JP2015125830A - Air magnesium battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an air magnesium battery which is excellent in water repellency, gas permeability and liquid leakage resistance, and capable of reaching the peak of discharge reaction soon, and discharging a current of a constant magnitude for a relatively long time.SOLUTION: In an air magnesium battery 10, a cathode body 20 is constituted of: a first layer consisting of a porous body formed by mixing a conductive carbon material and fluororesin; and a second layer consisting of a porous body bonded to one side of the first layer so as to come into contact with a reaction solution 24 in an outer frame 17, and formed by mixing active carbon and fluororesin.

Description

  The present invention relates to a fuel cell that generates power using a fuel such as air or water, and more particularly to an air magnesium cell.

  Conventionally, a fuel cell that uses a natural fuel such as air or water as a positive electrode and uses magnesium or the like as a negative electrode is known. For example, Patent Document 1 discloses a cathode body in which a mixture of catalyst powder, activated carbon and fluororesin powder is formed into a sheet, and a porous film (water repellent film) formed from a fluororesin is laminated on one surface of the sheet. A fuel cell used is disclosed.

JP-A-6-338355

    In the air battery disclosed in Patent Document 1, a cathode body excellent in water repellency and adhesion can be obtained by pressure-bonding a water-repellent film to a catalyst sheet. However, the water-repellent film is relatively thin and easily broken, and there is a problem in that the reaction solution leaks from the broken portion during use and charging / discharging cannot be performed sufficiently.

  An object of the present invention is to improve an air magnesium battery in the prior art, which is excellent in water repellency, air permeability and liquid leakage resistance, and immediately reaches the peak of the discharge reaction and has a constant size for a relatively long time. It is related with the provision of the air magnesium battery which can discharge the electric current.

  In order to solve the above problems, the present invention is directed to an air magnesium battery including an outer frame, a cathode body fixed to the outer frame, and an anode body located inside the outer frame. .

  In the air magnesium battery according to the present invention, the cathode body is in contact with the first layer made of a porous body formed by mixing a conductive carbon material and a fluororesin, and the reaction solution in the outer frame body. And a second layer made of a porous body formed by mixing activated carbon and fluororesin and bonded to one surface of the first layer.

  As one embodiment of the present invention, a third layer made of a conductive metal material is bonded to the other surface of the first layer located on the opposite side of the one surface.

  As another embodiment of the present invention, the mixing ratio of the fluororesin mixed in the first layer is about 10 to 50% by weight, and the mixing ratio of the fluororesin mixed in the second layer is Is about 3 to 30% by weight.

  As another embodiment of the present invention, the second layer has a smaller outer dimension than the first layer, and the third layer is narrower than the second layer.

  As still another embodiment of the present invention, the third layer is a porous body.

  As still another embodiment of the present invention, the outer frame body includes a liquid injection area composed of a reaction liquid injected into the inside, a space located above the liquid injection area, and the liquid injection area. A ventilation system comprising a float floating on a liquid surface and a ventilation pipe for exhausting the generated gas inside, one end of the ventilation pipe is connected to an opening formed on the outer surface of the outer frame body, The other end of the vent pipe is connected to a joint that penetrates the float, and an open end of the joint is located in the space.

  As still another embodiment of the present invention, the outer frame body has a convex cross section, and has a narrow part and a wide part that communicate with each other, and the anode body and the cathode body, Are positioned opposite to each other in either one of the narrow part and the wide part.

  As still another embodiment of the present invention, a pair of inner walls facing each other are provided between the narrow portion and the wide portion inside the outer frame body.

  In still another embodiment of the present invention, the average pore diameter in the first layer is about 1 to 200 nm, and the pore volume is 0.1 to 4.0 ml / g.

  In still another embodiment of the present invention, the average pore diameter in the second layer is about 1 to 200 nm, and the pore volume is 0.1 to 3.0 ml / g.

  As still another embodiment of the present invention, a light source electrically connected to the cathode body and the anode body is further included.

  As still another embodiment of the present invention, the apparatus further includes an operation unit operable to turn on / off the electric power supply to the light source.

  According to the air magnesium battery of the present invention, the cathode body is in contact with the first layer made of the porous body formed by mixing the conductive carbon material and the fluororesin, and the reaction liquid in the outer frame body. And a second layer made of a porous body formed by mixing activated carbon and fluororesin and bonded to one surface of the first layer, and is excellent in water repellency and air permeability and has a cathode body. As compared with the case where is formed only from the first layer or the second layer, the peak of the discharge reaction can be reached early and a constant current can be generated for a relatively long time. Further, since the entire cathode body is formed of a porous body, the specific surface area is increased and a large amount of oxygen can be taken in, so that a larger current can be generated.

The perspective view of the air magnesium battery in 1st Embodiment of this invention. (A) The partially broken top view of a cathode body, (b) Typical sectional drawing which follows the IIB-IIB line | wire of Fig.2 (a). Sectional drawing which follows the III-III line of FIG. The typical sectional view similar to FIG.2 (b) which shows an example of the example of a change of a cathode body. The graph which shows the mode of the time change of the discharge current value of an air magnesium battery at the time of changing the composition of a 1st-3rd layer, and the structure of a cathode body. The partially broken perspective view of the air magnesium battery in 2nd Embodiment. FIG. 7 is a schematic sectional view taken along line VII-VII in FIG. 6. Typical sectional drawing which follows the VIII-VIII line of FIG. Typical sectional drawing similar to FIG. 7 in the non-electromotive state of an air magnesium battery. The perspective view of the air magnesium battery in 3rd Embodiment. FIG. 11 is a schematic cross-sectional view taken along line XI-XI in FIG. 10. Typical sectional drawing similar to FIG. 11 which shows an example of the example of a change of the air magnesium battery in 3rd Embodiment. (A) The front view of the air magnesium battery in 4th Embodiment, (b) The partially broken side view of the air magnesium battery in 4th Embodiment.

<First Embodiment>
1 and 2, an air magnesium battery 10 according to the present embodiment has a longitudinal direction Y and a transverse direction X, and a thickness direction Z perpendicular thereto, and the first and second facing each other in the longitudinal direction Y. A rectangular outer surface having second surfaces 11, 12, third and fourth surfaces 13, 14 facing each other in thickness direction Z, and fifth surface 15 and sixth surface 16 facing each other in transverse direction X. A frame 17 is included. The air magnesium battery 10 has a dimension L1 in the longitudinal direction Y of about 50 to 100 mm, a dimension W1 in the thickness direction Z of about 20 to 70 mm, a dimension W2 in the transverse direction X of about 20 to 70 mm, and about 1.0. An electromotive force of up to 2.0V can be generated. The air magnesium battery 10 can also be used as a power source for an electromechanical device installed in a large tanker such as a ship or a power source in an emergency such as a disaster. In such a case, each dimension L1, W1, W2 Can have a size of several meters or more, and can generate more power by combining them in a composite manner.

  The outer frame body 17 is made of a hard plastic material, and a rectangular thin plate-like cathode body (air electrode) 20 is located on the third surface 13. The outer frame body 17 has a rod-shaped anode. The body 21 is inserted so that it can be inserted and removed. A required amount of the reaction liquid 24 can be injected into the outer frame body 17, and a liquid having a capacity of about 60 to 80% of the allowable capacity of the entire outer frame body 17 is injected into the outer frame body 17. A liquid injection area 25 and a space S located above the liquid injection area 25 are formed. A lid body 26 having an opening at the center is detachably screwed to the first surface 11 of the outer frame body 17, and the end 21 a of the anode body 21 is fixed to the opening while being inserted. The end 21a of the anode body 21 is provided with a through hole, and a lead wire 28 is attached to the through hole. A lead wire 29 is attached to the cathode body 20 and extends to the outside of the outer frame body 17.

  In the air magnesium battery 10 having such a configuration, when the reaction liquid 24 is injected into the outer frame body 17, the reaction liquid 24 acts as an oxidation catalyst, and an ionization reaction occurs between the cathode body 20 and the anode body 21. Occurs. Electrons generated from the ionized anode body 21 react with oxygen in the cathode body 20 and water in the reaction liquid 24 to cause a discharge reaction, and a potential difference is generated between the cathode body 20 and the anode body 21 to cause a predetermined occurrence. Generate power. By generating such an electrochemical reaction, magnesium hydroxide and a reactive gas (hydrogen gas) are generated in the outer frame body 17. As the reaction solution 24, a reaction solution such as salt water can be used in addition to water. By removing the lid body 26, the anode body 21 is extracted from the outer frame body 17, the electrochemical reaction ends, and no electromotive force is generated. Further, by removing the lid 26, it is possible to inject a liquid such as water into the outer frame 17 or to discharge the internal liquid in order to inject a new liquid. The anode body 21 can use an electrode active material having a relatively large ionization tendency, such as metal magnesium, aluminum, zinc, and the like.

  The cathode body 20 is formed by laminating a plurality of layers, and is formed on a first layer (electrode layer) 31 formed of a conductive material such as a carbon material and one surface 31 a of the first layer 31. A second layer (active layer) 32 formed from a positive electrode active material such as attached activated carbon, and a plate-like third layer (made of conductive metal) attached to the other surface 31b of the first layer 31 ( Current collecting layer) 33. In the cathode body 20, the side on which the second layer 32 is disposed is located in the outer frame body 17, and the first layer 31 is located so as to extend from the entire surface of the second layer 32 and the outer periphery of the second layer 32. One surface 31 a is in contact with the reaction solution 24 in the outer frame body 17.

  The first layer 31 has a porous sheet shape formed by mixing a fluororesin with a predetermined ratio in an air-impermeable and liquid-impermeable carbon material, and the mixing ratio (weight ratio) of the fluororesin is About 3 to 50% by weight, preferably about 10 to 50% by weight, more preferably about 20 to 40% by weight. This is because when the mixing ratio of the fluororesin is 50% by weight or more, the insulation property of the entire first layer 31 becomes high, and the conductivity as the electrode film may not be sufficiently exhibited. As the carbon material used for the first layer 31, for example, graphite or carbon black having water repellency and electric conductivity is preferably used. When carbon black is used, for example, acetylene black, channel black, furnace, and the like are used. Known materials such as black and ketjen black can be used. The fluororesin used for the first and second layers 31 and 32 preferably has a property of being converted into a fiber when a shearing force is applied. For example, polytetrafluoroethylene (PTFE), polytrifluoroethylene, polyvinylidene fluoride Etc. can be used.

  The “porous body” in the first layer 31 means that when a sheet is formed by mixing a fluorocarbon resin as a binder with a granular carbon material, it is between particles as compared with the case where a thermoplastic synthetic resin or the like is used as a binder. This means that the gap is maintained and air permeability is ensured. In addition, the first layer 31 is a porous body, so that air permeability is ensured. On the other hand, since the first layer 31 is a mixture of fluororesin, it has a required waterproof performance and can effectively prevent leakage of the reaction solution. it can. Further, the “air-impermeable liquid-impervious” of the first layer 31 is a porous body and has a function of preventing the reaction liquid from leaching out from the second layer 32 in contact with the reaction liquid and leaking to the outside. means. At this time, when the blending ratio of the fluororesin of the first layer 31 is higher than the blending ratio of the fluororesin of the second layer 32, a higher waterproof function can be exhibited.

  In the first layer 31 which is a porous body, the average pore diameter is about 1 to 200 nm, the pore volume is in the range of 0.1 to 4.0 ml / g, and preferably the average pore diameter is about 20 ˜50 nm, pore volume is 0.5 to 1.0 ml / g. Usually, when the average pore diameter and the volume of the porous body are relatively small, surface tension acts on the surface to prevent the permeation of the liquid, while the average pore diameter and the volume are relatively small. If it is too large, water penetrates into the porous body and oxygen is not supplied, so that the current value decreases. Further, when water permeates excessively, water may leak from the porous body. In the present invention, when the average pore diameter and volume of the first layer 31 are within such ranges, it is possible to prevent the reaction liquid from leaching through the pores, and from the pores. Sufficient breathability can be ensured, and both technical effects in a trade-off relationship can be achieved. Further, even after the reaction solution 24 has permeated into the second layer 32, the required current value can be maintained for a relatively long time.

  The second layer 32 is a porous body such as powder or a sheet having a plurality of apertures formed by mixing activated carbon and fluororesin at a predetermined ratio, and is applied to one surface 31 a of the first layer 31. It is fixed through a conductive adhesive. The mixing ratio (weight ratio) of the fluororesin is about 3 to 50% by weight, preferably about 3 to 30% by weight, and more preferably about 5 to 20% by weight. When the mixing ratio is 30% or more, the content of activated carbon is inevitably reduced, the electric capacity is lowered, the water repellency is extremely increased, the wettability is deteriorated, and the electric characteristics as an active layer may not be exhibited. Because there is. Activated carbon is generally used as an electrode material of this type, and an electrode having a large electric capacity per unit volume can be formed by having an extremely large specific surface area due to activation. The “porous body” of the second layer 32 means that when a sheet is formed by mixing a fluororesin as a binder with activated carbon, a gap between particles is maintained as compared with the case where a thermoplastic synthetic resin or the like is used as a binder. This means that the air permeability is ensured and the pore structure on the surface of the activated carbon is maintained and the adsorptivity is excellent.

  In the second layer 32 which is a porous body, the average pore diameter is in the range of about 1 to 200 nm and the pore volume is in the range of 0.1 to 3.0 ml / g. ˜40 nm, pore volume is 0.2˜1.5 ml / g. When the average pore diameter and volume of the second layer 32 are within such ranges, the permeation rate of the reaction solution 24 can be slowed, and the current peak retention time can be made relatively long.

  The third layer 33 is provided as necessary, and is in the form of a foil, a plate, or a sheet formed from at least one metal material such as copper, nickel, aluminum, stainless steel, and titanium. The first layer 31 is fixed via a conductive adhesive applied to the other surface 31b. For the third layer 33, a composite material in which a conductive metal material such as stainless steel (SUS) is coated with a good conductive metal such as gold or silver can be used, and the metal material is meshed by punching or the like. It is also possible to form a porous body formed into a shape or a net shape. When the third layer 33 is formed in a porous body (layer), all of the first to third layers 31, 32, and 33 are formed from the porous body, so that the air permeability is excellent and more oxygen is consumed. While being able to take in, the 3rd layer 33 can be joined to the other side 31b of the 1st layer 31 by pressure bonding instead of adhesion. The third layer 33 can be disposed between the first layer 31 and the second layer 32, but the other side opposite to the one surface 31a where the second layer 32 is located as in the present embodiment. By disposing in the direction 31b, the third layer 33 is not wetted by the reaction solution 24, and the air permeability of the first and second layers 31 and 32 is not hindered, so that a higher discharge current is obtained. be able to. In addition to the porous body, the third layer 33 is narrower than the second layer 32, so that sufficient ventilation can be secured to the first layer 31 and the second layer 32.

<Measuring method of average pore diameter and pore volume of first and second layers>
For the average pore diameter and volume of the first and second layers 31 and 32, the average pore diameter distribution (pore diameter 7.6 nm to 12.6 μm) by mercury porosimetry is used, and the pore distribution measurement made by CARLO ERBA INSTRUMENTS is used. Measured using a porosimeter 2000 model. Note that the average pore diameter and volume in the first and second layers 31 and 32 depend on the size of the carbon material and activated carbon particles and the inter-particle gap, so that the average pore diameter and volume are within the required ranges. Adjust particle size and molding conditions.

  Referring to FIG. 3, in the cathode body 20, the second layer 32 is disposed on the side in contact with the reaction solution 24. By disposing the second layer 32 in the outer frame body 17 in this way, the discharge reaction has a peak compared to the case where the first layer 31 is in direct contact with the reaction solution 24 without using the second layer 32. The time to reach can be shortened, and a larger current can be obtained. In other words, activated carbon has more oxygen adsorbed than carbon materials, and it reacts quickly with electrons, thereby shortening the time to reach the peak and generating a larger current. Can be made. Further, in the case of only the second layer 32 in which activated carbon and fluororesin are formed into a sheet shape, the reaction solution gradually permeates into the second layer 32, and it becomes difficult for air to flow into the inside, so the discharge reaction is weakened. Where there is a possibility, the first layer 31 that is impermeable to air flow is disposed on the outer side, so that the penetration of the reaction solution 24 can be prevented and air can be efficiently transmitted through the entire cathode body 20. The life of the discharge reaction in the layer 32 and, in turn, the life of the cathode body 20 as an electrode can be prolonged. Further, a part 35 of the extended portion of the first layer 31 located outside the outer periphery of the second layer 32 is located in the space S above the liquid injection area 25. In such a case, it is possible to prevent the generated gas filled inside from being released to the outside through the portion 35 and the inside of the outer frame body 17 from becoming a high pressure.

  In the present embodiment, regarding each dimension of each layer constituting the cathode body 20, the dimension L2 in the longitudinal direction Y is about 50 to 90 mm, the dimension W3 (width dimension) in the transverse direction X is about 20 to 60 mm, and the thickness. The dimension in the direction Z is about 1.0 to 1.5 mm. The second layer 32 is slightly smaller than the first layer 31 as a whole, and the dimension L3 in the longitudinal direction Y is about 30 to 70 mm, and the dimension W4 in the transverse direction X is about 15 to 55 mm. The third layer 33 has substantially the same dimension in the longitudinal direction Y as the first layer 31, but is narrower than the first and second layers 31, 32, and has a dimension (width dimension) W5 in the transverse direction X. Is about 15-30 mm. Since the third layer 33 is narrower than the first and second layers 31 and 32, the third layer 33 does not impede the permeation of air to the first and second layers 31 and 32. A constant current can be obtained.

  In the cathode body 20, the first layer 31 and the second layer 32 may have the same size. In addition, the configuration of the present embodiment can also be used for batteries of various sizes such as normal AA and AA, and large power supply devices in ships, semiconductor factories, and the like.

  FIG. 4 shows a modified example of the cathode body 20. The cathode body 20 has a three-layer structure in which the first to third layers 31, 32, and 33 are stacked, and the surface of the second layer 32. The outer periphery excluding the side is covered with the first layer 31. The lamination of the first and second layers 31 and 32 in such a configuration may be formed by laminating the first layer 31 having a slightly larger outer shape on the second layer 32 and rolling them. it can. In the cathode body 20 in the present embodiment, the outer periphery excluding the surface of the second layer 32 is covered with the first layer 31, thereby preventing the reaction solution 24 from leaching out of the entire second layer 32 and reacting. It is possible to effectively prevent the liquid 24 from leaking out of the outer frame body 17.

  FIG. 5 shows the first layer (electrode layer) 31 only (Comparative Examples 1 to 3), the second layer (active layer) 32 only (Comparative Example 4), and the third layer 33 bonded to one side. It is a graph which shows the electric current value (mA) and elapsed time (h) which generate | occur | produced when using the cathode body 20 which consists of 2 layer structure (Example 1 and 2) of the 1st layer 31 and the 2nd layer 32. . Regarding the dimensions of the air magnesium battery 10 used in this measurement, the dimensions L1, W1, and W2 of the outer frame body 17 are about 100 mm, about 60 mm, about 60 mm, and the dimensions L2 of the cathode body 20, respectively. L3, W3, W4, and W5 are about 72 mm, about 60 mm, about 40 mm, about 30 mm, and about 20 mm, respectively. About Example 1, 2, and Comparative Examples 1-5, it measured about 80 hours from the start, and about Comparative Examples 6 and 7, it measured about 60 hours from the start.

<Example 1>
Example 1 is formed from a mixture of a first layer 31 formed from a mixture of 77 wt% carbon material and 23 wt% fluororesin, and a mixture of 95 wt% activated carbon and 5 wt% fluororesin. In addition, a cathode body composed of a two-layer structure with the second layer 32 was used. The first layer 31 has an average pore diameter of 40 nm and a pore volume of 1 ml / g, and the second layer 32 has an average pore diameter of 40 nm and a pore volume of 1.5 ml / g.

<Example 2>
Example 2 includes a first layer 31 formed from a mixture of 77 wt% carbon material and 23 wt% fluororesin, 79 wt% activated carbon, 6 wt% carbon material, and 15 wt% A cathode body composed of a two-layer structure with a second layer 32 formed by mixing with a fluororesin was used. The average pore diameter of the first layer 31 is 40 nm, the pore volume is 1 ml / g, the average pore diameter of the second layer 32 is 30 nm, and the pore volume is 1.0 ml / g.

<Comparative Example 1>
In Comparative Example 1, a cathode body composed only of the first layer 31 formed by mixing 95% by weight of a carbon material and 5% by weight of a fluororesin was used.

<Comparative Example 2>
In Comparative Example 2, the cathode body is composed of only the first layer 31 formed by mixing 77% by weight of carbon material and 23% by weight of fluororesin.

<Comparative Example 3>
In Comparative Example 3, the cathode body is composed of only the first layer 31 formed by mixing 50% by weight of a carbon material and 50% by weight of a fluororesin.

<Comparative Example 4>
In Comparative Example 4, the cathode body is composed only of the second layer 32 formed by mixing 79% by weight of activated carbon, 6% by weight of carbon material, and 15% by weight of fluororesin.

<Comparative Example 5>
In Comparative Example 5, the first layer 31 formed from a mixture of 77 wt% carbon material and 23 wt% fluororesin, and a mixture of 40 wt% activated carbon and 60 wt% fluororesin is formed. In addition, the cathode body 20 having a two-layer structure with the second layer 32 was used.

<Comparative Example 6>
Comparative Example 6 includes a first layer 31 formed from a mixture of 77 wt% carbon material and 23 wt% fluororesin, 79 wt% activated carbon, 6 wt% carbon material, and 15 wt% The cathode body 20 composed of a two-layer structure with the second layer 32 formed by mixing with a fluororesin was used. The average pore diameter of the first layer 31 was 40 nm, the pore volume was 1 ml / g, the average pore diameter of the second layer 32 was 250 nm, and the pore volume was 4.0 ml / g.

<Comparative Example 7>
Comparative Example 7 includes a first layer 31 formed from a mixture of 77 wt% carbon material and 23 wt% fluororesin, 79 wt% activated carbon, 6 wt% carbon material, and 15 wt% The cathode body 20 composed of a two-layer structure with the second layer 32 formed by mixing with a fluororesin was used. The average pore diameter of the first layer 31 was 250 nm, the pore volume was 5.0 ml / g, the average pore diameter of the second layer 32 was 250 nm, and the pore volume was 4.0 ml / g.

  As shown in the graph of FIG. 5, in Examples 1 and 2, the current value reached a peak value (about 200 mA) relatively early (about 1 to 2 minutes from the start), and was stable and high until 40 to 50 hours. A current value could be generated. The time of the peak value of Example 1 is shorter than that of Example 2 because the ionization reaction with the anode body 21 proceeds by containing a relatively large amount of activated carbon, and the anode body 21 is consumed quickly. This is probably because On the other hand, in Comparative Examples 1 to 3, a constant current value can be generated over a relatively long time (about 80 hours) until the anode body 21 is consumed. It was 0.3 to 0.7 times the peak value. In Comparative Example 4, since the water penetrated into the activated carbon, the current value gradually started to decrease after about 15 hours, and the current value was about half of the peak value after 50 hours. In Comparative Example 5, since the mixing ratio of the fluororesin in the second layer 32 is high, the ratio of the activated carbon is greatly reduced and sufficient oxygen cannot be taken in, and the electron transfer is smoothly performed. Only a weak current was generated.

  As described above, the cathode body 20 constituted by the two-layer structure of the first layer 31 and the second layer 32 is relatively less than the case where the cathode body 20 is constituted by only the first layer 31 or only the second layer 32. The peak current of a predetermined magnitude is reached at an early stage, and the state can be maintained for a relatively long time without causing water penetration into the second layer 32 and a decrease in the current value. After 50 hours, the current value starts to gradually decrease, but the peak current value can be obtained again by exchanging the anode body 21 and the reaction liquid (water) 24.

  Further, when Example 2 and Comparative Examples 6 and 7 are compared, Example 2 and Comparative Examples 6 and 7 have the same mixing ratio of materials constituting the first layer 31 and the second layer 32. Only the average pore diameter and the pore volume differ. That is, when Example 2 and Comparative Example 6 are compared, the second layer 32 of Example 2 has an average pore diameter of 30 nm and a pore volume of 1 ml / g, whereas the second layer 32 of Comparative Example 6 has Have an average pore diameter of 250 nm and a pore volume of 4 ml / g. Referring to the graph, the current value of Comparative Example 6 is greatly reduced as time passes in comparison with Example 2. This is probably because the average pore diameter and pore volume of the second layer 32 are relatively large, so that water penetrates and oxygen is no longer supplied.

  In Comparative Example 7, the average pore diameter of the first layer 31 is 250 nm, the pore volume is 5 ml / g, the average pore diameter of the second layer 32 is 250 nm, and the pore volume is 4 ml / g. The average pore diameter and pore volume of the second layers 31 and 32 are relatively large. Therefore, as in Comparative Example 6, water penetrates into the second layer 32 and oxygen is not supplied with the passage of time, and the current value decreases. The value drops. Thus, in contrast to these comparative examples, it can be said that Example 2 can maintain electrical characteristics without deterioration for a long time because the average pore diameter and pore volume are in the optimum ranges.

Second Embodiment
Referring to FIGS. 6 and 7, in this embodiment, the air magnesium battery 10 is mounted on the mounting surface 49 and is a pair positioned on the third surface 13 and the fourth surface 14 of the outer frame body 17. Cathode bodies 20 </ b> A and 20 </ b> B, an anode body 21 inserted in the outer frame body 17, and a ventilation system for discharging the generated gas in the outer frame body 17. By arranging the pair of cathode bodies 20A and 20B so as to sandwich the anode body 21, it is possible to generate a larger current than when only one cathode body 20A is used. The anode body 21 is located closer to the sixth surface 16 than the center line (center axis) P that bisects the dimension in the transverse direction X of the outer frame body 17. A reaction liquid 24 having a capacity of about 50 to 65% of the entire allowable volume is injected into the outer frame body 17.

  It has a ventilation and water storage tank 41 located on the outer surface of the first surface 11 of the outer frame body 17, and a ventilation pipe 42 formed from a soft member such as silicone rubber connected to the tank 41. The tank 41 has an extending portion 44 that is inserted into an opening (attachment hole) provided in the first surface 11 via a rubber water stop seal 43. The tank 41 is attached to the outer frame body 17 so as to be able to rotate 360 degrees about the extending portion 44, and sliding between the extending portion 44 and the water seal 43 is repeated by repeated use. When the latter wears out, it can be replaced. The tank 41 has a vent hole 45 for exhausting the generated gas flowing into the tank 41 from the vent pipe 42 and a drain hole 46 for discharging the reaction liquid 24 flowing into the tank 41. The hole 46 is sealed with a plug 47. In the tank 41, a separation wall (inner wall) 48 is provided between the vent hole 45 and the drain hole 46, and enters the vent pipe 42 on the drain hole 46 side of the separation wall 48 and moves to the tank 41. The reaction liquid 24 is stored. A clearance 50 is formed between the inner wall of the tank 41 and the tip 48 a of the separation wall 48, and a metal weight 52 is disposed on the drain hole 46 side of the tank 41.

  Referring to FIG. 8, as described above, the tank 41 is rotatably connected to the outer frame body 17, and the weight 52 is located on the drainage hole 46 side. Even if it arrange | positions so that the 6th surface 16 may be located upside down from the aspect which 15 is located upside down, the tank 41 will rotate by the dead weight of the weight 52, and the drain hole 46 side will be located below.

  A rubber or plastic float 54 is connected to the other end of the vent pipe 42 via a joint 55 penetrating the central portion thereof. The float 54 is hollow, and a metal weight 56 is disposed on the other end side of the vent pipe 42. The weight 56 is adjusted so that about half of the weight of the float 54 is exposed from the liquid surface 24 a of the reaction solution 24. The end of the joint 55 that passes through the float 54 is tapered and has an open end 55a. In the present embodiment, the tank 41, the vent pipe 42, and the joint 55 that are connected to each other are configured separately, but some or all of them may be integrally formed.

  In the case of the present embodiment, the float 54 floats on the liquid surface, and the opening end 55a of the joint 55 is located in the space S. Therefore, a part of the generated gas in the space S passes through the opening end 55a. It flows into the trachea 42, moves into the tank 41, passes through the clearance 50, and is discharged to the outside. Thereby, since the pressure in the outer frame body 17 can be lowered, even if a large amount of gas is generated with the lapse of power generation time, it is possible to prevent the outer frame body 17 from being cracked by the internal pressure due to the generated gas. it can.

  Referring to FIG. 9, when the air magnesium battery 10 is disposed upside down in the transverse direction X, that is, when the fifth surface 15 is the upper surface and the sixth surface 16 is the lower surface, the anode body 21 is the center. A state in which the liquid surface 24a of the reaction liquid 24 is not in contact with the anode body 21 because the liquid surface 24a of the reaction liquid 24 is not in contact with the anode body 21 and no electromotive force is generated. It becomes. Thus, the on / off of the electromotive force can be adjusted only by changing the direction of the air magnesium battery 10.

<Third Embodiment>
Referring to FIGS. 10 and 11, the air magnesium battery 10 according to this embodiment is inserted into the outer frame body 17 having a convex cross section, the cathode body 20 located on the third surface 13 thereof, and the outer frame body 17. An anode body 21 and a ventilation system. The outer frame body 17 includes a narrow portion 60 through which the anode body 21 is inserted, and a wide portion 61 located below the narrow portion 60. The narrow portion 60 and the wide portion 61 communicate with each other, the reaction liquid 24 is injected into the outer frame body 17, and the float 54 floats on the liquid surface 24a.

  As described above, due to the electrochemical reaction between the anode body 21 and the cathode body 20, hydrogen gas is generated inside the outer frame body 17, and magnesium hydroxide accumulates as a precipitate 64. When the precipitate 64 is in contact with or covers the anode body 21, ionization of the anode body 21 is hindered, and a required electromotive force may not be generated. In the case of the present embodiment, the anode body 21 is located inside the narrow portion 60, and the precipitate 64 accumulates in the wide portion 61 having a wider internal space than the narrow portion 60. There is no contact with the anode body 21. In the present embodiment, the ventilation system is optional, but the outer frame body 17 has such a shape, and the ventilation system is disposed on the outer frame body 17, so that gases and precipitates generated by an electrochemical reaction are generated. 64 can be solved. In addition, as long as there exists such an effect, both the anode body 21 and the cathode body 20 may be located in the wide part 61 instead of the narrow part 60. FIG. However, in order for the electrochemical reaction to be performed effectively, the separation dimension R between the anode body 21 and the cathode body 20 is preferably about 2 to 30 mm. Accordingly, since the separation dimension R needs to be within a certain range, the cathode body 20 and the anode body 21 may be disposed in the narrow portion 60 and the wide portion 61 may have a larger accommodation space.

  Referring to FIG. 12, a pair of inner walls 68 a and 68 b that are separated from each other and face each other can be provided between the narrow portion 60 and the wide portion 61 inside the outer frame body 17. In such a case, the precipitate 64 moves to the wide portion 61 and is deposited through the separation portion 69 located between the inner walls 68a and 68b. The width dimension of the separation part 69 is smaller than the width dimension of the narrow part 60, and even if the narrow part 60 is arranged in a manner located below, there is a possibility that a large amount of the precipitate 64 moves to the narrow part 60. Absent.

<Fourth embodiment>
Referring to FIGS. 13A and 13B, the air magnesium battery 10 according to the present embodiment is a portable light having a power generation function, and an outer frame body 70 includes a cylindrical main body 72, a main body, And a lid 71 detachably attached to 72. Inside the outer frame 70, a rod-shaped anode body 73 is positioned to be deviated to one side in the transverse direction X with respect to the center line P, and a pair of cathode bodies 74 are arranged on the side surfaces. In the outer frame 70, as in the second embodiment, about 50 to 65% of the allowable volume of the reaction liquid 75 is injected. A plurality of light sources 76 such as LEDs and white bulbs are arranged inside the lid 71. A lead wire (not shown) extending from the anode body 73 and the cathode body 74 is electrically connected to the light source 76 and is lit by power generation by the air magnesium battery 10.

  The outer frame body is rotatably attached to a support frame 78 having a gripping portion 77, and an operator rotates the outer frame body 70 with respect to the support frame 78 to turn it upside down, that is, By preventing the anode body 21 from coming into contact with the liquid surface 24 a of the reaction solution 24, the battery 10 is brought into a state where no electromotive force is generated. The main body 71 is provided with an operation portion 79 for operating on / off of the electric power supply to the light source 76, so that the electric supply to the light source 76 can be cut off even when the air magnesium battery 10 is in an electromotive state. it can. As described above, the light source 76 is easily switched on / off by turning on / off the power by turning the outer frame 70 (first power switch) and turning on / off the power by the operation unit 79 (second power switch). be able to.

  As each member which comprises the air magnesium battery 10, the material used for this kind of goods other than the said material can be used without a restriction | limiting. Moreover, the various dimensions of each component in each embodiment can be appropriately changed according to the required electromotive force.

10 Air Magnesium Battery 17, 70 Outer frame 20, 74 Cathode body 21, 73 Anode body 24, Reaction liquid 24a Liquid surface 25 Injection area 31 First layer (electrode layer)
31a One side 32b of the first layer 32 The other side 32 of the first layer Second layer (active layer)
33 3rd layer (current collection layer)
42 Vent tube 54 Float 55 Joint 55a Open end 60 Narrow part 61 Wide parts 68a, 68b Inner wall 76 Light source 79 Operation part S Space

In order to solve the above problems, the first and second inventions of the present application provide an air including an outer frame body, a cathode body fixed to the outer frame body, and an anode body positioned inside the outer frame body. Intended for magnesium batteries.

In the first invention of the present application, the cathode body is in contact with a first layer made of a porous body formed by mixing a conductive carbon material and a fluororesin, and a reaction solution in the outer frame body. The outer frame body is composed of a second layer made of a porous body formed by mixing activated carbon and fluororesin and bonded to one surface of the first layer, and the outer frame body is a reaction injected into the inside. A ventilation system comprising: a liquid injection area composed of a liquid; a space located above the liquid injection area; a float floating on the liquid surface of the liquid injection area; and a vent pipe for exhausting the generated gas inside the liquid injection area. One end of the vent pipe is connected to an opening formed on the outer surface of the outer frame body, the other end of the vent pipe is connected to a joint that penetrates the float, and the open end of the joint is It is located in the space .

In the second invention of the present application, the cathode body is in contact with a first layer made of a porous body formed by mixing a conductive carbon material and a fluororesin, and a reaction solution in the outer frame body. The outer frame body is formed of a porous body formed by mixing activated carbon and fluororesin, which is bonded to one surface of the first layer, and the outer frame body has a convex cross section. A narrow portion and a wide portion that communicate with each other, and the anode body and the cathode body are positioned to face each other in either the narrow portion or the wide portion. Features.
As one embodiment of the present invention, a third layer made of a conductive metal material is bonded to the other surface of the first layer located on the opposite side of the one surface.

Claims (12)

In an air magnesium battery including an outer frame, a cathode body fixed to the outer frame, and an anode body located inside the outer frame,
The cathode body has a first layer made of a porous body formed by mixing a conductive carbon material and a fluororesin, and one surface of the first layer so as to be in contact with the reaction liquid in the outer frame body. The said air magnesium battery comprised from the joined 2nd layer which consists of a porous body formed by mixing activated carbon and a fluororesin.   The air magnesium battery according to claim 1, wherein a third layer made of a conductive metal material is joined to the other surface of the first layer located on the opposite side of the one surface.   The mixing ratio of the fluororesin mixed in the first layer is about 10 to 50% by weight, and the mixing ratio of the fluororesin mixed in the second layer is about 3 to 30% by weight. Or the air magnesium battery of 2.   The air magnesium battery according to any one of claims 1 to 3, wherein the second layer has a smaller outer dimension than the first layer, and the third layer is narrower than the second layer.   The air magnesium battery according to any one of claims 1 to 4, wherein the third layer is a porous body.   The outer frame exhausts a liquid injection area composed of a reaction liquid injected into the inside, a space located above the liquid injection area, a float floating on the liquid surface of the liquid injection area, and a gas generated in the inside. A vent system comprising: a vent system comprising: a vent system, wherein one end of the vent pipe is connected to an opening formed in an outer surface of the outer frame body, and the other end of the vent pipe is a joint that penetrates the float The air magnesium battery according to any one of claims 1 to 5, wherein the air magnesium battery is connected to the joint, and an opening end of the joint is located in the space.   The outer frame body is convex in cross section, and has a narrow portion and a wide portion that communicate with each other inside, and the anode body and the cathode body are the narrow portion and the wide portion, respectively. The air magnesium battery according to any one of claims 1 to 6, wherein the air magnesium battery is positioned so as to face each other.   The air magnesium battery according to claim 7, wherein a pair of inner walls that are spaced apart from each other and provided between the narrow portion and the wide portion are provided inside the outer frame body.   The air magnesium battery according to any one of claims 1 to 8, wherein the first layer has an average pore diameter of about 1 to 200 nm and a pore volume of 0.1 to 4.0 ml / g.   The air magnesium battery according to any one of claims 1 to 9, wherein an average pore diameter in the second layer is about 1 to 200 nm, and a pore volume is 0.1 to 3.0 ml / g.   The air magnesium battery according to any one of claims 1 to 10, further comprising a light source electrically connected to the cathode body and the anode body.   The air magnesium battery according to claim 11, further comprising an operation unit operable to turn on / off the electric supply to the light source.

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