Carbon-iodine-binder composite positive electrode sheet for aqueous zinc-iodine battery, and dry manufacturing method for same

Abstract

The present invention relates to: a carbon-iodine-binder composite positive electrode sheet for an aqueous zinc-iodine battery; and a method for manufacturing same and, more specifically, to a carbon-iodine-binder composite positive electrode sheet for an aqueous zinc-iodine battery and a dry manufacturing method for same, the positive electrode sheet for an aqueous zinc-iodine battery being characterized by comprising porous carbon particles in which iodine is adsorbed and complexed in pores, a conductive material, and a fibrous polymer binder forming a network between the carbon particles and the conductive material.

Description

Carbon-iodine-binder composite anode sheet for aqueous zinc-iodine batteries and dry manufacturing method thereof

[0001] The present invention relates to a carbon-iodine-binder composite anode sheet for an aqueous zinc-iodine battery and a dry manufacturing method thereof.

[0002] The need for Energy Storage Systems (ESS) is growing for the efficient storage of renewable energy sources such as solar, wind, ocean, and geothermal energy. Unlike LIBs, which prioritize miniaturization, ESSs have fewer constraints on volume and weight; therefore, low production costs and maintenance expenses are considered critical factors, while high energy density, fast charge / discharge speeds, and high stability are required. Aqueous zinc ion batteries (AZIBs) are attracting attention as next-generation energy storage devices that satisfy these requirements. In particular, AZIBs have been the subject of extensive research as a suitable candidate for grid systems. Indeed, the number of studies on supercapacitors and secondary batteries utilizing zinc ions has increased rapidly over the past few years. Compared to organic solvent electrolytes, which are flammable and pose a fire risk due to oxygen gas generated during the charge / discharge process, AZIBs offer the following advantages.

[0003] First, since water is used as the electrolyte solvent, safe operation is guaranteed as there is no risk of ignition even if a short circuit occurs after long-term battery cycles. Furthermore, aqueous electrolytes are non-toxic and exhibit faster ion conductivity characteristics compared to organic solvents. In addition, zinc metal exhibits multi-electron exchange and high density (7.13 g cm⁻³ at 25°C). -3 It has a high capacity per volume (5851 mAh cm⁻¹) reaching three times that of a lithium metal anode. -3It has the significant advantage of enabling a wide operating voltage and high energy density due to its low redox potential. In addition, zinc is an abundant material on Earth, and has the advantages of being environmentally friendly and inexpensive.

[0004] In particular, aqueous zinc-iodine (Zn-I2) batteries are a very promising energy storage system due to the abundant resources, the non-flammability of water, and high theoretical capacity of Zn 2+ It is a battery system that uses ions as a charge transfer medium. It operates with a positive electrode composed of C / I2 and a negative electrode composed of metallic Zn, and the electrolyte is mainly an aqueous solution such as ZnSO4, and Zn 2+ It consists of an aqueous solution in which a salt containing is dissolved in water.

[0005] However, aqueous zinc-iodine batteries face challenges such as increased polarization caused by the electronic insulation properties of I2 at the iodine anode, self-discharge phenomena resulting from the migration of formed polyiodide ions to the anode, and difficulty in achieving high energy density due to the limited active material content. Furthermore, in addition to corrosion caused by polyiodide ions, the Zn cathode exhibits issues such as dendrite formation, hydrogen evolution, water-related corrosion, and passivation; the situation becomes more complex when these problems are intermingled.

[0006] Researchers have made significant efforts to address these challenges. For example, porous carbon material hosts are being designed to limit iodine species and improve iodine utilization, new electrolytes are being developed to suppress the formation of polyiodine intermediates, functional membranes are being utilized to suppress polyiodine ion shuttlering, and coating layers are being built on the anode to protect the Zn metal.

[0007] In particular, since porous carbon materials possess unique characteristics including a rigid framework, high conductivity, and high porosity, making them ideal for storing significant amounts of iodine, a technique for encapsulating iodine in porous activated carbon via simple physical adsorption has been reported. According to this, the dissolution of polyiodine can be effectively suppressed and cycle stability ensured, and the porous conductive carbon matrix promotes the conversion reaction between I2 and ZnI2, resulting in a significant improvement in the electrochemical performance of SZIB. However, there is a limitation in that the pore size of the activated carbon is relatively large (5 μm), causing iodine to easily aggregate on the surface of such macroporous activated carbon, which consequently hinders the efficient conversion of polyiodine and leads to dissolution in the electrolyte.

[0008] In addition, when manufacturing the cathode of an aqueous secondary battery, a wet slurry process is conventionally used in which three components—C / I2, a conductive material, and a binder—are dispersed in a solvent to form a slurry, then coated onto a current collector and dried to complete the electrode. However, due to the high solubility of I2, there is a problem in that I2 dissolves rather than is dispersed in the solvent during cathode manufacturing, resulting in a failure to maintain its original structural characteristics. Furthermore, since it has the characteristic of sublimating at around 113°C, there is a risk that I2 may sublimate when heated to dry the solvent of the slurry, thereby losing its function as a cathode active material.

[0009]

[0010] Accordingly, in order to solve the technical limitations described above, the inventors manufactured a positive electrode using a dry process, and infused iodine while forming a rigid structure with a carbon material using a binder, thereby manufacturing a positive electrode composite sheet for an aqueous zinc-iodine battery and completing the present invention.

[0011] Accordingly, the present invention has as its technical problem to provide a carbon-iodine-binder composite anode sheet for an aqueous zinc-iodine battery.

[0012] In addition, the present invention has another technical problem to solve by providing a dry manufacturing method for a carbon-iodine-binder composite anode sheet for an aqueous zinc-iodine battery.

[0013] In addition, the present invention has another technical problem to solve by providing an aqueous zinc-iodine battery comprising the carbon-iodine-binder composite anode sheet described above.

[0014] In order to solve the above technical problem, the present invention relates to a positive electrode sheet for an aqueous zinc-iodine battery, wherein

[0015] Porous carbon particles complexed with adsorbed iodine within the pores;

[0016] Challenge material; and

[0017] The present invention provides a carbon-iodine-binder composite anode sheet for an aqueous zinc-iodine battery, characterized by comprising a fibrous polymer binder that forms a network between the carbon particles and the conductive material.

[0018] In the present invention, the carbon particles, conductive material, and fibrous polymer binder are characterized by being included in a weight ratio of 80-90: 5-10: 5-10.

[0019] In addition, in the present invention, the composite sheet is characterized by having a thickness of several tens of micrometers to several hundred micrometers.

[0020]

[0021] In addition, to solve the above other technical problems, the present invention provides a method for manufacturing an anode sheet for a water-based zinc-iodine battery, wherein

[0022] (1) a step of preparing a mixture by mixing porous carbon particles, a conductive material, and a polymer binder, and then kneading the mixture to fiberize the polymer binder; (2) a step of preparing a mixture powder by grinding the mixture; (3) a step of preparing a carbon-iodine-binder composite by adding iodine powder to the mixture powder, mixing, and then heat-treating so that the iodine sublimes and is injected into the mixture powder to form a composite; and (4) a step of preparing a carbon-iodine-binder composite sheet by sheeting the composite through a calendering process; wherein the composite is manufactured by including the above steps.

[0023] In the above step (1), the fiberized polymer binder forms a network between the carbon particles and the conductive material, and

[0024] The present invention provides a dry method for manufacturing a carbon-iodine-binder composite anode sheet for an aqueous zinc-iodine battery, characterized in that, in step (3) above, the iodine sublimated by the heat treatment is adsorbed into the pores of the porous carbon particles within the mixture powder to form a carbon-iodine-binder composite.

[0025] In the present invention, the composite sheet is characterized as being a positive electrode sheet for a water-based zinc-iodine battery as described above.

[0026] In addition, the present invention is characterized by being one or more selected from the group consisting of polyethylene oxide (PEO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylpyrrolidinone (PVP), polyvinylidene fluoride (PVDF), and polytetrafluoroethylene (PTFE).

[0027] In addition, the present invention is characterized in that, in step (3), the granulated mixture and the iodine powder are included in a weight ratio of 1:1 to 5.

[0028] In addition, the present invention is characterized in that the heat treatment in step (3) is performed at 120 to 160 ℃.

[0029] In addition, to solve the other technical problems mentioned above, the present invention provides an aqueous zinc-iodine battery comprising the carbon-iodine-binder composite anode sheet described above.

[0030] According to the present invention, a composite can be formed without a separate solvent by fiberizing a polymer binder through a step of mixing and kneading dry raw material powders, and then, through heat treatment in a ground state, iodine is adsorbed into the pores of carbon particles to produce a carbon-iodine-binder composite, which can then be formed into a sheet through a calendering process. Accordingly, it is possible to manufacture a thick-film anode sheet by controlling the calendering process, and since it is manufactured in an environmentally friendly manner through a dry process and does not use a slurry, a current collector is not required, thereby enabling the production of an anode sheet with improved energy density. Furthermore, when manufacturing an anode sheet using a conventional wet process, I2 may be lost during the manufacturing process, such as by dissolving or sublimating; however, since the present invention is manufactured using a dry process, it is possible to accurately quantify the material.

[0031] Figure 1 shows the manufacturing process of the anode sheet of the present invention.

[0032] Figure 2 shows an anode sheet manufacturing process according to Example 1 of the present invention.

[0033] Figure 3 shows an initial CV graph during charging and discharging according to one embodiment of the present invention.

[0034] FIGS. 4 and 5 show the discharge capacity according to charging and discharging at a rate of 0.5C after charging and discharging five times at a C-rate of 0.1C according to one embodiment of the present invention.

[0035] The present invention will be described in detail below.

[0036] Furthermore, throughout the specification, when a part is described as "including" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0037] Zn-I2 aqueous secondary batteries are Zn 2+ It is a battery system that uses ions as a charge transfer medium, and operates with a positive electrode composed of C / I2 and a negative electrode composed of metallic Zn. The electrolyte is mainly an aqueous solution such as ZnSO4, and Zn 2+ It is an aqueous solution in which a salt containing is dissolved in water. In the present invention, a composite cathode sheet in which a carbon-iodine-binder is composited is manufactured by introducing a dry manufacturing process that does not require the use of a solvent or a drying process to compensate for the disadvantages of the conventional wet manufacturing process when manufacturing a composite cathode for a Zn-I2 aqueous secondary battery.

[0038] Accordingly, in one embodiment, the present invention provides a carbon-iodine-binder composite anode sheet for a water-based zinc-iodine battery, characterized by comprising: porous carbon particles in which iodine is adsorbed and composited within the pores; a conductive material; and a fibrous polymer binder that forms a network between the carbon particles and the conductive material. Fig. 1 illustrates a manufacturing process for the anode sheet of the present invention. Referring thereto, the composite sheet can be provided as an anode without a separate current collector by forming a composite in which a fibrous polymer binder forms a network between porous carbon particles in which iodine is injected and composited, and a conductive material. Accordingly, it becomes possible to increase the energy density of the water-based zinc-iodine battery.

[0039] In the present invention, the composite sheet may contain carbon particles, a conductive material, and a fibrous polymer binder in a weight ratio of 80-90: 5-10: 5-10. In the composite, the carbon particles serve as a carrier for iodine in the electrode, the conductive material serves to supplement the insufficient electrical conductivity of iodine, and the polymer binder provides mechanical properties that allow the electrode to be molded. If the electrode is manufactured with a composition deviating from the above weight ratio, the capacitance may be insufficient, or the rigidity of the electrode may be weak, leading to problems such as electrode breakage or damage.

[0040] In particular, when carbon particles are included within the above range as active material particles, they can be compounded in a state of adsorption by injecting iodine gas into the pores of the carbon particles, thereby preventing the aggregation of iodine and improving the performance of the anode. At this time, the porous carbon particles may be activated carbon.

[0041] In addition, the conductive material can be used without limitation as long as it is generally available in the industry, and when a composite is formed within the above range, conductivity can be increased to improve the performance of the anode. Preferably, the conductive material may be one or more selected from the group consisting of graphite, soft carbon, hard carbon, carbon black, acetylene black, ketjen black, carbon fiber, carbon nanotube, and graphene.

[0042] In addition, the polymer binder is characterized by being included in a fibrous state to form a network between porous carbon particles and a conductive material. Therefore, the content of the polymer binder must be included within the above range so that the active material content can be optimized and the cathode performance improved as the network formed by the polymer binder forms a sheet. Preferably, the polymer binder is a polymer capable of fibrosis and may include one or more selected from the group consisting of polyethylene oxide (PEO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylpyrrolidinone (PVP), polyvinylidene fluoride (PVDF), and polytetrafluoroethylene (PTFE).

[0043] As described above, the carbon-iodine-binder composite anode sheet of the present invention can be manufactured without a process of dispersing active material particles and conductive binder in a solvent by using a fiberized polymer binder and porous carbon particles injected with iodine. FIG. 1 illustrates a manufacturing process for an anode sheet for a zinc-iodine battery according to the present invention. Referring to FIG. 1, in another embodiment, the present invention comprises: (1) a step of preparing a mixture dough in which porous carbon particles, conductive material, and polymer binder particles are mixed and then kneaded to fiberize the polymer binder; (2) a step of preparing a mixture powder by grinding the mixture; (3) a step of preparing a carbon-iodine-binder composite in which iodine powder is added to the mixture powder, mixed, and then heat-treated so that iodine is injected into the mixture powder as it sublimates to form a composite. The present invention relates to a method for manufacturing an anode sheet for an aqueous zinc-iodine battery, characterized by comprising the steps of: (4) forming the composite into a sheet using a calendering process to produce a carbon-iodine-binder composite sheet.

[0044] The following steps are divided and explained in detail.

[0045] First, step (1) is a step of preparing a mixture dough in which porous carbon particles, conductive material, and polymer binder particles are mixed and then kneaded to fiberize the polymer binder. It is important to ensure that the polymer binder is fiberized during the kneading process. This is because a network is formed between the carbon particles and the conductive material by the fiberized polymer binder, thereby forming a rigid structure and enabling a dry process.

[0046] Next, step (2) is a step of grinding the mixture to produce a mixture powder, wherein the fibrous polymer binder is ground in a state where it forms a network, thereby enabling the carbon particles, conductive material, and polymer binder to later form a composite.

[0047] Next, step (3) is a step of manufacturing a carbon-iodine-binder composite by adding iodine powder to the mixture powder, mixing, and then heat-treating so that the iodine is sublimated and injected into the mixture powder to form a composite, wherein the sublimated iodine is adsorbed into the pores of the porous carbon particles within the mixture powder to form a composite. At this time, it is preferable to mix the mixture powder and the iodine powder in a weight ratio of 1:1 to 5. If the iodine powder is mixed in a ratio below the above range, the iodine content is low, which causes a problem of excessively reduced energy density of the electrode, and if it exceeds the above range, there is a problem of rapid capacity degradation due to the isolation of iodine and reduced electrode conductivity caused by an excess amount of iodine participating in charging and discharging.

[0048] In addition, the above heat treatment is performed by heating to a temperature at which iodine can sublimate, so it is preferable to heat treat at 90 to 160 ℃ to avoid affecting the polymer binder.

[0049] Finally, step (4) is a step of manufacturing a carbon-iodine-binder composite sheet by forming the composite into a sheet using a calendering process. That is, in conventional wet processes, it is difficult to manufacture a thick anode sheet due to phenomena such as binder migration, where the binder is not evenly distributed within the coating layer. However, in the present invention, the gap between the rolls is controlled during the calendering process, and thick film formation is made possible through multiple sheeting operations. Preferably, the composite sheet can be manufactured with a thickness of tens of µm to hundreds of µm. By manufacturing a thick sheet, the active material content of the electrode can be increased, and because a current collector is not required due to the dry process, the weight ratio occupied by the current collector is drastically reduced, thereby improving energy density.

[0050] As such, the present invention is characterized by the ability to form a composite without a separate solvent by fiberizing a polymer binder through a step of mixing and kneading dry raw material powders, and then to manufacture a carbon-iodine-binder composite by adsorbing iodine into the pores of carbon particles through heat treatment in a ground state, followed by forming it into a sheet through a calendering process. Accordingly, it is possible to manufacture a thick-film anode sheet by controlling the calendering process, and since it is manufactured in an environmentally friendly manner through a dry process and does not use a slurry, a current collector is not required, thereby enabling the production of an anode sheet with improved energy density. Furthermore, when manufacturing anode sheets using a conventional wet process, I2 may be lost during the manufacturing process due to dissolution or sublimation; however, since the present invention is manufactured using a dry process, accurate quantification of the material becomes possible.

[0051] FIG. 2 shows an anode sheet according to a preferred embodiment of the present invention. After mixing activated carbon, a conductive material, and PTFE in powder form, the PTFE is fiberized in a dry environment to produce a composite. Then, a measured amount of I2 powder is added and mixed, and the temperature is raised in a sealed environment so that I2 sublimes and is adsorbed between the pores of the activated carbon. The composite powder produced in this way can be fed between interlocking rotating rolls to produce a sheet-type dry anode film.

[0052] In this way, a stable C / I2-based thick film electrode can be manufactured without I2 loss through a dry process, and based on this, it can be applied to a Zn-I2 aqueous secondary battery with increased energy density. Accordingly, in another embodiment, the present invention relates to an aqueous zinc-iodine battery comprising a carbon-iodine-binder composite cathode sheet for an aqueous zinc-iodine battery.

[0053] The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

[0054] <Example> Preparation of Composite Electrode

[0055] BET is 3410 m 2 / g and particle size (D 50 Activated carbon (MSC-300) with a particle size of 60㎛, carbon black conductive material, and PTFE as a binder were prepared. Subsequently, the activated carbon (C):conductive material (super-P):binder (PTFE) were mixed in a weight ratio of 86:4:10, and then 100 o PTFE fiberization was carried out by kneading with a twin screw blade at 20 rpm for 1 hour in a C environment. Afterward, the material was ground with a grinder to produce activated carbon-conductive material-binder granules.

[0056] Subsequently, the manufactured powder and I2 were mixed in a weight ratio of 1:2, and then 120 in a sealed environment o A composite powder was prepared dry by heat treatment at C for 6 hours.

[0057] Next, the manufactured composite powder was fed between two interlocking rolls to produce a sheet. The thickness of the sheet was controlled by adjusting the gap between the rolls. The final gap was set to 100–150 µm.

[0058] The electrode loading amount is 15 mg / cm² 2 And, the I2 content was 66.6%.

[0059] The manufacturing process according to the present embodiment is shown in FIG. 2.

[0060]

[0061] <Comparative Example>

[0062] Activated carbon (MSC-300) and I2 powder were prepared, and then the activated carbon (C) and I2 were mixed in a weight ratio of 1:2. A C / I2 composite was prepared by heat treatment at 90°C for 6 hours in a sealed environment. An active material (C / I2), conductive material (super-P), and binder (PVdf) were mixed in an 80:10:10 ratio and dispersed in an NMP solvent to prepare a slurry. The slurry was applied to a Ti current collector, and 100 o A composite electrode was prepared by drying at C. At this time, although thick film formation is difficult due to the characteristics of the wet process, such as coating layer delamination or cracking when the loading amount is increased, the electrode was prepared by maximizing the film thickness. The electrode loading amount was 4.5 mg / cm². 2 A composite with an I2 content of 53.3% was prepared, and an electrode was fabricated.

[0063]

[0064] <Test Example>

[0065] Cell performance was evaluated by comparing the electrodes of the examples and comparative examples. The manufacturing conditions for each electrode are as shown in Table 2 below. In the case of the examples, since they were manufactured as sheet-type electrodes by a dry process, a current collector was not required during electrode manufacturing.

[0066] Example Comparative Example Cathode: Composite of Example (I2 content: 66.6%) Composite of Comparative Example (I2 content: 53.3%) Current Current Collector: No foil (No Lamination) Ti foil Cathode: Zn foil 16 Φ (50 µm) Separator: 1 sheet of GFC (200 µm) 2 sheets of GFC (200 µm) Electrolyte: 2M ZnSO4

[0067] When evaluating cell performance, the charge and discharge conditions are as follows.

[0068] * Charge / Discharge Conditions

[0069] - Voltage: 0.6 - 1.6 V

[0070] - HL: 0.1C 5cyc, 0.5C 1000 cyc

[0071]

[0072] The results are shown in Figures 3 to 5.

[0073] Figure 3 shows the initial CV graph when charging and discharging at a C-rate of 0.1C. It was confirmed that the discharge capacity in the example was significantly improved to 171.2 mAh / g compared to the comparative example, which had an initial discharge capacity of 106.5 mAh / g. It is understood that the iodine impregnation method using a vaporization method proceeded very effectively after the preparation of the dry powder, and the proportion of activated iodine within the electrode was significantly higher than that of the wet process electrode.

[0074] In addition, Figure 4 shows the discharge capacity according to charge / discharge at a rate limit of 0.5C after 5 charge / discharge cycles at a C-rate of 0.1C. Based on the rate limit of 0.5C, the example, which showed an initial discharge capacity approximately 1.5 times higher than the comparative example, was confirmed to continuously exhibit superior capacity even in a charge / discharge test of 100 cycles. This means that when a composite is manufactured by the dry manufacturing method of the present invention, the leaching of iodine and degradation do not occur during the solvent dispersion / drying process of the wet process, thereby improving the initial cell performance and lifespan characteristics.

[0075] With reference to Fig. 4, when preparing the composite of the above example, the prepared activated carbon-conductive material-binder powder and I2 were mixed in weight ratios of 1:2, 1:1.5, and 1:2.5 to prepare the composite, designated as Examples 1-1, 1-2, and 1-3, respectively. Cells were fabricated using these composites, and the cell performance was further evaluated and is shown in Fig. 5. It was confirmed that the higher the weight ratio of I2, the higher the capacity exhibited not only in the initial discharge capacity but also in the 100-cycle charge-discharge test. This implies that the energy density improved as the iodine content increased.

[0076] Based on the results of the above examples, it is determined that according to the present invention, by fiberizing a polymer binder through a step of mixing and kneading dry raw material powders, preparing a carbon-iodine-binder composite by adsorbing iodine into the pores of carbon particles through heat treatment, and preparing a thick-film anode sheet through a calendering process, the cell performance can be improved when applied to an aqueous-zinc-iodine secondary battery.

Claims

1. In a positive electrode sheet for an aqueous zinc-iodine battery, Porous carbon particles complexed with adsorbed iodine within the pores; Challenge material; and Characterized by including a fibrous polymer binder that forms a network between the carbon particles and the conductive material. Carbon-iodine-binder composite anode sheet for aqueous zinc-iodine batteries.

2. In Paragraph 1, A carbon-iodine-binder composite positive electrode sheet for an aqueous zinc-iodine battery, characterized in that the carbon particles, conductive material, and fibrous polymer binder are included in a weight ratio of 80-90: 5-10: 5-10.

3. In Paragraph 1, A carbon-iodine-binder composite positive electrode sheet for an aqueous zinc-iodine battery, wherein the binder is characterized by one or more selected from the group consisting of polyethylene oxide (PEO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylpyrrolidinone (PVP), polyvinylidene fluoride (PVDF), and polytetrafluoroethylene (PTFE).

4. A method for manufacturing a positive electrode sheet for an aqueous zinc-iodine battery, (1) A step of preparing a mixture dough in which porous carbon particles, conductive material and polymer binder particles are mixed and then kneaded to fiberize the polymer binder; (2) A step of grinding the above mixture to produce a powder of the mixture; (3) A step of preparing a carbon-iodine-binder composite by adding iodine powder to the above mixture powder, mixing, and then heat-treating so that the iodine is sublimated and injected into the above mixture powder to form a composite; and (4) A step of manufacturing a carbon-iodine-binder composite sheet by forming the above composite into a sheet using a calendering process; and manufactured including, In the above step (1), the fiberized polymer binder forms a network between the carbon particles and the conductive material, and In the above (3) step, the iodine sublimated by the heat treatment is adsorbed into the pores of the porous carbon particles within the mixture powder to form a carbon-iodine-binder complex. Dry manufacturing method of a carbon-iodine-binder composite anode sheet for an aqueous zinc-iodine battery.

5. In Paragraph 4, A dry method for manufacturing a carbon-iodine-binder composite anode sheet for an aqueous zinc-iodine battery, characterized in that the composite sheet is a composite sheet according to any one of claims 1 to 3.

6. In Paragraph 4, A dry method for manufacturing a carbon-iodine-binder composite anode sheet for an aqueous zinc-iodine battery, characterized in that the composite sheet has a thickness of several tens of micrometers to several hundred micrometers.

7. In Paragraph 4, A dry method for manufacturing a carbon-iodine-binder composite anode sheet for a water-based zinc-iodine battery, characterized in that in step (3) above, the mixture powder and the iodine powder are included in a weight ratio of 1:1 to 5.

8. In Paragraph 4, A dry method for manufacturing a carbon-iodine-binder composite anode sheet for a water-based zinc-iodine battery, characterized in that the heat treatment in step (3) above is performed at 120 to 160 ℃.

9. A water-based zinc-iodine battery characterized by including an anode sheet according to any one of claims 1 to 3.

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