A wide-temperature-range micro zinc-iodine battery and a preparation method thereof

Abstract

The application discloses a wide-temperature-range micro zinc-iodine battery and a preparation method thereof, and comprises the following steps: after a micro electrode is prepared through 3D printing, an iodine anode is formed by loading iodine on the surface of the micro electrode; a zinc cathode matching the shape of the iodine anode is prepared through laser engraving; water, hyaluronic acid, hydrophilic silicon dioxide, zinc perchlorate and zinc bromide are uniformly mixed to form a gel electrolyte; the iodine anode, the gel electrolyte and the zinc cathode are sequentially laminated on a substrate, and then the wide-temperature-range micro zinc-iodine battery is obtained after packaging. In the gel electrolyte, the hyaluronic acid and the hydrophilic silicon dioxide lock water through hydrogen bonds with water molecules, inhibit the evaporation of water at high temperature, and the perchlorate ion inhibits the freezing of water at low temperature by destroying the hydrogen bond structure between water molecules in the gel network, so that the wide-temperature-range micro battery is realized; meanwhile, the bromide ion in the electrolyte is transmitted to the anode through the interface to excite the four-electron reaction of iodine, so that the energy density of the micro zinc-iodine battery is improved.

Description

Technical Field

[0001] This invention relates to the field of zinc-iodine battery technology, specifically to a wide-temperature-range micro zinc-iodine battery and its preparation method. Background Technology

[0002] The rapid development of autonomous microelectronic devices and microsystems has placed higher demands on the efficiency and stability of on-chip micro energy units. Among various micro energy storage technologies, micro batteries have an effective electrode area at the miniaturization scale (generally less than 1 cm²). 2 High-energy-density (on the order of magnitude) and easily integrated into microelectronic devices, these batteries have become ideal power sources for autonomous microelectronic devices due to their high energy density and ease of integration. Among them, micro zinc batteries show broad application prospects due to their excellent safety and low cost. However, current micro zinc batteries have insufficient energy density and cannot operate normally in a wide temperature range exceeding 0-25℃, thus failing to meet the energy requirements of autonomous microsystems.

[0003] To address these challenges, researchers have primarily focused on improving the energy density of micro zinc batteries and their performance under extreme temperature conditions. Regarding increasing energy density, existing research has achieved an areal energy density of 2 mWh / cm² by developing high-capacity iodine cathodes. -2 The above basically meets the energy requirements of autonomous microsystems, but the operating temperature range of this micro zinc battery is limited. Patent CN121319408A extends the operating temperature of the gel electrolyte to -20 ℃ to 25 ℃ by introducing ethylene glycol into the gel electrolyte, but this system has not yet been applied to micro batteries.

[0004] In summary, existing technologies struggle to balance the high energy density and wide operating temperature range of micro zinc batteries. Designing a micro zinc battery that combines high energy density with excellent wide temperature adaptability remains a critical technical challenge that urgently needs to be overcome. Summary of the Invention

[0005] This invention addresses the shortcomings of existing technologies by providing a wide-temperature-range micro zinc-iodine battery and its preparation method. It optimizes the gel electrolyte, where hyaluronic acid and hydrophilic silica form hydrogen bonds with water molecules to lock in water and inhibit water evaporation at high temperatures. Perchlorate ions disrupt the hydrogen bond structure between water molecules in the gel network, inhibiting water solidification at low temperatures, thus achieving a wide temperature range for the micro battery. Simultaneously, bromide ions in the electrolyte are transported to the positive electrode through the interface to excite the four-electron reaction of iodine, improving the energy density of the micro zinc-iodine battery. This solves the problem in existing technologies where micro batteries cannot simultaneously achieve high energy density and a wide operating temperature range.

[0006] To address the aforementioned technical problems, the first aspect of this invention provides a method for preparing a wide-temperature-range micro zinc-iodine battery, comprising the following steps:

[0007] S1. After 3D printing to prepare microelectrodes, iodine is loaded onto the surface of the microelectrodes to form an iodine positive electrode;

[0008] S2. Laser engraving is used to prepare a zinc anode that matches the shape of the iodine cathode;

[0009] S3. Mix water, hyaluronic acid, hydrophilic silica, zinc perchlorate and zinc bromide evenly to form a gel electrolyte;

[0010] S4. The iodine positive electrode, gel electrolyte and zinc negative electrode are sequentially stacked on the substrate and then encapsulated to obtain the wide-temperature-range micro zinc-iodine battery.

[0011] This invention incorporates hydrophilic silica and zinc perchlorate in its gel electrolyte. Hyaluronic acid and hydrophilic silica form hydrogen bonds with water molecules to lock in water and inhibit water evaporation at high temperatures. Perchlorate ions disrupt the hydrogen bond structure between water molecules in the gel network, inhibiting water solidification at low temperatures. This enables a wide temperature range for the micro battery, allowing it to operate from -40 ℃ to 60 ℃. Bromine ions in the electrolyte are transported to the positive electrode through the interface to excite the four-electron reaction of iodine, improving the energy density of the micro zinc-iodine battery. In summary, this invention achieves high energy density and a wide temperature range for the micro battery.

[0012] Furthermore, in S1, the loading of iodine onto the surface of the microelectrode specifically involves dissolving 1-hexyl-3-methylimidazole bromide and elemental iodine in an organic solvent to form a mixture. The microelectrode is then immersed in this mixture and subsequently dried. The uniform mixing of 1-hexyl-3-methylimidazole bromide and elemental iodine forms an ionic liquid. This ionic liquid, with its excellent wettability, fully penetrates the microporous, mesoporous, and nanoporous structures, allowing iodine to be uniformly distributed within the microelectrode in either a dissolved or complexed state, thus achieving a more uniform loading and avoiding the problem of iodine crystal agglomeration. In addition, the 1-hexyl-3-methylimidazole bromide cation further enhances the material's high-temperature stability and interfacial structural stability over a wide temperature range through its interaction with the halide anion.

[0013] Furthermore, the molar ratio of 1-hexyl-3-methylimidazole bromide to elemental iodine is (0.5-1):1.

[0014] Furthermore, in S1, the 3D-printed microelectrode has a mesh-like structure, and the printing ink used includes conductive materials and binders. The mesh-like positive electrode structure significantly increases the contact area between the gel electrolyte and the active material, effectively improving the ion transport efficiency at the electrolyte-electrode interface, thereby further increasing the energy density of the battery.

[0015] Furthermore, the conductive material is selected from one or more of carbon nanotubes, graphene, activated carbon, carbon fiber, conductive carbon black, and MXene.

[0016] The adhesive is selected from one or more of polyvinylidene fluoride, polyacrylonitrile, and polyvinylpyrrolidone.

[0017] Furthermore, in S2, the zinc negative electrode is selected from zinc foil, zinc sheet, or zinc foam.

[0018] Furthermore, in S3, the concentration of hyaluronic acid in the gel electrolyte is 0.05-0.15 g / mL, the concentration of hydrophilic silica is 0.15-0.25 g / mL, the concentration of zinc perchlorate is 3.5-4.5 mmol / mL, and the concentration of zinc bromide is 0.1-0.5 mmol / mL.

[0019] Furthermore, in S3, the hyaluronic acid is selected from one or more of sodium hyaluronate, potassium hyaluronate, and zinc hyaluronate.

[0020] Furthermore, in S4, the material of the substrate is selected from one or more of polyethyleneimine, polyimide, and polyethylene terephthalate.

[0021] The second aspect of the present invention provides a wide-temperature-range micro zinc-iodine battery prepared by the preparation method described in the first aspect.

[0022] The beneficial effects of this invention are:

[0023] In this invention, hyaluronic acid and hydrophilic silica in the gel electrolyte lock in water by forming hydrogen bonds with water molecules, thus inhibiting water evaporation at high temperatures; perchlorate ions inhibit water solidification at low temperatures by disrupting the hydrogen bond structure between water molecules in the gel network, thereby achieving a wide temperature range for the micro battery.

[0024] In this invention, bromide ions in the gel electrolyte are transported to the positive electrode through the interface to excite the four-electron reaction of iodine, thereby improving the energy density of the micro zinc-iodine battery. At the same time, the grid-like positive electrode structure significantly increases the contact area between the gel electrolyte and the active material, effectively improving the ion transport efficiency at the electrolyte-electrode interface, and further improving the energy density of the battery.

[0025] This invention utilizes a homogeneous mixture of 1-hexyl-3-methylimidazolium bromide and elemental iodine to form an ionic liquid. This liquid, with its excellent wettability, fully penetrates microporous, mesoporous, and nanoporous structures, allowing iodine to be uniformly distributed within the microelectrode in either a dissolved or complexed state. This results in a more uniform loading and avoids the problem of iodine crystal agglomeration. Furthermore, the 1-hexyl-3-methylimidazolium bromide cation enhances the material's high-temperature stability and interfacial structural stability over a wide temperature range through interactions with halogens or between halogen anions.

[0026] The preparation process of this invention can be completed in an air environment, and the process is simple, low-cost, and has good potential for large-scale preparation. Attached Figure Description

[0027] To more clearly illustrate the technical solution of the present invention, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0028] Figure 1 This is the differential scanning calorimetry curve of the gel electrolyte obtained in Example 1 of the present invention;

[0029] Figure 2 These are the charge-discharge curves of the miniature zinc-iodine battery obtained in Example 1 of the present invention at different temperatures;

[0030] Figure 3 These are the cycling curves of the micro zinc-iodine battery obtained in Example 1 of the present invention at different temperatures;

[0031] Figure 4 These are the charge-discharge curves of the miniature zinc-iodine battery obtained in Comparative Example 1 at different temperatures. Detailed Implementation

[0032] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and 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 scope of protection of the present invention.

[0033] This embodiment relates to a method for preparing a wide-temperature-range micro zinc-iodine battery, comprising the following steps:

[0034] S1. After 3D printing to prepare microelectrodes, iodine is loaded onto the surface of the microelectrodes to form an iodine positive electrode;

[0035] S2. Laser engraving is used to prepare a zinc anode that matches the shape of the iodine cathode;

[0036] S3. Mix water, hyaluronic acid, hydrophilic silica, zinc perchlorate and zinc bromide evenly to form a gel electrolyte;

[0037] S4. The iodine positive electrode, gel electrolyte and zinc negative electrode are sequentially stacked on the substrate and then encapsulated to obtain the wide-temperature-range micro zinc-iodine battery.

[0038] In this embodiment, hydrophilic silica and zinc perchlorate are incorporated into the gel electrolyte. Hyaluronic acid and hydrophilic silica form hydrogen bonds with water molecules to lock in water and inhibit water evaporation at high temperatures. Perchlorate ions inhibit water solidification at low temperatures by disrupting the hydrogen bond structure between water molecules in the gel network. This enables the micro battery to operate in a wide temperature range from -40 ℃ to 60 ℃. Bromine ions in the electrolyte are transported to the positive electrode through the interface to excite the four-electron reaction of iodine, thereby improving the energy density of the micro zinc-iodine battery. In summary, high energy density and a wide temperature range are achieved for the micro battery.

[0039] In a preferred embodiment, in S1, loading iodine onto the surface of the microelectrode specifically involves dissolving 1-hexyl-3-methylimidazole bromide and elemental iodine in an organic solvent to form a mixture. The microelectrode is then immersed in this mixture and subsequently dried. Preferably, the molar ratio of 1-hexyl-3-methylimidazole bromide to elemental iodine is (0.5-1):1. The uniform mixing of 1-hexyl-3-methylimidazole bromide and elemental iodine forms an ionic liquid. This ionic liquid, with its excellent wettability, fully penetrates the microporous, mesoporous, and nanoporous structures, allowing iodine to be uniformly distributed within the microelectrode in a dissolved or complexed state, thus achieving a more uniform loading and avoiding the problem of iodine crystal agglomeration. Furthermore, the 1-hexyl-3-methylimidazole bromide cation, through its interaction with halide anions, further enhances the material's high-temperature stability and interfacial structural stability over a wide temperature range.

[0040] In a preferred embodiment, in S1, the microelectrode prepared by 3D printing has a mesh-like structure, and the printing ink used includes conductive materials and a binder. The mesh-like positive electrode structure significantly increases the contact area between the gel electrolyte and the active material, effectively improving the ion transport efficiency at the electrolyte-electrode interface, thereby further increasing the energy density of the battery. The conductive material is selected from one or more of carbon nanotubes, graphene, activated carbon, carbon fibers, conductive carbon black, and MXene; the binder is selected from one or more of polyvinylidene fluoride, polyacrylonitrile, and polyvinylpyrrolidone.

[0041] In a preferred embodiment, in S2, the zinc negative electrode is selected from zinc foil, zinc sheet, or zinc foam.

[0042] In a preferred embodiment, in step S3, the concentration of hyaluronic acid in the gel electrolyte is 0.05-0.15 g / mL, the concentration of hydrophilic silica is 0.15-0.25 g / mL, the concentration of zinc perchlorate is 3.5-4.5 mmol / mL, and the concentration of zinc bromide is 0.1-0.5 mmol / mL. The hyaluronic acid is selected from one or more of sodium hyaluronate, potassium hyaluronate, and zinc hyaluronate.

[0043] In a preferred embodiment, in S4, the material of the substrate is selected from one or more of polyethyleneimine, polyimide, and polyethylene terephthalate.

[0044] The second aspect of the present invention provides a wide-temperature-range micro zinc-iodine battery prepared by the preparation method described in the first aspect.

[0045] Example 1

[0046] This embodiment relates to a method for fabricating a wide-temperature-range micro zinc-iodine battery, comprising the following steps:

[0047] (1) Conductive ink was obtained by uniformly dispersing activated carbon, graphene, and polyvinylidene fluoride in N-methylpyrrolidone at a mass ratio of 1.4:0.1:0.1. The conductive ink was then fabricated into a 7 mm × 7 mm mesh microelectrode using 3D printing technology. The microelectrode was placed in a mixed solution of 1-hexyl-3-methylimidazolium bromide, elemental iodine, and N-methylpyrrolidone in a molar ratio of 2:2:3 and allowed to stand for 4 h. Subsequently, it was dried at 80 ℃ for 6 h to obtain an iodine positive electrode.

[0048] (2) Zinc sheet is selected as the zinc negative electrode material, and the zinc sheet is processed into a square structure that matches the area and shape of the iodine positive electrode by laser engraving process.

[0049] (3) Dissolve 4 mmol zinc perchlorate and 0.5 mmol zinc bromide in 1 mL deionized water, then add 0.1 g sodium hyaluronate and 0.2 g hydrophilic silica, mix well, and obtain gel electrolyte. Figure 1 The differential scanning calorimetry curve of the gel electrolyte obtained in Example 1 shows that it has excellent stability from -40℃ to 60℃.

[0050] (4) Iodine cathode, gel electrolyte and zinc anode were stacked sequentially on polyethylene terephthalate substrate and then encapsulated with polypropylene glue to obtain micro zinc-iodine battery and its performance was tested. Figure 2 These are the charge-discharge curves of the micro zinc-iodine battery obtained in Example 1 at different temperatures, at 2 mA cm⁻¹. -2 Under the given current, the micro zinc-iodine battery achieved discharge capacities of 2.8 mAh cm⁻¹ at temperatures of -40 °C, 25 °C, and 60 °C. -2 5.9 mAh cm -2 and 5.5 mAh cm -2 . Figure 3 The cycling curves of the micro zinc-iodine battery obtained in Example 1 at different temperatures show that after 120 cycles, the capacity retention rate of the micro battery is more than 80%.

[0051] Example 2

[0052] (1) Graphene, carbon fiber and polyvinylidene fluoride were uniformly dispersed in N-methylpyrrolidone at a mass ratio of 0.8:0.9:0.1 to obtain conductive ink. The conductive ink was prepared into a 7 mm × 7 mm grid microelectrode using 3D printing technology. The microelectrode was placed in a mixed solution of 1-hexyl-3-methylimidazolium bromide, iodine and N-methylpyrrolidone in a molar ratio of 2:2:3 and allowed to stand for 4 h. Then it was dried at 80 °C for 6 h to obtain an iodine positive electrode.

[0053] (2) Zinc foil is selected as the zinc negative electrode material, and the zinc foil is processed into a square structure that matches the area of ​​the iodine positive electrode by laser engraving process.

[0054] (3) Dissolve 3.5 mmol zinc perchlorate and 0.2 mmol zinc bromide in 1 mL deionized water, then add 0.05 g sodium hyaluronate and 0.2 g hydrophilic silica, mix well, and obtain gel electrolyte.

[0055] (4) An iodine positive electrode, a gel electrolyte, and a zinc negative electrode were sequentially stacked on a polyimide substrate, and then encapsulated with silicone to obtain a micro zinc-iodine battery. Performance tests were then conducted: at 2 mA cm⁻¹ -2 Under the given current, the prepared micro zinc-iodine battery achieved discharge capacities of 2.7 mAh cm⁻¹ at temperatures of -40 °C, 25 °C, and 60 °C. -2 5.5 mAh cm -2 and 5.1mAh cm -2 After 120 cycles, the capacity retention rate of the micro battery is over 80%.

[0056] Example 3

[0057] This embodiment relates to a method for fabricating a wide-temperature-range micro zinc-iodine battery, comprising the following steps:

[0058] (1) Activated carbon, conductive carbon black, and polyvinylidene fluoride were uniformly dispersed in N-methylpyrrolidone at a mass ratio of 1.4:0.1:0.1 to obtain conductive ink. The conductive ink was then fabricated into a 7 mm × 7 mm mesh microelectrode using 3D printing technology. The microelectrode was placed in a mixed solution of 1-hexyl-3-methylimidazolium bromide, elemental iodine, and N-methylpyrrolidone at a molar ratio of 2:2:3 and allowed to stand for 4 h. Subsequently, it was dried at 80 ℃ for 6 h to obtain an iodine positive electrode.

[0059] (2) Select zinc foam as zinc negative electrode material, and process the zinc sheet into a square structure that matches the area and shape of the iodine positive electrode by laser engraving process.

[0060] (3) Dissolve 4 mmol zinc perchlorate and 0.5 mmol zinc bromide in 1 mL deionized water, then add 0.1 g sodium hyaluronate and 0.2 g hydrophilic silica, mix well, and obtain gel electrolyte.

[0061] (4) An iodine cathode, a gel electrolyte, and a zinc anode were sequentially stacked on a polyethylene terephthalate substrate, and then encapsulated with polypropylene adhesive to obtain a micro zinc-iodine battery. Performance tests were then conducted: at 2 mA cm⁻¹ -2 Under the given current, the micro zinc-iodine battery achieved a discharge capacity of 2.4 mAh cm⁻¹ at temperatures of -40 °C, 25 °C, and 60 °C. -2 5.7 mAh cm -2 and 5.5 mAh cm -2 After 120 cycles, the micro battery retains more than 80% of its capacity.

[0062] Comparative Example 1

[0063] The difference between this comparative example and Example 2 is that zinc perchlorate is not added in step (3), while other steps and parameters remain unchanged, resulting in a micro zinc-iodine battery, and its performance is tested. Figure 4 The figures show the charge-discharge curves of the micro zinc-iodine battery obtained in Comparative Example 1 at different temperatures, at 2 mA cm⁻¹. -2 Under the given current, the micro zinc-iodine battery achieved a discharge capacity of 2.5 mAh cm⁻¹ at temperatures of 0 ℃, 25 ℃, and 60 ℃. -2 5.3mAh cm -2 and 5.7 mAh cm -2 At temperatures below zero, water molecules arrange themselves into a stable, ordered crystal structure, disrupting the solvation structure of ions and preventing ion transport, thus preventing the micro-battery from charging and discharging.

[0064] Comparative Example 2

[0065] The difference between this comparative example and Example 2 is that in step (1), the microelectrode and iodine are encapsulated in the same glass bottle, and then kept at 80 °C for 6 h to obtain an iodine positive electrode. Other steps and parameters remain unchanged to obtain a micro zinc-iodine battery, and performance testing is performed: at 2 mA cm⁻¹ -2 Under the specified current, the micro zinc-iodine battery achieved a discharge capacity of 1.2 mAh cm⁻¹ at temperatures of -40 °C, 25 °C, and 60 °C. -2 3.4 mAh cm -2 and 3.1 mAh cm -2After 120 cycles, the capacity retention rate of the micro battery was over 50%. It is evident that the discharge capacity and capacity retention rate after 120 cycles of the battery obtained in this comparative example are significantly lower than those of Example 1.

[0066] In summary, the hyaluronic acid and hydrophilic silica in the gel electrolyte of this invention lock in water by forming hydrogen bonds with water molecules, inhibiting water evaporation at high temperatures. Perchlorate ions, by disrupting the hydrogen bond structure between water molecules in the gel network, inhibit water solidification at low temperatures, thus achieving a wide temperature range for the micro battery. Bromine ions in the gel electrolyte are transported to the positive electrode through the interface to excite the four-electron reaction of iodine, improving the energy density of the micro zinc-iodine battery. Simultaneously, the mesh-like positive electrode structure significantly increases the contact area between the gel electrolyte and the active material, effectively improving the ion transport efficiency at the electrolyte-electrode interface, thereby further enhancing the battery's energy density. An ionic liquid is formed by uniformly mixing 1-hexyl-3-methylimidazolium bromide with elemental iodine. Its excellent wettability allows it to fully penetrate microporous, mesoporous, and nanoporous structures, enabling iodine to be uniformly distributed within the microelectrode in either a dissolved or complexed state. This results in a more uniform loading and avoids the problem of iodine crystal agglomeration. Furthermore, the 1-hexyl-3-methylimidazolium bromide cation enhances the material's high-temperature stability and interfacial structural stability over a wide temperature range through interactions with halogens or between halogen anions. The preparation process can be completed in air, is simple, and inexpensive, demonstrating good potential for large-scale production.

[0067] The present invention has been described in detail above with reference to specific embodiments and exemplary examples; however, these descriptions should not be construed as limiting the present invention. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and embodiments of the present invention without departing from the spirit and scope of the invention, and all such modifications and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the appended claims.

Claims

1. A method for preparing a wide-temperature-range micro zinc-iodine battery, characterized in that, Includes the following steps: S1. After fabricating microelectrodes using 3D printing, iodine is loaded onto the surface of the microelectrodes to form an iodine positive electrode. Specifically, loading iodine onto the surface of the microelectrodes involves dissolving 1-hexyl-3-methylimidazole bromide and elemental iodine in an organic solvent to form a mixture. The microelectrodes are then immersed in this mixture and subsequently removed and dried. The molar ratio of 1-hexyl-3-methylimidazole bromide to elemental iodine is (0.5-1):

1. S2. Laser engraving is used to prepare a zinc anode that matches the shape of the iodine cathode; S3. Mix water, hyaluronic acid, hydrophilic silica, zinc perchlorate, and zinc bromide evenly to form a gel electrolyte; the concentration of hyaluronic acid in the gel electrolyte is 0.05-0.15 g / mL, the concentration of hydrophilic silica is 0.15-0.25 g / mL, the concentration of zinc perchlorate is 3.5-4.5 mmol / mL, and the concentration of zinc bromide is 0.1-0.5 mmol / mL; S4. The iodine positive electrode, gel electrolyte and zinc negative electrode are sequentially stacked on the substrate and then encapsulated to obtain the wide-temperature-range micro zinc-iodine battery.

2. The method for preparing a wide-temperature-range micro zinc-iodine battery as described in claim 1, characterized in that, In S1, the microelectrode prepared by 3D printing has a mesh structure, and the printing ink used includes conductive materials and binders.

3. The method for preparing a wide-temperature-range micro zinc-iodine battery as described in claim 2, characterized in that, The conductive material is selected from one or more of carbon nanotubes, graphene, activated carbon, carbon fiber, conductive carbon black, and MXene. The adhesive is selected from one or more of polyvinylidene fluoride, polyacrylonitrile, and polyvinylpyrrolidone.

4. The method for preparing a wide-temperature-range micro zinc-iodine battery as described in claim 1, characterized in that, In S2, the zinc negative electrode is selected from zinc foil, zinc sheet, or zinc foam.

5. The method for preparing a wide-temperature-range micro zinc-iodine battery as described in claim 1, characterized in that, In S3, the hyaluronic acid is selected from one or more of sodium hyaluronate, potassium hyaluronate, and zinc hyaluronate.

6. The method for preparing a wide-temperature-range micro zinc-iodine battery as described in claim 1, characterized in that, In S4, the material of the substrate is selected from one or more of polyethyleneimine, polyimide, and polyethylene terephthalate.

7. A wide-temperature-range micro zinc-iodine battery prepared by the preparation method according to any one of claims 1-6.

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