WO2004082060A1

WO2004082060A1 - High current capacity battery

Info

Publication number: WO2004082060A1
Application number: PCT/JP2003/011154
Authority: WO
Inventors: Masahiko Hirata; Kazumi Fujiwara
Original assignee: Apex Energy Inc.
Priority date: 2003-03-13
Filing date: 2003-09-01
Publication date: 2004-09-23
Also published as: KR20050107500A; AU2003261869A1; KR101012086B1; JP4575783B2; JPWO2004082060A1

Abstract

A high current capacity air battery comprising at least one (4,5) of air storage structure (4) capable of retaining and passing oxygen as a positive electrode active material and electrolyte (5) capable of absorbing moisture from air. The air storage structure (4) comprises multiple particulate porous ceramics (41) composed mainly of carbon. The multiple porous ceramics (41) are in contact with each other, and the air storage structure (4) contains oxygen as a positive electrode active material in interstices (42) of the multiple porous ceramics (41). The electrolyte (5) comprises at least one of aluminum chloride and calcium chloride. Aluminum or an aluminum alloy is used as a negative electrode active material (2).

Description

'Specifications High current capacity batteries Technical field

The present invention relates to a battery having a high current capacity, that is, a battery having a long duration (discharge time). More specifically, the present invention relates to the electrolyte water and the positive electrode active material required for an electrochemical oxidation-reduction reaction. It is related to batteries that supplement oxygen and air from the air to sustain its redox reaction. Kyokyo technology

The principle of the battery is that a reducing agent and an oxidizing agent are reacted via an ionic conductor, and the free energy released during this oxidation-reduction reaction is directly converted into electric energy using two electrodes. Utilize the electromotive force.

1. Primary battery

A primary battery is a battery in which the oxidation-reduction reaction for extracting electrical energy proceeds in only one direction and cannot be charged. In other words, primary batteries are disposable batteries, unlike secondary batteries.

Manganese batteries as an example of a primary battery generally comprises manganese dioxide as a positive electrode active material (Mn_〇 _2), and zinc as a negative electrode active material (Zn). The manganese dry cell also has a solid electrolyte of ammonium chloride (NH ₄ C 1) solution as the electrolyte. The oxidation-reduction reaction of a manganese dry battery is expressed by the following equation.

Zn + 2NH ₄ C 1 + 2Mn0 ₂

_{_{→ Zn (NH 3) 2 C}} 1 2 + 2MnOOH ··· (1)

Manganese batteries are widely used because they are inexpensive. However, manganese dry batteries cannot be easily disposed of because manganese dioxide is used as the positive electrode active material.

Aluminum batteries as examples of primary batteries generally include manganese dioxide as a positive electrode active material and an aluminum alloy as a negative electrode active material (eg, aluminum Chromium alloy) and an aqueous solution of aluminum chloride as an electrolyte. The main oxidation-reduction reaction of an aluminum battery is expressed by the following equation.

A 1 + 3 0 ₂ + 6 H ₂ 〇

-> 4 A 1 (OH) 3… (2)

Aluminum batteries that use an aluminum alloy instead of zinc as the negative electrode active material have a higher current capacity (higher wattage per unit weight) than manganese dry batteries. The reason is that the discharge characteristics of aluminum are higher than those of zinc. In other words, in the reaction of equation (1), zinc dissolves in the electrolyte on the negative electrode side, and as a result, 4 e- electrons are generated, while in the reaction of equation (2), aluminum dissolves on the negative electrode side in the electrolyte. Because, as a result, three times as many electrons as 1 2 e are generated. However, the electrolyte (aluminum chloride aqueous solution) of the aluminum battery corrodes the negative electrode active material or the negative electrode (aluminum alloy), and hydrogen is generated on the negative electrode side along with the reaction of equation (2). This can cause the battery to swell and, in the worst case, cause the battery to burst.

In order to reduce such generation of hydrogen, the negative electrode active material of the aluminum battery is not an aluminum simple substance but an aluminum alloy. However, the generation of hydrogen cannot be avoided to the extent that it can be marketed. In order to further reduce such generation of hydrogen, Japanese Patent Application Laid-Open No. H06-18979 discloses an aluminum battery in which a stabilizer such as an alkyl group is added to a negative electrode active material. . However, it seems that this aluminum battery cannot avoid the generation of hydrogen to the extent that it can be sold.

2. Air battery

An air battery that uses oxygen (O ₂ ) in the air instead of an oxidizing agent such as manganese dioxide as the positive electrode active material has a higher current capacity than a primary battery. The reason is that oxygen in the air as a positive electrode active material is not consumed. The air battery further includes a metal (for example, zinc, aluminum, or the like) as a negative electrode active material, and an electrolytic solution (for example, an aqueous solution of potassium hydroxide, an aqueous solution of aluminum hydroxide, or the like) as an electrolyte. On the positive electrode side of the air battery, oxygen in the air is reduced as expressed by the following equation. 0 ₂ + 2 H ₂ 0 + 4 e

→ 4〇H— (3)

As shown in equation (3), an air battery requires water used for the oxidation-reduction reaction, and the water is supplied from the water in the electrolyte. Such water consumption depends on the type and amount of the metal as the negative electrode active material. On the other hand, the amount of such water supply depends on the type and amount of the electrolyte. Thus, if the water consumption is greater than the water supply, i.e., if the water content of the electrolyte is exhausted, the air cell will not operate before its full current capacity is removed. Such a phenomenon is known as dry-up. For example, in the case of a commercially available potan-type zinc-air battery (negative electrode active material: zinc), the amount of water consumed is less than the amount of water supplied, so that the water content of the electrolyte is hardly consumed. However, when increasing the amount of zinc as a negative electrode active material to produce an air battery with a high current capacity, it is necessary to consider the problem of dry-up. Alternatively, in order to avoid the problem of dry-up, it is necessary to increase the amount of the electrolyte in proportion to the increase in the amount of zinc. As a result, there is a problem that the air battery becomes large. In an air aluminum battery (negative electrode active material: aluminum) as an example of an air battery, water consumption is generally larger than water supply. For this reason, air aluminum batteries dry up faster than zinc air batteries. Furthermore, for example, when an aqueous solution of aluminum hydroxide is used as the electrolyte, hydrogen is generated on the negative electrode side.

Air batteries are generally expected to improve discharge efficiency by promoting the oxygen reduction reaction.

An air battery is a battery in which the oxidation-reduction reaction for extracting electric energy proceeds in only one direction, and is essentially a primary battery.

3. Fuel cell

A fuel cell using hydrogen (H ₂ ) instead of a metal such as zinc or aluminum as the negative electrode active material has a higher current capacity than a primary battery or an air battery. The reason is that hydrogen as a negative electrode active material is not consumed. The main oxidation-reduction reaction of a fuel cell is expressed by the following equation, and water is generated from hydrogen and oxygen. Negative electrode: H ₂ → 2 H ⁺ + 2 e

Positive electrode: 2 H ++ (1/2) 0 ₂ + 2 e → H ₂ 0… (4)

Fuel cells are generally expected to improve discharge efficiency by promoting the oxygen reduction reaction and / or the hydrogen oxidation reaction. Disclosure of the invention

Therefore, an object of the present invention is to solve the problem of dry-up in an air battery and to make the performance of the battery sufficiently function.

Another object of the present invention is to improve the safety of a battery by dealing with hydrogen generated on the negative electrode side of a primary battery or an air battery.

A further object of the present invention is to provide a commercially available air battery that uses aluminum or an aluminum alloy as the negative electrode active material by addressing the hydrogen generated on the negative electrode side.

It is a further object of the present invention to improve discharge efficiency by promoting a chemical reaction in an air cell or fuel cell.

It is a further object of the present invention to provide an environmentally friendly battery by using an alternative to manganese dioxide.

Other objects of the present invention will become apparent by referring to the embodiments of the invention described below.

In order to achieve the above object, the high current capacity air battery of the present invention has an air storage structure (4) for holding and passing oxygen, which is a positive electrode active material, and has a performance of inhaling moisture in the air. At least one (4, 5) of the electrolytes (5) is provided. The air containment structure (4) includes a plurality of granular porous ceramics (41) containing carbon as a main component. The plurality of porous ceramics (41) are in contact with each other, and the air containment structure (4) contains oxygen, which is a positive electrode active material, in gaps (42) between the plurality of porous ceramics (41). The electrolyte (5) includes at least one of aluminum chloride and calcium chloride. The negative electrode active material (2) is aluminum or an aluminum alloy. The gas storage structure for a battery according to the present invention includes a plurality of granular porous ceramics containing carbon as a main component for storing at least one of hydrogen and oxygen. The electrolyte solution (5) for an air battery according to the present invention includes at least one of aluminum chloride and calcium chloride. BRIEF DESCRIPTION OF THE FIGURES

The advantages and principles of the present invention will become apparent to those skilled in the art with reference to the accompanying drawings and the description of the best mode for carrying out the invention set forth below.

FIG. 1 is a perspective view showing the appearance of the air battery of the present invention.

FIG. 2 is a cross-sectional view of the air battery shown in FIG.

FIG. 3 is a detailed view of the air containment structure 4 shown in FIG.

FIG. 4 is a schematic cross-sectional view of an air battery of the present invention including a partition and a gas permeable membrane. FIG. 5 is a schematic cross-sectional view of an air battery of the present invention including a semipermeable membrane as a separator.

FIG. 6 is a schematic sectional view of a primary battery of the present invention having a gas storage structure.

FIG. 7 is a schematic perspective view of a fuel cell of the present invention having a gas storage structure. BEST MODE FOR CARRYING OUT THE INVENTION

As shown in FIGS. 1 to 3, the air battery 1 of the present invention generally includes an air storage structure 4 for holding and passing oxygen as a positive electrode active material, a negative electrode active material (negative electrode) 2, and an electrolyte 5. Prepare. The air battery 1 further includes a collecting electrode (positive electrode) 8, a separator 3, a negative electrode terminal 6, a positive electrode terminal 7, and a container 10.

As the negative electrode active material (negative electrode) 2, metals, alloys, and other similar materials (for example, zinc, magnesium, lithium, and aluminum) can be used. Preferably, the negative electrode active material 2 is aluminum or an aluminum alloy having high discharge characteristics (for example, an alloy mainly composed of aluminum such as duralumin or an alloy of aluminum and iron). The periphery of the negative electrode active material 2 is covered with a separator 3 to prevent direct contact with oxygen (positive electrode active material) in the air storage structure 4.

As the separator 3, a hydrophilic or water-resistant separator (eg, viscose, chemical fiber, foamed polymer, etc.) can be used. Separation area 3 shown in Fig. 2 is hydrophilic The electrolyte 5 described below is retained inside the separator 3. Separee 3 shown in FIG. 5 has water resistance and functions as a container for the electrolyte 5. The air cell 1 that uses a hydrophilic separator as shown in Fig. 2 has a higher electrolyte retention property, and therefore has a longer duration than the air cell 1 that uses a water-resistant separator as shown in Fig. 5. A small current can be passed over the entire area. The air battery 1 employing a water-resistant separator as shown in FIG. 5 can pass a larger current than the air battery 1 employing a hydrophilic separator as shown in FIG.

As the hydrophilic separator 3 shown in FIG. 2, for example, viscose, hydrophilic foamed polymer, or the like can be used. Preferably, the hydrophilic separator 3 is highly hygroscopic in order to bring the electrolyte 5 into uniform contact with the negative electrode active material 2. The hydrophilic separator 3 prevents direct contact between the negative electrode active material 2 and oxygen (positive electrode active material) in the air storage structure 4 and also allows the electrolyte 5 to efficiently contact the negative electrode active material 2 with a separator. 3 requires a thickness, and the separator 3 works as long as it is 1 m or more. However, since the electrical resistance increases when the separator 3 is too thick, the thickness of the separator 3 is preferably 1 mm to 10 mm. The area around Separe Night 3 is in contact with the air in the air containment structure 4 and the air in the container 10.

As the water-resistant separator 3 shown in FIG. 5, for example, a chemical fiber, a water-resistant foamed polymer, or the like can be used. Preferably, the water-resistant separator 3 has a high ionic conductivity in order to promote a redox reaction. The water-resistant separator 3 prevents separation of the negative electrode active material 2 from oxygen (positive electrode active material) in the air storage structure 4 directly, and separates the electrolyte 5 from the negative electrode active material 2. 3 functions as a container for electrolyte 5. The thickness of the separator 3 is preferably from 0.01 mm to 10 mm, since the electrical resistance increases when the separator 3 is too thick. The area around Separee 3 is in contact with the air in the air containment structure 4 and the air in the container 10. The air storage structure 4 holds and passes oxygen, which is a positive electrode active material. The element 41 of the air containment structure 4 shown in FIG. 3 is, for example, a granular porous ceramic mainly composed of carbon. Preferably, element 41 is a spherical porous ceramic. Methods for producing spherical porous ceramics include: a) for example, at least one of ground cuticle, ground coal, and tar refined from petroleum. And zinc chloride or copper sulfate are mixed and kneaded.b) The kneaded product is molded into, for example, a 0.5 mm particle size.c) The molded product is carbonized in an oxygen-free state. ) The carbonized material is activated by steam. The activated spherical porous ceramic is, for example, $ 700 OH-3J available from Nippon Environmental Chemicals Co., Ltd. Preferably, the diameter of the spherical porous ceramic is approximately between 0.5 mm and 1.2 mm. In addition, the porous ceramic is preferably as low in ash content as possible. This is because ash is a component of internal resistance. Although the internal resistance due to the presence of a large amount of ash deteriorates the discharge characteristics of the negative electrode active material, the ash content of a generally available porous ceramic is about 4% by weight. No deterioration is noticeable. Therefore, preferably, the ash content of the porous ceramic is not more than 4% by weight. In addition, the specific surface area of the porous ceramic is preferably 1000 m ² / g or more, more preferably 2000 m ² Zg or more.

d) After activating the carbonized porous ceramic with steam, e) Wash the activated material with purified water, and f) Dry the washed material. e) By washing with purified water, powdery porous ceramics or non-granulated porous ceramics can be removed. If powdered porous ceramic is used as the element 41 of the air containment structure 4, the powdered porous ceramic enters the hydrophilic separator 3, resulting in the powdered graphite ceramic. There is a problem that oxygen (the positive electrode active material) and the negative electrode active material 2 come into direct contact with each other, that is, a problem that the hydrophilic separation 3 does not function. In other words, by using a granular (preferably spherical) porous ceramic as the element 41 of the air containment structure 4, the hydrophilic separator 3 can continue to function. Since the powdery porous ceramic does not enter into the water-resistant separator 3, the activated granular (preferably spherical) porous ceramic does not need to be washed.

The elements 41 (granular (preferably spherical) porous ceramics) produced in this manner are brought into contact with each other, and oxygen 42, which is a positive electrode active material, is contained in the gaps between the elements 41. The air containment structure 4 as shown is obtained. Preferably, the spherical elements 41 are arranged in a container 10 in a hexagonal close-packed structure. The air storage structure 4 retains oxygen 42 in the air, and the oxygen 42 as the positive electrode active material passes through the air storage structure 4. Such an air storage structure 4 makes it possible to promote the chemical reaction (reduction reaction of oxygen) of the air battery, thereby improving the discharge efficiency. The air storage structure 4 (element 4 1) in contact with the periphery of the separator 3 has a thickness of 1 mm or more based on the surface of the negative electrode active material 2-. The oxygen contained in the air storage structure 4 is-. Function as In other words, the positive electrode active material is substantially consumed unless oxygen as the positive electrode active material is supplied to the positive electrode to some extent. Conversely, when oxygen as the positive electrode active material is continuously supplied to the positive electrode side, oxygen as the positive electrode active material is continuously reduced at the positive electrode side, and the positive electrode active material is not consumed. It was experimentally confirmed that the positive electrode active material continuously reacted when the thickness of the air containment structure 4 (element 41) was 10 mm or more with respect to the surface of the negative electrode active material 2.

Preferably, in producing the air containment structure 4, f) after drying the element 41 (porous ceramic), g) placing the element 41 in, for example, a 4% aqueous sodium chloride solution, or An aqueous solution of sodium chloride is impregnated into the element 41, thereby increasing the contact area between the elements 41. This makes it easier for the electrons discharged from the negative electrode active material 2 to pass through the air storage structure 4 and lowers the internal resistance. Therefore, a high current capacity can be obtained.

As shown in FIG. 2, the collector electrode (positive electrode) 8 is provided so as to be in contact with the positive electrode active material (air storage structure 4), so that current can be extracted from the collector electrode 8. The container 10 houses the negative electrode active material 2, the separator 3, the air storage structure 4 (oxygen as the positive electrode active material), the electrolyte 5, and the collector 8. Negative electrode terminal 6 and positive electrode terminal 7 are electrically connected to negative electrode active material 2 and collector electrode 8, respectively. The negative electrode terminal 6 and the positive electrode terminal 7 are provided through the container 10. Since the gap between at least one of the negative electrode terminal 6 and the positive electrode terminal 7 and the container 10 is not closed, oxygen in the air outside the container 10 is taken into the outside of the container 10 from the gap. Can be. In addition, by closing the gap between the negative electrode terminal 6 and the positive electrode terminal 7 and the container 10 and providing the container 10 with a ventilation hole or a vent, oxygen in the air can be taken into the container 10. Good.

As shown in FIG. 4, in the air battery 1 of the present invention, the element 41 of the air storage structure 4 is fixed to some extent, and the lead wire connecting the electrode and the terminal and the electrode are corroded (by the electrolyte 5). In order to prevent corrosion of the air, a partition 11 covering the upper part of the air containment structure 4 can be provided. The partition 11 is, for example, a non-corrosive substance (for example, plastic). A part of the partition 11 is provided with a ventilation means 12 (for example, a ventilation film), and air (oxygen and moisture) taken in from the outside of the container 10 is supplied to the air through the ventilation means 12. Taken into storage structure 4. The ventilation means 12 is, for example, Goatex fiber.

Returning to FIG. 2, the collecting electrode 8 is, for example, carbon or a carbon compound. Preferably, collector electrode 8 is graphitized carbon or a carbon compound. For carbon or carbon compounds, the lower the ash content, the better. This is because ash is a component of internal resistance. Although the internal resistance due to the presence of a large amount of ash deteriorates the discharge characteristics of the negative electrode active material, usually available ash of carbon or carbon compound is about 4% by weight. No worsening is observed. Therefore, preferably, the ash content of the carbon or carbon compound is not more than 4% by weight.

Electrolyte 5 has the ability to inhale moisture in the air. One example of the electrolyte 5 is an aqueous solution of aluminum chloride. Another example of electrolyte 5 is an aqueous solution of calcium chloride. Electrolyte 5 has the ability to inhale moisture in the air, so even if the amount of water used for the oxidation-reduction reaction is large, water corresponding to that amount can be taken in from the air. it can. In other words, the electrolyte 5 not only supplies water by its own internal moisture, but also removes the moisture in the air from the ventilation means of the container 10 (the connection between the negative electrode terminal 6 and the positive electrode terminal 7 and the container 10). The air can be taken in through a gap between them, a vent or a vent provided in the container 10) and, if the vent 12 is provided, through the vent 12 of the partition 11. As a result, the water consumption is balanced with the water supply, and as a result, the dry-up phenomenon can be avoided, and the performance of the battery can be fully functioned.

In addition, even when hydrogen chloride is generated on the negative electrode side using an aqueous solution of aluminum chloride as the electrolyte 5, the air containment structure (gas containment structure) 4 retains oxygen 42 in the air, The hydrogen generated on the side can be retained. Thereby, the safety of the battery can be improved. In other words, even if aluminum or an aluminum alloy having high discharge characteristics is used as the negative electrode active material 2, The problem of hydrogen generated on the side can be avoided. The problem of hydrogen generated in the container (collapse of the container) can be avoided by configuring the container 10 with a non-corrosive substance (eg, plastic) instead of a corrosive substance (eg, aluminum). can do.

Preferably, the electrolytic solution 5 is an aqueous solution in which a substance capable of inhaling moisture is dissolved to a saturated concentration (for example, a saturated aluminum chloride aqueous solution, a saturated calcium chloride aqueous solution, and the like). The reason is that even if the electrolyte 5 inhales the moisture in the air, the concentration of the electrolyte 5 is constant at the saturation concentration. That is, when the concentration of the electrolytic solution 5 is stabilized, a stable current value and voltage value can be supplied. It should be noted that the Shiridani calcium aqueous solution has a higher water absorption than the aluminum chloride aqueous solution, so that more stable current and voltage values can be supplied.

More preferably, the electrolytic solution 5 is an aqueous solution in which both aluminum chloride and calcium chloride are dissolved to a saturation concentration. The aqueous solution of calcium chloride takes in oxygen dioxide in the air and produces an aqueous solution of carbon dioxide, while the aqueous solution of calcium chloride reacts with carbon dioxide to produce a substance that inhibits electricity (calcium carbonate). However, since the Ph of an aqueous solution containing not only calcium chloride but also a chloride salt (for example, aluminum chloride) is smaller (more acidic) than the pH of an aqueous solution of carbon dioxide, aluminum chloride and chloride An aqueous solution in which both calcium are dissolved has a property that aluminum chloride and carbon dioxide gas are unlikely to react with each other, and it is difficult to generate a current-carrying substance (calcium carbonate). Therefore, the discharge efficiency can be improved when the electrolytic solution 5 contains both aluminum chloride and calcium chloride. In addition, when the negative electrode active material (negative electrode) 2 is aluminum or an aluminum alloy, the chloride salt is preferably aluminum chloride. Since the aqueous solution in which both aluminum chloride (chloride salt) and calcium chloride are dissolved has aluminum as an ion of the same element as the negative electrode, the redox reaction can be promoted. Thereby, the discharge efficiency can be improved.

Also, preferably, the electrolyte 5 further comprises a neutral salt (eg, sodium chloride, calcium chloride, ammonium chloride, potassium chloride, and the like, and combinations thereof). When the concentration of neutral salt exceeds 0.1% by weight To the extent neutral salts can function and increase the ionic conductor, thereby improving discharge efficiency. Preferably, the concentration of the neutral salt is a saturating concentration.

When the electrolyte 5 is liquid and acidic More preferably, the electrolyte 5 further contains a compound of a halide and hydrogen (for example, hydrogen chloride). When the concentration of hydrogen chloride is greater than 0.1% by weight, it functions to convert poorly soluble products (eg, A 1 (OH) ₃ in the formula (2)) generated by the redox reaction into water soluble. be able to. That is, the poorly soluble product which is a current blocking substance is removed, thereby improving the discharge efficiency. However, it is not preferable that a large amount of hydrogen chloride is present in the electrolyte 5. The reason is that a large amount of hydrogen chloride actively dissolves the negative electrode active material (eg, aluminum) in addition to the reaction as a battery. Thus, preferably, the concentration of hydrogen chloride is 0.1% by weight.

If the electrolyte 5 is liquid and alkaline, more preferably, the electrolyte 5 further comprises a water-soluble base (e.g., sodium hydroxide, ammonium, calcium hydroxide, and the like, and combinations thereof). ) including. The water-soluble base functions in the range of 0.1% by weight or more and 10% by weight or less to form a poorly soluble product (for example, A 1 (OH) ₃ in the formula (2)) generated by the redox reaction. ) Can be changed to water-soluble. In other words, poorly soluble products that are current-disturbing substances are removed, thereby improving discharge efficiency.

The electrolyte 5 may be held inside the separator 3 and the air containment structure 4 as shown in FIG. 2, or may be stored inside the separator 3 as a container as shown in FIG. And may be held inside the air containment structure 4.

In addition, the use of oxygen in the air instead of manganese dioxide as the positive electrode active material, and the elimination of manganese dioxide for element 4 1. of the air containment structure 4 allows for environmentally friendly batteries. Can be provided.

It should be noted that the air battery of the present invention is not limited to the above-described embodiment and examples described later, and it is needless to say that various changes can be made without departing from the gist of the present invention.

For example, as shown in FIG. 6, the air storage structure 4 of the air battery could be adopted as the gas storage structure 63 of the primary battery. This allows the primary battery electrolyte and 3 011154

Even when hydrogen is generated on the negative electrode 65 side using an aluminum chloride aqueous solution, the gas storage structure 63 can hold the hydrogen generated on the negative electrode side. A primary battery generally includes a positive electrode 61, a collector electrode 62, a gas storage structure 63 that holds oxygen as a positive electrode material, a separator 64, and a negative electrode active material (negative electrode) 65. I can.

Also, as shown in FIG. 7, the air storage structure 4 of the air cell could be adopted as the gas storage structure 72, 74 of the fuel cell. Thereby, the oxidation-reduction reaction of the fuel cell can be promoted. The fuel cell (single cell) generally includes a separator 71, a fuel electrode 72 using a gas storage structure, an electrolyte 73, and an air electrode 74 using a gas storage structure.

Example 1

One example of the air battery 10 shown in FIG. 2 will be described below. The negative electrode active material (negative electrode) 2 is an aluminum plate, the thickness is 3 mm, the width is 55 mm, the length is 90 mm, and the weight of the aluminum plate is 4 2 g. Separe Ichi 3 is a hydrophilic separee, a 1 mm thick rayon fiber corroded cloth mainly composed of fibrous viscose. The aluminum plate is covered with a rayon fiber corroded cloth to prevent direct contact with other components. The aluminum plate covered with the rayon fiber corroded cloth is placed in a container 10 capable of securing a thickness of 10 mm or more in any direction from the surroundings of the rayon fiber corroded cloth. The width of the container 10 is 57 mm, the thickness is 15 mm, and the height is 92 mm.

The element 41 of the air containment structure 4 is {700} -3 available from Nippon Environmental Chemicals Co., Ltd., and is a spherical porous ceramic. The average diameter of the spherical porous ceramic is about 5 mm. The spherical porous ceramic is washed with purified water, and the washed one is dried. 50 g of the spherical porous ceramic thus washed with the purified water is filled around an aluminum plate (rayon fiber corroded cloth) placed in the container 10. The specific surface area of the porous ceramic spherical is ^{1 0 0 0 m 2 Z g} .

The collector electrode 8 is a graphite plate mainly composed of carbon, has a thickness of 0.5 mm, a width of 55 mm, and a length of 90 mm. Place the graphite plate in the air containment structure 4 (required (Between element 41).

As the electrolyte 5, an electrolytic solution obtained by adding 1 weight of hydrochloric acid to an aqueous solution in which aluminum chloride is dissolved to a saturation concentration is used. The electrolyte is poured into the corroded rayon cloth at 40 cc so that the electrolyte is retained inside the corroded rayon fiber cloth covering the aluminum plate. At this time, the electrolyte is also retained in the element 41 of the air containment structure 4. One of the voltmeter clips was connected to an aluminum plate (negative electrode), and the other clip was connected to a graphite plate (positive electrode) .The electromotive voltage between both electrodes was measured, and an electromotive voltage of 1.2 V was obtained. . Furthermore, an ammeter with a 0.1 Ω resistor connected to it (for example, a DC current / voltmeter 2012 available from Yokogawa Electric Corporation) was connected in parallel. A current of 1 A was obtained. When the 0.1 Ω resistor was removed and the short-circuit current was measured, a current of 2.8 A was obtained.

Furthermore, when an ammeter connected to a 20Ω resistor was connected in parallel to the voltmeter, a current of 50 mA was obtained. When this state was left for 30 days, the electromotive voltage was IV and the current remained at 50 mA.

When the discharge capacity thus far was calculated, the discharge capacity of Example 1 was 1.1VX0.05AX (24 hours × 30 days) = 39.6 Wh.

When the aluminum plate after such a redox reaction was washed and its weight was measured, the weight of the aluminum plate was 38 g, which was 4 g less than before the reaction.

Comparative Example 1

As a comparative example, a similar test was conducted using a commercially available single manganese electrode. The electromotive voltage was 1.5 V, and a voltage drop from 1.5 V to 1.0 V was observed in 48 hours. Was called. The current during the voltage drop was 50 mA. When the discharge capacity in this case was calculated, the discharge capacity of Comparative Example 1 was 1.25 VX 0.05 mAX (24 hours × 2 days) = 3 Wh.

The total weight of the components of the air battery of Example 1 employing an aluminum plate as the negative electrode was 150 g. The weight of the single battery as Comparative Example 1 was also 150 g. Therefore, the discharge capacity of the air battery of Example 1 employing aluminum as the negative electrode was 13 times or more that of a single battery that is widely used. Example 2 With respect to another example of the air battery 10 shown in FIG. 2, only differences from the first embodiment will be described below. Instead of the electrolyte 5 of Example 1, the electrolyte 5 of Example 2 was prepared by adding 420 g / 'J liter of calcium chloride and 20 cc / liter of ammonia (a water-soluble base) to 1 liter of purified water. Use electrolyte. Pour 50 cc of this electrolyte into a rayon fiber corroded cloth.

One of the voltmeter clips was connected to an aluminum plate (negative electrode), and the other clip was connected to a graphite plate (positive electrode). The electromotive voltage between both electrodes was measured, and an electromotive voltage of 1.5 V was obtained. . Furthermore, when an ammeter connected to a 0.1 Ω resistor was connected in parallel to the voltmeter, a current of 1.1 A was obtained. When the 0.1 Ω resistor was removed and the short-circuit current was measured, a current of 2.2 A was obtained.

Prepare a voltage and current measuring instrument with the 0.1 Ω resistor connected to the ammeter replaced by 3 Ω. That is, prepare one with a 3 Ω resistor connected in series with an ammeter in series with a voltmeter in parallel. Connect one of the clips for the voltmeter and the ammeter to the aluminum plate (negative electrode). Is connected to a graphite plate (positive electrode). The electromotive voltage and current were measured with a final voltage of 1.0 V. At 7 days, 2 hours and 17 minutes, the electromotive voltage of the air battery of Example 2 reached the cutoff voltage.

When a similar test was performed using the manganese single battery of Comparative Example 1, the electromotive voltage of the unit battery of Comparative Example 1 reached the cutoff voltage in 5 hours and 49 minutes.

The starting voltage of both the air battery of Example 2 and the single battery of Comparative Example 1 was 1.5 V, and the current at the starting voltage was 0.5 A. In addition, the current at the final voltage was 0.34 A in both cases.

The discharge capacity of the air battery of Example 2 and the single battery of Comparative Example 1 were calculated using the following formula.

Discharge capacity = ((1.5 + 1.0) / 2) X ((0.5 + 0.34) / 2) X (discharge time (hr))

As a result of the calculation, the discharge capacity of the air battery of Example 2 was 89.4 Wh, and the discharge capacity of the single battery of Comparative Example 1 was 3. OWh. The weight of both the air battery of Example 2 and the single battery of Comparative Example 1 was 150 g. From the above, it can be seen that the air battery of Example 2 has about 30 times the discharge capacity in the practical range as compared with the single battery of Comparative Example 1. It turned out.

Example 3

With respect to another example of the air battery 10 shown in FIG. 2, only differences from the first embodiment will be described below.

The thickness of the aluminum plate as the negative electrode active material (negative electrode) 2 is 5 mm, the width is 100 mm, the length (height) is 150 mm, and the weight of the aluminum plate is 2 10 g It is. The width of the container 10 made of vinyl chloride is 50 mm, the thickness is 50 mm, and the height is 160 mm. The hydrophilic separator 3 is a sponge made of a foamed melamine resin which is a fiber. Around the aluminum plate (sponge) placed in the container 10, 940 cc (676 g) of spherical porous ceramic washed with purified water is filled. The thickness of the graphite plate as the collecting electrode 8 is lmm, the width is 100 mm, and the length is 150 mm. The same electrolytic solution as in Example 1 (an electrolytic solution obtained by adding 1% by weight of hydrochloric acid to an aqueous solution in which aluminum chloride is dissolved to a saturation concentration) is poured into a sponge at 150 cc.

Six air cells manufactured in this way were prepared, and these air cells were connected in a state of being electrically connected in series. The LED was turned on when an air-battery connected in series was connected to an arrow wing (6 V, averaging 50 mA consumption type), which is a road sign used in heavy snowfall areas. An air battery and arrow blades were installed outdoors, and the LED was turned on continuously. The LED turned off on the 372th day.

After this experiment, the aluminum plate was washed out and its weight was measured. The weight of the aluminum plate was 10 g, which was 200 g less than before the experiment. Thus, a discharge capacity of 2678 Wh could be obtained from 200 g of aluminum. That is, the air battery of Example 3 generated 13.4 Wh per g of aluminum.

Example 4

With respect to another example of the air battery 10 shown in FIG. 2, only differences from the third embodiment will be described below. In place of the electrolyte 5 of the example 3, the electrolyte 5 of the example 2 was prepared by adding 420 g, liter of calcium chloride and 20 cc, no liter of ammonia to 1 liter of purified water in the same manner as in the example 2. Electrolyte. Pour 150 cc of this electrolyte into the sponge. Six air cells manufactured in this way were prepared, and these air cells were connected in a state of being electrically connected in series. When three high-brightness white LEDs (operating at 5 V or more and 0.5 A) are connected in parallel to the air batteries connected in series in this way, the white LEDs are connected. Lights up. The white LED was on. The lighting test was continued for more than 100 days at 20 degrees Celsius, normal temperature of 1 atmosphere and normal pressure. After the 100th day, the white LED continued to light.

Example 5

Regarding another example of the air battery 10 shown in FIG. 2, only differences from the first embodiment will be described below. Instead of the separator 3 in Example 1, the separator in Example 5 is a natural pulp material. Further, instead of the electrolyte 5 of the example 1, the electrolyte 5 of the example 5 is obtained by adding 745 g / liter of calcium chloride and 450 gZ liter of aluminum chloride hexahydrate to 1 liter of purified water. Use the added electrolyte. That is, the electrolyte 5 of Example 5 is an aqueous solution in which both calcium chloride and aluminum chloride in a weight ratio of 5: 3 are dissolved to a saturation concentration. This electrolytic solution is poured into a natural pulp material at 42 cc.

When one of the voltmeter clips was connected to an aluminum plate (negative electrode) and the other clip was connected to a graphite plate (positive electrode), and the electromotive voltage between both electrodes was measured, the electromotive voltage of 1.15 V was measured. Obtained. Further, when an ammeter connected to a 0.1 Ω resistor was connected in parallel to the voltmeter, a current of 1.9 A was obtained. When the 0.1 Ω resistor was removed and the short-circuit current was measured, a current of 2.1 A was obtained.

Example 6

Regarding one example of the air battery 10 shown in FIG. 5, only differences from the fifth embodiment will be described below. Instead of the separation 3 of Example 5, the water-resistant separation 3 of Example 6 is cellophane. In addition, the same electrolyte solution as in Example 5 (chloride strength of 5: 3, an aqueous solution in which both calcium and aluminum chlorides were dissolved to a saturation concentration) was added to 3 cc of cellophane as a container and 39 cc to an air containment structure 4. Pour cc. At this time, the surface of the aluminum plate in the cellophane is in contact with the electrolyte.

One of the voltmeter clips was connected to an aluminum plate (negative electrode), and the other was connected to a graphite plate (positive electrode). The electromotive voltage between both electrodes was measured. An electromotive voltage was obtained. Furthermore, an ammeter with a 0.1 Ω resistor connected in parallel to the voltmeter resulted in a current of 2.85 A. The 0.1 Ω resistor was removed, and the short-circuit current was measured.

Claims

The scope of the claims

1. a high current capacity air battery,

An air storage structure (4) that holds and passes oxygen, which is the positive electrode active material, and an electrolyte (5) that has the ability to inhale moisture in the air.

2. The high current capacity air battery according to claim 1, wherein

A high current capacity air battery in which the air containment structure (4) includes a plurality of granular porous ceramics (41) containing carbon as a main component.

3. The high current capacity air battery according to claim 2, wherein

Multiple porous ceramics (41) contact each other,

A high current capacity air battery in which the air storage structure (4) contains oxygen as a positive electrode active material in gaps (42) between a plurality of porous ceramics (41).

4. The high current capacity air battery according to claim 3, wherein

The high current capacity air battery includes a separator (3) between the air storage structure (4) and the negative electrode active material (2),

A high current capacity air battery in which the thickness of the air containment structure (4) is at least lmm based on the surface of the negative electrode active material (2).

5. The high current capacity air battery according to claim 4, wherein

A high-current-capacity air battery in which the thickness of the air containment structure (4) is 1 Omm or more based on the surface of the negative electrode active material (2).

6. The high current capacity air battery according to claim 2, wherein

A high current capacity air battery with a granular porous ceramic (41) that is hydrophilic.

7. The high current capacity air battery according to claim 1, wherein

A high current capacity air battery, wherein the electrolyte (5) comprises at least one of aluminum chloride and calcium chloride.

8. The 髙 current capacity air battery according to claim 7, wherein

The high current capacity air battery, wherein the electrolyte (5) is an aqueous solution in which at least one of aluminum chloride and calcium chloride is dissolved to a saturation concentration.

9. The high current capacity air battery according to claim 1, wherein The high current capacity air battery, wherein the negative electrode active material (2) of the high current capacity air battery is aluminum or an aluminum alloy.

10. Gas storage structure for battery,

A gas storage structure comprising a plurality of granular porous ceramics containing carbon as a main component for storing at least one of hydrogen and oxygen.

11. The gas containment structure according to claim 10, wherein

Multiple porous ceramics contact each other,

A gas storage structure in which the gas storage structure contains oxygen, which is a positive electrode active material, in gaps between a plurality of porous ceramics.

12. The gas containment structure according to claim 10, wherein

Multiple porous ceramics contact each other,

A gas storage structure for a fuel cell, wherein the gas storage structure contains hydrogen, which is a negative electrode active material, in a gap between a plurality of porous ceramics.

1 3. Electrolyte (5) for air battery,

An electrolytic solution comprising at least one of aluminum chloride and calcium chloride.