onto the positive current collector to form the fiber positive electrode. A cellulose membrane is wrapped around the surface of the fiber manganese dioxide positive electrode and twisted with the fiber gel zinc powder negative electrode to prepare a wound-structured fiber-based aqueous zinc-ion battery. The integrated organic gel zinc powder negative electrode and the aqueous electrolyte form a two-phase interface through phase separation. Wherein: Preparation of the organic gel precursor solution: The organic gel precursor solution is prepared by ultrasonic dissolution. First, zinc bis(trifluoromethanesulfonyl)imide (Zn(TFSI)2) electrolyte salt is added to 5-10 mL of tris(2,2,2-trifluoroethyl) phosphate (TFEP) organic solvent, and ultrasonically dissolved in an ultrasonic cleaner. Then, polyethylene glycol dimethacrylate (PEGDMA) monomer is added to the obtained organic electrolyte solution and stirred until the solution is uniform and transparent. Then, 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP) is added as a photoinitiator for ultraviolet light polymerization. Finally, the obtained organic gel precursor solution is wrapped in aluminum foil to block light and then stirred evenly on a magnetic stirring table. Preparation of the fiber gel zinc powder anode: The prepared zinc powder slurry is loaded into a slurry cylinder, and the motor is turned on to make the customized copper wire fiber current collector pass through the cylinder containing the zinc powder slurry at a uniform speed. After passing through a temperature gradient hot air drying tube, it is wound and rolled up to obtain the fiber zinc powder anode. In a glove box, the obtained fiber zinc powder anode is immersed in an organic gel precursor solution and then passed through an ultraviolet light irradiation device. After in-situ photo-initiated free radical polymerization, it is wound up to obtain the fiber gel zinc powder anode.

2. A method for preparing a fiber-based aqueous zinc-ion battery based on a gelled zinc powder anode, characterized in that, The specific steps are as follows: (1) Preparation of organic gel precursor solution: The organic gel precursor solution was prepared by ultrasonic dissolution. First, zinc bis(trifluoromethanesulfonyl)imide (Zn(TFSI)2) electrolyte salt was added to 5-10 mL of tris(2,2,2-trifluoroethyl) phosphate (TFEP) organic solvent and ultrasonically dissolved in an ultrasonic cleaner. Then, polyethylene glycol dimethacrylate (PEGDMA) monomer was added to the obtained organic electrolyte solution and stirred until the solution was uniform and transparent. Then, 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP) was added as a photoinitiator for ultraviolet light polymerization. Finally, the obtained organic gel precursor solution was wrapped in aluminum foil to block light and then stirred evenly on a magnetic stirring table. (2) Preparation of electrode paste: For zinc powder paste, firstly, polyvinylidene fluoride (PVDF) powder is added to N-methylpyrrolidone (NMP) solvent and magnetically stirred until completely dissolved to obtain a binder solution; then, zinc powder, multi-walled carbon nanotube powder and tin powder are mixed and ground in a mortar, and then added to the above binder solution, and continuously stirred until uniformly mixed to obtain zinc powder paste; For manganese dioxide electrode paste, firstly, a certain amount of polyvinylidene fluoride (PVDF) powder is weighed and added to N-methylpyrrolidone (NMP) solvent and stirred until completely dissolved to obtain a binder solution; then, a certain amount of manganese dioxide powder and conductive carbon black are weighed and ground in a mortar, and then added to the above binder solution, and continuously stirred until uniformly mixed to obtain manganese dioxide electrode paste; (3) Preparation of fiber gel zinc powder anode: The prepared zinc powder slurry is loaded into the slurry cylinder, and the motor is turned on to make the customized copper wire fiber current collector pass through the cylinder containing the zinc powder slurry at a uniform speed. After passing through the temperature gradient hot air drying tube, it is wound and rolled up to obtain the fiber zinc powder anode. The obtained fiber zinc powder anode is immersed in organic gel precursor liquid in the glove box and then passed through the ultraviolet light irradiation device. After in-situ photo-initiated free radical polymerization, it is wound up to obtain the fiber gel zinc powder anode. (4) Preparation of fiber manganese dioxide positive electrode: The prepared manganese dioxide electrode slurry is loaded into the slurry cylinder, the motor is turned on so that the customized nickel wire fiber current collector passes through the cylinder containing manganese dioxide slurry at a uniform speed, and then the slurry is wound and rolled up after passing through the temperature gradient hot air drying tube to obtain the fiber manganese dioxide positive electrode. (5) Assembly of fiber-based aqueous zinc-ion full cell: First, the obtained fiber manganese dioxide positive electrode is wound with a cellulose membrane through a membrane winding device. Then, it is twisted with the fiber gel zinc powder negative electrode through a twisting device to obtain the cell of the wound structure fiber-based aqueous zinc-ion battery. The cell is encapsulated with FEP tube and injected with bis(trifluoromethanesulfonyl)imide zinc (Zn(TFSI)2) liquid electrolyte. The tabs are led out and the two ends of the fiber are sealed with hot melt glue to obtain the fiber-based aqueous zinc-ion full cell.

3. The preparation method according to claim 2, characterized in that, The specific preparation process of the organic gel precursor solution in step (1) is as follows: First, add 1.56-12.5 g of zinc bis(trifluoromethanesulfonyl)imide (Zn(TFSI)2) electrolyte salt to 5-10 mL of tri(2,2,2-trifluoroethyl) phosphate (TFEP) organic solvent, and place it in an ultrasonic cleaner for 50-120 minutes until the zinc salt is completely dissolved to obtain an organic electrolyte solution of 0.5-2 mol / L; then add 1-5 g of polyethylene glycol dimethacrylate (PEGDMA) monomer to the above solution and stir magnetically for 10-30 minutes until the solution is uniform and transparent; then add 3 wt%-8 wt% of 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP) as a photoinitiator for ultraviolet light polymerization; finally, wrap the obtained organic gel precursor solution with aluminum foil to block light and place it on a magnetic stirring table for uniform stirring for 30-60 minutes.

4. The preparation method according to claim 2, characterized in that, The specific preparation process of the electrode paste in step (2) is as follows: Prepare a zinc powder paste with a solid content of 40 wt%-43 wt%. First, weigh 6 wt%-10 wt% of polyvinylidene fluoride (PVDF) powder and add it to 5-10 ml of N-methylpyrrolidone (NMP) solvent. Stir for 5-10 hours until completely dissolved. Then, weigh 70 wt%-80 wt% of zinc powder, 8 wt%-12 wt% of multi-walled carbon nanotube powder, and 5 wt%-10 wt% of tin powder into a mortar and grind for 20-40 minutes. Then add it to the above binder solution and stir continuously for 12-24 hours until uniformly mixed to obtain the zinc powder paste. For the manganese dioxide electrode paste with a solid content of 16 wt%-20 wt%, first weigh 8 wt%-12 wt% of the solid... wt% of polyvinylidene fluoride (PVDF) powder is added to 5-10 ml of N-methylpyrrolidone (NMP) solvent and stirred for 5-10 hours until completely dissolved. Then, 65 wt%-75 wt% of manganese dioxide powder and 15 wt%-25 wt% of conductive carbon black are weighed into a mortar and mixed and ground for 20-40 minutes. The mixture is then added to the binder solution and stirred continuously for 12-24 hours until uniformly mixed to obtain manganese dioxide electrode slurry.

5. The preparation method according to claim 2, characterized in that, The specific preparation process of the fiber gel zinc powder anode in step (3) is as follows: the prepared zinc powder slurry is loaded into the slurry cylinder, the motor is turned on so that the customized copper wire fiber current collector passes through the cylinder containing the zinc powder slurry at a speed of 2-6 revolutions per minute. Then it passes through the temperature gradient hot air drying tube. The drying temperatures of the front, middle and back sections are 170-190 degrees Celsius, 130-150 degrees Celsius and 90-110 degrees Celsius, respectively. Then it is wound and rolled up to obtain the fiber zinc powder anode. After that, the obtained fiber zinc powder anode is immersed in organic gel precursor liquid in a vacuum glove box and then irradiated with ultraviolet light for 1-3 minutes. After in-situ photo-initiated free radical polymerization, it is wound up to obtain the fiber gel zinc powder anode.

6. The preparation method according to claim 2, characterized in that, The specific preparation process of the fiber manganese dioxide positive electrode in step (4) is as follows: the prepared manganese dioxide electrode slurry is loaded into the slurry cylinder, the motor is turned on so that the customized nickel wire fiber current collector passes through the cylinder containing the manganese dioxide slurry at a speed of 2-6 revolutions per minute, and then passes through the temperature gradient hot air drying tube. The drying temperatures of the front, middle and back sections are 130-150 degrees Celsius, 90-110 degrees Celsius and 50-70 degrees Celsius, respectively. Then, the fibers are wound and rolled up to obtain the manganese dioxide positive electrode.

7. The preparation method according to claim 2, characterized in that, The specific assembly process of the fiber-water-based zinc-ion full battery in step (5) is as follows: First, the fiber manganese dioxide positive electrode is wound with a cellulose membrane with a width of 2-4 mm through a membrane winding device. Then, it is twisted with the fiber gel zinc powder negative electrode through a twisting device to obtain a fiber zinc-ion battery cell with a winding structure. The cell is then packaged with an FEP tube and injected with a bis(trifluoromethanesulfonyl)imide zinc (Zn(TFSI)2) liquid electrolyte with a concentration of 0.5-2 mol / L. The tabs are then led out and the two ends of the fiber are sealed with hot melt adhesive to obtain the fiber-water-based zinc-ion full battery.

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