KR100301091B1 - Zinc Sulfate Aqueous Secondary Battery with Manganese (II) Salt - Google Patents

Abstract

When an aqueous zinc sulfate solution is used as an electrolyte for a manganese dioxide-zinc secondary battery, the manganese content of the manganese dioxide anode decreases due to incomplete charging or other side reactions, and the surface of the electrode deteriorates due to the formation of basic zinc sulfate hydrate, thereby freeing ions and materials. By making the electrode reaction difficult by obstructing entry and exit, there is a problem in that the capacity decreases severely as the charge and discharge are repeated. Therefore, in order to solve such a problem, the present invention solves the problem of gradually decreasing the content of manganese from the manganese dioxide anode by adding manganese (II) salt to the electrolyte or electrode material, and also by adding manganese (II) salt to the electrolyte. This more acidic solution can be used to inhibit or eliminate the production of basic zinc sulfate hydrates that can destroy the electrode surface structure. From these results, it can be confirmed that the manganese dioxide / zinc sulfate / zinc aqueous solution battery to which manganese (II) salt is added has excellent capacity and reversibility as a secondary battery.

Description

Zinc Sulfate Aqueous Secondary Battery with Manganese (II) Salt

The present invention relates to a secondary battery using manganese dioxide as a positive electrode material, zinc (Zn) as a negative electrode material, and a zinc sulfate (ZnSO ₄ ) aqueous solution as an electrolyte, in particular, a battery which appears as a result of repeated charge and discharge. It is characterized by adding an appropriate amount of manganese (II) salt in order to suppress a decrease in dose.

Batteries are widely used as power sources for electronic / electrical devices. Due to recent trends such as miniaturization, light weight, high performance, portable use, and personal use of such devices, there is a strong demand for development of secondary battery power supplies that can be used for a long time and economically. The need to develop and produce secondary batteries replaces the growing demand for primary batteries that are discarded after one discharge, and further begins with serious reflections on energy savings and environmental issues. Considering the fact that the energy required to produce a primary cell is about 10 times more than the energy that can be obtained by using the cell, it is possible to save a very heavy waste of energy. In addition, considering the fact that it is a waste of renewable materials and its environmental problems, the development of a secondary battery can have several benefits. In view of these various aspects, research and development on secondary batteries, in particular, nickel-cadmium batteries, nickel-hydrogen batteries, and alkaline manganese dioxide-zinc secondary batteries are being conducted. In particular, alkaline secondary batteries are evaluated to have advantages of high energy density and low price by using zinc as a negative electrode material. In addition, the demand for these batteries can be expected to increase further when sanctions are applied to toxic lead-acid batteries and nickel-cadmium batteries.

However, secondary batteries using zinc as a negative electrode material have the problems and disadvantages of instability and short lifespan of the negative electrode material zinc in common. The main reason for deteriorating the performance of the zinc electrode is that as charging and discharging are repeated, uneven dissolution in the discharging process and electrodeposition in the charging process appear. That is, during the discharging process, zinc dissolves into a non-uniform and uneven shape due to a slight difference in the surface state of the zinc electrode, and as a result, the surface of the zinc electrode becomes rougher as the discharge proceeds further. The distortion of appears. On the contrary, the electrodeposition of zinc during the charging process is dendritic growth, and the dendritic growth proceeds in the direction of the anode as the charge and discharge are repeated, penetrates the separator, and eventually internal short-circuit. ).

In addition, the limitations due to irreversibility remain in the manganese dioxide anode as well as the problems associated with the zinc cathode. For example, to achieve 100 times of charge and discharge performance, the discharge capacity must be limited to not more than 25% of the one-electron theoretical capacity. This is because MnOOH, the product of the 1-electron discharge process, loses its electrochemical activity. The possibility of charging (oxidizing) manganese dioxide using most of the discharge capacity (deep discharged) is only limited to the initial several times and also entails a sharp decrease in capacity. This irreversibility is explained for a variety of reasons, including loss of surface conductivity, increased internal resistance of the reaction intermediate or product, production of Mn ₂ O ₃ , Mn ₃ O ₄ or ZnO.Mn ₂ O ₃ . According to McBreen (Electrochim. Acta, 7, 449 (1962)), amorphous MnOOH is produced by the destruction of the initial crystal lattice during the 1-electron discharge process, which produces Mn (OH) during the next 2-electron discharge. ) Is reduced to ₂ . It is explained that it accumulates with Mn ₃ O ₄ or ZnO.Mn ₂ O ₃ irreversible during the charging process, deteriorating the performance of the entire battery and changing the charging to be impossible.

Alkaline manganese dioxide-zinc batteries are the most widely used systems in the primary battery market. They are not only reliable, but also cause less environmental problems, use relatively inexpensive and abundant materials, and are easy to achieve high rate discharge and stable discharge performance. Dots raise expectations for this battery system. However, it has been shown to have a decisive disadvantage in that the charging performance is reduced without using a new design of manganese dioxide, an electrolyte system, and high purity zinc. In this regard, the conventional manganese dioxide-zinc aqueous solution cell system will be described in more detail as follows.

Conventional Manganese Dioxide-Zinc Aqueous Cell System

A manganese dioxide-aqueous zinc battery system is one of the most used primary cells with a long history and is supplied in the form of a Le Clanche battery, a zinc-duty battery and an alkaline battery. This uses almost the same electrochemical reaction except for some differences in the composition, purity, additives, etc. of manganese dioxide and zinc, and the composition of each electrolyte.

Manganese dioxide has the advantage of low price and does not cause much environmental problems, and zinc also has the advantages of low cost and high energy density in aqueous solution. Therefore, research and commercialization of manganese dioxide-zinc primary batteries having such advantages have been made for a long time. It has been the subject of much interest. Therefore, many attempts have been made to improve such a battery system into a secondary battery having sufficient reversibility and a large energy density, but at present no remarkable results have been obtained. The reason for this is that the reversibility of manganese dioxide is low, and that corrosion and dendritic growth of zinc are emerging as major problems.

Research on improving a LeClanche battery or a zinc chloride battery using a strong acid electrolyte into a secondary battery has not been achieved so far, and alkaline secondary batteries have not been showing excellent results. Particularly, problems of corrosion, heterogeneous dissolution and electrodeposition of zinc, and internal short circuit due to dendritic growth in alkaline electrolytes have been highlighted, and irreversible phase (ZnO · Mn ₂ O) is caused by the reaction of zinc products with manganese dioxide. _The problem remains to solve the problem of reversibility of manganese dioxide, such as the formation of hetaerolite.

Therefore, zinc sulfate electrolyte having excellent reversibility with respect to manganese dioxide and zinc can be considered. This electrolyte has a temperature conductivity of about 50 mS / cm, which is smaller than an alkaline electrolyte (> 400 mS / cm), which is also a problem of zinc corrosion, but it is the electricity between manganese dioxide / manganese ion (II) and zinc / zinc ion (II). Since the reversibility of the chemical oxidation / reduction reaction is very large, research is being conducted as a new electrolyte. Zinc salts that have been used as electrolytes include zinc chloride (ZnCl ₂ ), zinc bromide (ZnBr ₂ ), zinc acetate (Zn (O ₂ CCH ₃ ) ₂ ), zinc nitrate (Zn (NO ₃ ) ₂ ), etc. Among these, zinc sulfate is known to show the best performance. It can be guessed from the fact that it contains the sulfate anion most preferred in the electrodeposition of zinc, and it can be considered that the sulfate anion is also adopted in the production process of electrolytic manganese dioxide.

Shoji et al. Reported the results of a new system using several types of manganese dioxide as anode material and using 2M zinc sulfate aqueous solution as an electrolyte (Inorg. Chim. Acta, 117, L27 (1986), J. Appl. Electrochem., 18, 521 (1988), J. Electroanal. Chem., 362, 153 (1993), Japan Patent Publication 05166540 (1993)), and there is room for development of cells with improved reversibility and good capacity. Yamamoto also reports similar results (Japan Patent Publication 06044975 (1994)). Askar et al. Also reported experimental results on batteries using 1M zinc sulfate solution as an electrolyte (J. Power Sources, 48, 303 (1994)). There is a problem that can not be restored / restored to a state, and there is no clear mention of reversibility.

However, the sulfate ion (SO ₄ ^2-) of zinc / zinc ion (Ⅱ) as the oxidation / reduction reaction, as well as between boindago a significant effect on the reversibility of the reaction between manganese dioxide / manganese ion (Ⅱ) is known, zinc sulphate electrolyte system Can be considered to have a very positive effect on the development of manganese dioxide-zinc cell systems as secondary batteries.

However, it cannot be concluded that the use of zinc sulfate electrolyte completely improves the reversibility of the manganese dioxide-zinc cell system. Chiba et al. Explained that the cause of irreversibility in manganese dioxide / zinc sulfate / zinc aqueous solution secondary battery is due to internal short-circuit phenomenon due to zinc dendritic growth. As a solution, the surface of substrate or base layer of zinc anode is solved. The results of replacing with lead (Pb) or an alloy of lead was published (US Patent 4,968,569 (1990)). However, this attempt to solve the problem by improving the zinc cathode seems to have not shown a great performance. That is, even when the improved zinc anode is used, the capacity decrease after about 50 charge / discharge cycles is about 18% to 39%. Similarly, as shown by the results of Shoji et al., It is pointed out that the use of electrolytes consisting only of zinc sulfate shows a continuous reduction in capacity despite having excellent initial capacity, and Asuka et al.

As can be judged from these results, it can be seen that the main cause of irreversibility in manganese dioxide / zinc sulfate / zinc solution secondary batteries is directly related to the problem of manganese dioxide anode, in particular, incomplete charging problem. The main reason for this problem of capacity reduction or incomplete charging is the primary cause of dissolution of manganese and subsequent loss of material during side reactions during repeated charging and discharging, and basic zinc sulfate on the surface of the manganese dioxide anode It can be judged that the hydrate, ZnSO ₄ · 3Zn (OH) ₂ · nH ₂ O is formed.

The problem of reducing the capacity of a cell by dissolving manganese from the cathode material of manganese oxide has already been reported by various researchers, and the reactor mechanism has been described in various ways. Thackeray et al. Reported dissolution mainly through disproportionation in the manganese (III) state (Solid State Ionics, 69, 59 (1994)), and Jan et al. Is reported to proceed through side reactions of electrolytes or conductive materials (J. Electrochem. Soc, 143, 2204 (1996)).

The zinc sulfate electrolyte used in the present invention has the advantage of enabling a 2-electron reaction between manganese dioxide (IV) / manganese ions (II), from the solid state of manganese dioxide during the discharge process. It is reduced to manganese ions (II) in aqueous solution (a reaction involving two electrons for one manganese element), allowing its reverse reaction to proceed during the charging process. By the way, this electrolyte has a very high solubility in manganese ions (II) (»2M), and if the manganese ions (II) dissolved in the electrolyte during discharge are not completely recovered into manganese dioxide during the charging process, Material loss (reduced total amount of manganese used as the anode material) and incomplete filling will occur, and capacity reduction will continue in the long run.

In addition, since the discharge reaction is a reaction that consumes hydrogen ions in the electrolyte, the pH rises locally on the surface of the manganese dioxide anode. For this reason, basic zinc sulfate hydrate, that is, ZnSO ₄ · 3Zn (OH) ₂ · nH ₂ O Will be created. The basic zinc sulfate hydrate thus formed accumulates near the surface of the electrode (the interface between the electrolyte and the electrode) and acts as a factor that hinders charge transfer and mass transfer, which may be considered to cause incomplete charging and capacity reduction. By the way, the basic zinc sulfate hydrate has a stable range of a specific pH range (pH> 2.8), and is generally unstable as the pH of the aqueous solution is lowered, so that the basic zinc sulfate hydrate is dissolved or its production is inhibited. Has In order to accurately determine the formation of basic zinc sulfate hydrate, according to Bear et al. (Aust. J. Chem., 40, 539 (1987)) basic zinc sulfate hydrate (3-hydrate, 4-hydrate, 5-hydrate) was synthesized and compared.

In summary, when the zinc sulfate aqueous solution is used as the electrolyte of the manganese dioxide-zinc secondary battery, the capacity may decrease as charge and discharge are repeated due to the following two causes. First, the manganese content of the manganese dioxide anode decreases due to incomplete charging or other side reactions. Second, due to the production of basic zinc sulfate hydrate, the electrode surface structure is deteriorated, which makes the electrode reaction difficult by preventing free entry of ions and materials.

Accordingly, an object of the present invention is to suppress the problems appearing in zinc and manganese dioxide electrodes in constructing an aqueous secondary battery using universal manganese dioxide as a cathode material and zinc (Zn) as a cathode material. Is to develop electrolyte system with long-term charge and discharge stability and reversibility. In more detail, a positive electrode is composed of a mixture of manganese dioxide, a conductive material and a binder, a mixture of zinc metal powder, a conductive material and a binder, or a zinc metal is used as a negative electrode, and an aqueous solution of zinc sulfate (ZnSO ₄ ) is used as an electrolyte. In the secondary battery described above, an appropriate amount of manganese (II) salt is added to suppress a decrease in battery capacity caused by repeated charging and discharging.

1 is an analysis diagram comparing changes in discharge capacity according to the number of constant current charge and discharge cycles of manganese dioxide-zinc secondary batteries manufactured according to the present invention (Examples 1 and 2) and Comparative Example (Example 8), respectively.

Figure 2 is a comparison of the change in the discharge capacity according to the number of constant current charge and discharge of the manganese dioxide-zinc secondary battery produced according to the present invention (Examples 3, 4, 5, 6 and 7) and Comparative Example (Example 8), respectively One analysis,

3 is an analysis diagram comparing changes in discharge capacity according to the number of constant current charge / discharge cycles of the manganese dioxide-zinc secondary batteries manufactured according to the present invention (Examples 9 and 10) and Comparative Example (Example 11), respectively.

4 is an analysis diagram comparing changes of manganese content in the manganese dioxide anode according to the number of constant current charge and discharge cycles of the manganese dioxide-zinc secondary battery manufactured according to the present invention (Example 12) and Comparative Example (Example 13),

5 is a comparison of the results of X-ray diffraction analysis of the manganese dioxide anode according to the number of times of constant current charge and discharge of the manganese dioxide-zinc secondary battery manufactured according to the present invention (Example 14) and Comparative Example (Example 15), respectively. One analysis diagram.

In order to achieve the above object and to develop a secondary battery having the above characteristics, in the present invention, a secondary battery including a cathode, an anode, and an electrolyte is configured as follows. The positive electrode, the negative electrode, and the electrolyte are the most basic constituent materials of the battery, and in addition, additional constituent materials such as a separator may be included.

Manganese dioxide used as the anode material is, for example, stoichiometric obtained by natural manganese dioxide, chemically synthesized manganese dioxide, electrolytic manganese dioxide, or other methods. ) Or any manganese dioxide that is nonstoichiometric. That is, all manganese dioxide used or known as a cathode material of a battery can be applied. Although it is possible to form an anode with only manganese dioxide, it is preferable to use a mixture with a conductive material and a binder having electrical conductivity. In general, as the conductive material, carbon powders such as acetylene black, furnace black, graphite, activated carbon, and the like are used, and as a binder, manganese dioxide, a conductive material and a current collector are used. High molecular materials that can maintain or improve bonding strength, such as polyvinylalcohol (PVA), polyvinylchloride (PVC), polytetrafluoroethylene (PTFE), polyvinylidenedifluoro Lead (polyvinyliden difluoride (PVdF)), polymethylmethacrylate (polymethylmeth acrylate: PMMA) and the like are used.

Zinc used as a cathode material may be used in the form of a metal foil (foil, sheet), or similar to the case of manganese dioxide anode, a metal powder may be mixed with a conductive material and a binder. The higher the purity of the zinc metal, the better.

Each of the positive and negative electrode materials in the form of the mixture thus obtained is press-molded and formed into pellets or formed into a thin film by screen printing, and then combined with a current collector. In addition, it may be used as a gel type by mixing with an electrolyte and a gelling agent. The manufacturing method, constituents, compositions, and molding methods of such a mixture electrode material may be selected in consideration of the shape and characteristics of the battery. The present invention does not compare the advantages and disadvantages of each method and the above optional matters do not limit the object and scope of the present invention.

As the electrolyte, zinc salts, in particular zinc sulfate aqueous solution, are used, but only zinc sulfate is not added. In this case, the water used as the solvent is preferably ultrapure water, and the higher the purity of zinc sulfate, the more advantageous it is preferably 99% or more. The concentration of zinc sulfate is suitably 0.5M to 3M, more preferably 1M to 2.5M. Such zinc sulfate electrolytes have the advantage of being easily prepared and handled and being fairly stable by using water as a solvent. In addition, there is an advantage that the charge and discharge performance of the battery can be improved by excellent electrical conductivity.

However, when the zinc sulfate aqueous solution is used as the electrolyte of the manganese dioxide-zinc secondary battery, as described above, due to the following two causes, the capacity decreases severely as the charge and discharge are repeated. First, the manganese content of the manganese dioxide anode decreases due to incomplete charging or other side reactions. Second, due to the production of basic zinc sulfate hydrate, the electrode surface structure is deteriorated, which makes the electrode reaction difficult by preventing free entry of ions and materials. Therefore, in order to solve this problem, a new design for electrolyte or battery constituent materials, compositions, and the like is required. For example, a change in the manganese dioxide crystal structure, an improvement in the anode manufacturing conditions, or a change in the composition of the anode material may be considered.

The present invention proposes a method to solve this problem by introducing a new additive as an electrolyte or battery component. In other words, by adding manganese (II) salt as an electrolyte or battery constituent material, the problem of reducing the manganese content of the manganese dioxide anode is reduced, and the addition of manganese (II) salt makes the electrolyte a stronger acidic solution. Thus, it is possible to suppress or eliminate the production of basic zinc sulfate hydrate that can destroy the electrode surface structure.

Manganese (II) salts added are manganese sulfate (MnSO ₄ ), manganese nitrate (Mn (NO ₃ ) ₃ ), manganese acetate (Mn (CO ₂ CH ₃ ) ₂ ), manganese chloride (MnCl ₂ ), manganese bromide (MnBr ₂ ) and one or more selected from the group consisting of manganese perchlorate (Mn (ClO ₄ ) ₂ ) may be used, and among them, manganese sulfate is preferably included. The higher the purity of the added manganese (II) salt is, the more advantageous it is, and the concentration is preferably 2 M or less and at the same time the zinc sulfate or less, and more preferably 0.5 M or less. Manganese (II) salt may be added directly to the electrolyte, and in some cases, all or part of the manganese (II) salt to be added may be mixed with the electrode material to be molded. After the battery is constructed, the manganese (II) salt is dissolved into the electrolyte from the electrode or the electrode material, and thus does not show a significantly different result from the method of adding directly to the electrolyte. Therefore, the following cases were regarded as the same conditions when directly added to the electrolyte and when mixed with the electrode material to be dissolved therefrom. At this time, the concentration of manganese (II) salt in the electrolyte was regarded as a value for the case where all of the manganese (II) salt added to the battery was dissolved in the electrolyte. At this time, the amount of manganese (II) salt added with the electrode material should be adjusted at an appropriate level in consideration of the electrolyte volume, the composition of the electrode material, and the final concentration of manganese (II) salt. However, if the amount to be mixed with the electrode material is too large, care should be taken because there is a risk of loss of the bonding of the electrode. In general, the total weight of each of the positive or negative electrode materials is preferably 20% or less, more preferably 10% or less.

For example, when manganese sulfate is added as the manganese salt, the pH and electrical conductivity of the aqueous electrolyte according to the concentration change of zinc sulfate and manganese sulfate are summarized in Table 1 below. As can be seen from Table 1, as manganese sulfate is added to the 2M zinc sulfate aqueous solution, the pH of the aqueous electrolyte rapidly decreases and the electrical conductivity decreases little by little. Although the conductivity decreases, the level is acceptable for use as an electrolyte for secondary batteries. On the other hand, by decreasing the pH of the aqueous electrolyte, it is possible to obtain an advantage of suppressing or eliminating the production of basic zinc sulfate hydrate that can destroy the electrode surface structure.

Table 1.

Changes in pH and Electrical Conductivity of Aqueous Electrolytes with Concentrations of Zinc Sulfate and Manganese Sulfate

Concentration (m) pH Room temperature electrical conductivity (mS / cm) Zinc sulfate Manganese sulfate One 0 5.02 43.8 2 0 4.32 50.5 2 0.1 3.06 50.0 2 0.2 2.74 49.4 2 0.5 2.31 47.0 2 1.0 1.94 41.5 2 2.0 1.48 26.4

Hereinafter, the configuration and charge and discharge test results of the battery using the zinc sulfate aqueous solution according to the present invention through the examples will be described in detail. However, these Examples do not limit the content of the present invention.

Composition and charge / discharge experiment of manganese dioxide / zinc sulfate / zinc solution secondary battery

Example 1

Electrolytic manganese dioxide anode material, acetylene black conductive material and PTFE (polytetrafluoroethylene) binder are mixed in a weight ratio of 20: 4: 1, and dispersed in isopropanol to form a paste, which is applied to a stainless steel mesh. After pressing to dry in room temperature air to form a positive electrode. Zinc metal powder (325 mesh, 99.5%), acetylene black conductive material and Teflon were mixed in a weight ratio of 200: 2: 1 to form a negative electrode in the same manner as the positive electrode manufacturing process. Zinc sulfate (99.7%) was dissolved in ultrapure water at a concentration of 2M, and an electrolyte in which manganese sulfate (99.3%) was dissolved at a concentration of 0.5M was used. After discharging up to 1.0V (vs. Zn / Zn ²⁺ ) with a constant current (0.4 C), it was charged up to 1.9V (vs. Zn / Zn ²⁺ ) at the same rate. This one time discharge-one time charging process was performed by charging and discharging once. The change result of the discharge capacity according to the number of charge and discharge cycles is shown as (A) in FIG. 1. It can be seen that there is almost no decrease in dose.

Example 2

Manganese dioxide anodes were constructed in the same manner as in Example 1. Zinc metal powder (325 mesh, 99.5%), manganese sulfate (99.3%), acetylene black conductive material and Teflon were mixed in a weight ratio of 200: 20: 2: 1 to form a negative electrode in the same manner as the positive electrode manufacturing process. An electrolyte in which zinc sulfate (99.7%) was dissolved in ultrapure water at a concentration of 2M was used. The final concentration of manganese sulfate in the electrolyte dissolved from the negative electrode was about 0.1M. Constant current charge and discharge experiments were performed in the same manner as in Example 1. The change result of the discharge capacity according to the number of charge and discharge cycles is shown as (B) in FIG. 1. It can be seen that there is almost no decrease in dose.

Example 3

A manganese dioxide anode and a zinc cathode were constructed in the same manner as in Example 1. Zinc sulfate (99.7%) was dissolved in ultrapure water at a concentration of 2M, and an electrolyte in which manganese nitrate (99.9%) was dissolved at a concentration of 0.1M was used. Constant current charge and discharge experiments were performed in the same manner as in Example 1. The change result of the discharge capacity according to the number of charge and discharge cycles is shown as (C) in FIG. 2. It can be seen that there is not much reduction in dose.

Example 4

A manganese dioxide anode and a zinc cathode were constructed in the same manner as in Example 1. Zinc sulfate (99.7%) was dissolved in ultrapure water at a concentration of 2M, and an electrolyte in which manganese acetate (99.5%) was dissolved at a concentration of 0.1M was used. Constant current charge and discharge experiments were performed in the same manner as in Example 1. The change result of the discharge capacity according to the number of charge and discharge cycles is shown as (D) in FIG. 2. It can be seen that there is no decrease in dose.

Example 5

A manganese dioxide anode and a zinc cathode were constructed in the same manner as in Example 1. Zinc sulfate (99.7%) was dissolved in ultrapure water at a concentration of 2M, and an electrolyte in which manganese chloride (99%) was dissolved at a concentration of 0.1M was used. Constant current charge and discharge experiments were performed in the same manner as in Example 1. The change result of the discharge capacity according to the number of charge and discharge cycles is shown as (E) in FIG. 2. It can be seen that there is not much reduction in dose.

Example 6

A manganese dioxide anode and a zinc cathode were constructed in the same manner as in Example 1. Zinc sulfate (99.7%) was dissolved in ultrapure water at a concentration of 2M, and an electrolyte in which manganese bromide (99%) was dissolved at a concentration of 0.1M was used. Constant current charge and discharge experiments were performed in the same manner as in Example 1. The change result of the discharge capacity according to the number of charge and discharge cycles is shown as (F) in FIG. 2. It can be seen that there is not much reduction in dose.

Example 7

A manganese dioxide anode and a zinc cathode were constructed in the same manner as in Example 1. Zinc sulfate (99.7%) was dissolved in ultrapure water at a concentration of 2M, and an electrolyte in which manganese perchlorate (99%) was dissolved at a concentration of 0.1M was used. Constant current charge and discharge experiments were performed in the same manner as in Example 1. The change result of the discharge capacity according to the number of charge and discharge cycles is shown as (G) in FIG. 2. It can be seen that there is not much reduction in dose.

Example 8 (comparative example from Example 1 to Example 7)

A manganese dioxide anode and a zinc cathode were constructed in the same manner as in Example 1. An electrolyte in which zinc sulfate (99.7%) was dissolved in ultrapure water at a concentration of 2M was used. The difference between the present embodiment and the first to seventh embodiments is the fact that no manganese (II) salt was added to the electrolyte or the electrode material. Constant current charge and discharge experiments were performed in the same manner as in Example 1 to Example 7. The change result of the discharge capacity according to the number of charge and discharge cycles is shown as (H) in FIG. 1 or FIG. 2. It can be seen that in the absence of manganese (II) salt, the capacity decrease occurs very rapidly during the initial several charge and discharge processes.

Example 9

Synthetic manganese dioxide anode material, acetylene black conductive material and PTFE (polytetrafluoroethylene) binder are mixed in a weight ratio of 20: 4: 1, dispersed in isopropanol to make a paste, and applied to a stainless steel mesh. After pressing to dry in room temperature air to form a positive electrode. Zinc metal powder (325 mesh, 99.5%), acetylene black conductive material and Teflon were mixed in a weight ratio of 200: 2: 1 to form a negative electrode in the same manner as the positive electrode manufacturing process. Zinc sulfate (99.7%) was dissolved in ultrapure water at a concentration of 2M, and an electrolyte in which manganese sulfate (99.3%) was dissolved at a concentration of 0.5M was used. After discharging up to 1.0V (vs. Zn / Zn ²⁺ ) with a constant current (0.4 C), it was charged up to 1.9V (vs. Zn / Zn ²⁺ ) at the same rate. This one time discharge-one time charging process was performed by charging and discharging once. The change result of the discharge capacity according to the number of charge and discharge cycles is shown as (I) in FIG. 3. It can be seen that the reduction in dose was significantly suppressed.

Example 10

In the same manner as in Example 9, a manganese dioxide anode and a zinc cathode were configured. Zinc sulfate (99.7%) was dissolved in ultrapure water at a concentration of 2M, and an electrolyte in which manganese sulfate (99.3%) was dissolved at a concentration of 0.1M was used. Constant current charge and discharge experiments were performed in the same manner as in Example 9. The change result of the discharge capacity according to the number of charge and discharge cycles is shown as (J) in FIG. 3. It can be seen that there is almost no decrease in dose.

Example 11 (comparative example compared to Example 9 and Example 10)

In the same manner as in Example 9, a manganese dioxide anode and a zinc cathode were configured. An electrolyte in which zinc sulfate (99.7%) was dissolved in ultrapure water at a concentration of 2M was used. The difference between Example 9 and Example 10 is that the manganese (II) salt was not added to the electrolyte. Constant current charge and discharge experiments were performed in the same manner as in Example 9 and Example 10. The change result of the discharge capacity according to the number of charge and discharge cycles is shown as (K) in FIG. 3. It can be seen that in the absence of manganese (II) salt, the capacity decrease occurs very rapidly during the initial several charge and discharge processes.

Example 12

A battery was constructed in the same manner as in Example 10, and a charge and discharge experiment was performed. After repeated charging and discharging any number of times, the manganese dioxide anode was separated to analyze the content of manganese elements present in the electrode. The change of manganese content according to the number of charge and discharge cycles with respect to the initial manganese content (100%) is shown as (L) in FIG. 4. It can be seen that there is almost no decrease in manganese content.

Example 13 (comparative example to Example 12)

A battery was constructed in the same manner as in Example 11, and a charge and discharge experiment was performed. After repeated charging and discharging any number of times, the manganese dioxide anode was separated to analyze the content of manganese elements present in the electrode. The change of manganese content according to the number of charge and discharge cycles with respect to the initial manganese content (100%) is shown as (M) in FIG. 4. It can be seen that the manganese (II) salt is not added very rapidly during the initial several charge and discharge process.

Example 14

A battery was constructed in the same manner as in Example 9, and a charge and discharge experiment was performed. After 10 charge and discharge cycles, the cell was dismantled and the manganese dioxide anode was separated and subjected to X-ray diffraction analysis to compare with the initial crystal structure of the manganese dioxide anode. The crystal structure analysis result of the manganese dioxide anode after 10 charge / discharge cycles is shown as (N) in FIG. 5. It was found that even after 10 charge and discharge cycles, the initial crystal structure was completely maintained and no basic zinc sulfate hydrate was found.

Example 15 (comparison to Example 14)

A battery was constructed in the same manner as in Example 11, and a charge and discharge experiment was performed. After 10 charge and discharge cycles, the cell was dismantled and the manganese dioxide anode was separated and subjected to X-ray diffraction analysis to compare with the initial crystal structure of the manganese dioxide anode. The crystal structure analysis result of the manganese dioxide anode after 10 charge / discharge cycles is shown as (O) in FIG. 5. It can be seen that after 10 charge and discharge, a very large amount of basic zinc sulfate 4-hydrate, ZnSO ₄ · 3Zn (OH) ₂ · 4H ₂ O, was formed. For accurate comparison, basic zinc sulfate hydrates (3-hydrate, 4-hydrate, 5-hydrate) were respectively synthesized according to the method of Bare et al., And the results of X-ray diffraction analysis of basic zinc sulfate 4-hydrate were shown. Shown as 5 at (P).

As can be seen from the results of the charge / discharge experiment of the battery constructed by the present invention, as shown in FIGS. 1, 2, and 3 only by addition of manganese (II) salt, the decrease in capacity due to charge and discharge repetition can be almost suppressed. It can be seen that. The reason why the decrease in capacity is suppressed is, as can be seen in Figures 4 and 5, the above two causes of the capacity reduction by the addition of manganese (II) salt, first, manganese dioxide anode by incomplete charging or other side reactions The manganese content of the decrease is reduced, and secondly, the surface structure of the electrode is deteriorated due to the production of basic zinc sulfate hydrate, thereby preventing the electrode reaction from being difficult by preventing free access of ions and materials. From these results, it can be confirmed that the manganese dioxide / zinc sulfate / zinc aqueous solution battery to which manganese (II) salt is added has excellent capacity and reversibility as a secondary battery.

Claims (5)

In a secondary battery composed of a positive electrode, a negative electrode and an electrolyte, the positive electrode material is manganese dioxide, the negative electrode material is zinc, the electrolyte is a mixed aqueous solution of zinc sulfate and manganese (II) salt, and the concentration of zinc sulfate in the electrolyte is 0.5M to 3M. Secondary battery. The method of claim 1, wherein the manganese (II) salt of the electrolyte is manganese sulfate (MnSO ₄ ), manganese nitrate (Mn (NO ₃ ) ₃ ), manganese acetate (Mn (CO ₂ CH ₃ ) ₂ ), manganese chloride (MnCl ₂ ), one or more selected from the group consisting of manganese bromide (MnBr ₂ ) and manganese perchlorate (Mn (ClO ₄ ) ₂ ), and the concentration of manganese (II) salt in the electrolyte is less than 2M and at the same time less than the concentration of zinc sulfate Secondary battery. In the secondary battery comprising the positive electrode, the negative electrode, and the electrolyte, the positive electrode material is manganese dioxide, the negative electrode material is zinc, the electrolyte is 0.5M to 3M zinc sulfate aqueous solution, and the electrode material of the positive electrode or the negative electrode is respectively A secondary battery having a manganese (II) salt added to 20% by weight or less based on the total weight. 4. The secondary battery according to claim 3, wherein, after the battery configuration, all or part of the manganese (II) salt added to the electrode material is dissolved toward the electrolyte to form a mixed aqueous solution with zinc sulfate. Claim 3 or 4 wherein said positive electrode or manganese added to the electrode material for the negative electrode (Ⅱ) salt is manganese sulfate (MnSO _4), manganese nitrate to _{(Mn (NO 3) 3)} , manganese acetate (Mn (CO ₂ CH ₃ ) ₂ ), one or more selected from the group consisting of manganese chloride (MnCl ₂ ), manganese bromide (MnBr ₂ ) and manganese perchlorate (Mn (ClO ₄ ) ₂ ), and all of the manganese salts are dissolved in an electrolyte. The secondary battery has a concentration of less than 2M and a concentration of zinc sulfate.