WO2013108839A1

WO2013108839A1 - Liquid-injection-type metal-air battery

Info

Publication number: WO2013108839A1
Application number: PCT/JP2013/050808
Authority: WO
Inventors: 佳子塚田; 宮澤　篤史; 長山　森
Original assignee: 日産自動車株式会社
Priority date: 2012-01-19
Filing date: 2013-01-17
Publication date: 2013-07-25
Also published as: JP6032018B2; JP2013168360A; TW201349629A

Abstract

This liquid-injection-type metal-air battery is provided with: a negative electrode that is mainly composed of a metal that has a higher ionization tendency than hydrogen; and a coating layer that is configured of a material different from the above-mentioned metal and is formed on at least a part of the surface of the negative electrode so as to suppress the hydrogen generating reaction between the negative electrode and an electrolyte solution. In this liquid-injection-type metal-air battery, corrosion or wear of the negative electrode metal is suppressed during the liquid injection period, namely from the beginning of the injection of the electrolyte solution to the beginning of an electrical discharge. As a result, the capacity utilization rate and the energy density of this liquid-injection-type metal-air battery are improved.

Description

Injection metal-air battery

The present invention relates to a metal-air battery. In particular, the present invention relates to a liquid-injection-type metal-air battery that can be used by injecting an electrolyte or water for electrolyte during use.

A metal-air battery is a battery that uses oxygen in the air as a positive electrode active material and a metal such as aluminum (Al), iron (Fe), or zinc (Zn) as a negative electrode active material. Such a battery is attracting attention as a battery that has a high energy density and can be reduced in size and weight.

As one type of metal-air battery, for example, as described in Patent Document 1, an infusion type in which an electrolytic solution is injected at the time of use and brought into a usable state by bringing the electrolytic solution into contact with an electrode. There is a battery. Such a liquid injection type battery is suitable as an emergency or emergency power source because the battery reaction does not proceed unless an electrolytic solution is injected, and long-term storage is possible.

Patent Document 2 describes a liquid-injection-type metal-air battery using a metal electrode that is configured so that at least the electrolyte side surface is in a liquid state at least temporarily in order to prevent dendrite growth during charging. Yes. More specifically, an example in which a Ga alloy containing 3% by mass of Hg is used as the negative electrode metal is described.

JP 2002-151167 A JP 2008-098075 A

However, when the alloy and the electrolytic solution in Patent Document 2 come into contact with each other, a hydrogen generation reaction proceeds. That is, there is a problem that the alloy is corroded by the electrolytic solution when the electrolytic solution is injected.

The present invention has been made in view of such problems of the conventional technology. The object of the present invention is to suppress the corrosion or consumption of the negative electrode metal from the start of the injection of the electrolyte until the electrolyte penetrates the whole, and the capacity utilization rate and the energy density are improved. The object is to provide an injection-type metal-air battery.

An injection-type metal-air battery according to an embodiment of the present invention is composed of a negative electrode mainly composed of a metal having a higher ionization tendency than hydrogen and a material different from the metal, and is formed on at least a part of the negative electrode surface. And a coating layer that suppresses a hydrogen generation reaction between the negative electrode and the electrolytic solution.

FIG. 1 is a schematic view showing a state of Zn coating treatment on the negative electrode substrate in Example 5. FIG. FIG. 2 is a schematic diagram showing an apparatus used for evaluating the amount of hydrogen generation when discharging was performed using the negative electrode samples according to Examples and Comparative Examples. FIG. 3 is a graph showing the amount of hydrogen generation in Examples 1 and 2 and the comparative example over time. FIG. 4 is a schematic cross-sectional view showing an example of an electrode structure of a liquid injection type metal-air battery according to one embodiment of the present invention.

Hereinafter, the injection-type metal-air battery according to an embodiment of the present invention will be described in detail. In the present specification, “%” means mass percentage unless otherwise specified. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may differ from actual ratios.

First, the basic structure of the injection-type metal-air battery according to one embodiment of the present invention and the materials constituting them will be described. The liquid-injection-type metal-air battery according to the present embodiment is used for, for example, an electrode structure including a positive electrode (air electrode) and a negative electrode, an electrode storage unit that stores the electrode structure, and an electrolytic solution or an electrolytic solution. And a tank for storing the solvent.

As shown in FIG. 4, the electrode structure 20 of the injection type metal-air battery of the present embodiment includes a negative electrode layer 21, a coating layer 25, an electrolyte layer 23, a positive electrode layer 22, a liquid tight ventilation member 24, Can be configured to be stacked in this order. The positive electrode layer 22 may include a liquid-tight ventilation member 24 on the outer layer side. And the negative electrode layer 21 is provided with the coating layer 25 in at least one part of the surface in this form. As shown in FIG. 4, the coating layer 25 is formed on the surface of the negative electrode layer 21 facing the electrolyte layer 23, thereby suppressing the reaction that the electrolytic solution contained in the electrolyte layer 23 corrodes the negative electrode layer 21. it can. The electrode storage portion is a case for storing an electrolytic solution together with the electrode structure, and has a structure that prevents leakage of the electrolytic solution. That is, the case is made of a material resistant to the electrolytic solution. The tank has an integral structure with the electrode structure or a separation structure. In other words, the electrolytic solution or solvent in the tank can be injected into the electrode storage part that stores the electrode structure by an appropriate means.

[Positive electrode]
The positive electrode uses oxygen as a positive electrode active material. That is, a positive electrode including a catalyst component that functions as an oxygen redox catalyst and a conductive catalyst carrier that supports the catalyst component can be obtained.

As the catalyst component, for example, a metal oxide such as manganese dioxide or tricobalt tetroxide can be used. In addition, platinum (Pt), ruthenium (Ru), iridium (Ir), rhodium (Rh), palladium (Pd), osmium (Os), tungsten (W), lead (Pb), iron (Fe), chromium Select from metals such as (Cr), cobalt (Co), nickel (Ni), manganese (Mn), vanadium (V), molybdenum (Mo), gallium (Ga) and aluminum (Al), and alloys thereof. Can do.

The shape and size of the catalyst component are not particularly limited, and the same shape and size as those of conventionally known catalyst components can be employed. However, the shape of the catalyst component is preferably granular, and the average particle size of the catalyst particles is preferably 1 to 30 nm. When the value of the average particle diameter of the catalyst particles is within the above range, the balance between the catalyst utilization and the ease of loading can be appropriately controlled. The catalyst utilization rate is related to the effective electrode area that is important in causing the electrochemical reaction to proceed.

In the present specification, the value of “average particle diameter” refers to particles observed in several to several tens of fields using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The value calculated as the average value of the particle diameters of the particles shall be adopted. The average particle size of other constituents can be defined in the same manner.

The catalyst carrier not only functions as a carrier for supporting the above-described catalyst component, but also functions as an electron conduction path material involved in the transfer of electrons between the catalyst component and other members. The catalyst carrier is not particularly limited as long as it has a specific surface area for supporting the catalyst component in a desired dispersed state and has sufficient electron conductivity, and the main component may be carbon. preferable. Specific examples of the catalyst carrier include carbon particles made of carbon black, activated carbon, coke, natural graphite, artificial graphite, and the like. In the present specification, the “main component” means that the content of the component is 50% by mass or more with respect to the whole. The main components of the other constituent components can be defined similarly.

The size of the catalyst carrier is not particularly limited, but it is preferable that the average particle diameter is about 5 to 200 nm from the viewpoint of easy loading, catalyst utilization, and control of the catalyst layer thickness within an appropriate range. . More preferably, it is about 10 to 100 nm.

The amount of the catalyst component supported on the catalyst carrier is preferably 10 to 80% by mass, more preferably 30 to 70% by mass, based on the total amount of the catalyst and the carrier carrying the catalyst. When the supported amount of the catalyst component is within such a range, the balance between the degree of dispersion of the catalyst component on the catalyst carrier and the catalyst performance is appropriate. In addition, about the above-mentioned catalyst component and the kind of support | carrier which carry | supports this, it is not limited only to what was mentioned above, A conventionally well-known material can be used suitably as what is applied to an air battery.

[Liquid-tight ventilation member]
The liquid-tight ventilation member is a member that is disposed on the outer layer side of the positive electrode and has liquid-tightness (water-tightness) with respect to the electrolytic solution and air-permeability with respect to oxygen. As a material, a material composed of a water-repellent porous resin such as polyolefin or fluororesin can be adopted, which enables oxygen supply to the positive electrode while preventing the electrolyte from leaking to the outside. Demonstrate.

[Negative electrode]
For the negative electrode, a metal having a higher ionization tendency than hydrogen is used as a main component. That is, a single metal whose standard electrode potential is lower than that of hydrogen, or an alloy containing these metals can be used. Specific examples of constituent components of the negative electrode include simple metals such as zinc (Zn), iron (Fe), aluminum (Al), and magnesium (Mg). Examples of the alloy include those obtained by adding one or more metal elements or non-metal elements to these metal elements. However, the present invention is not limited to these, and any conventionally known material that is applied to an air battery can be applied as long as it meets the above purpose.

[Separator]
As the separator, for example, glass paper that has not been subjected to water repellent treatment, or a microporous film made of polyolefin such as polyethylene or polypropylene can be used. However, the material is not limited to these, and a conventionally known material applied to the air battery can be applied. Note that the separator is not necessarily required as long as a space is ensured between the positive electrode and the negative electrode.

[Electrolyte]
As the electrolytic solution, for example, an aqueous solution of potassium chloride, sodium chloride, potassium hydroxide, sodium hydroxide, or the like can be used. However, it is not limited to these, The conventionally well-known electrolyte solution applied to an air battery can be applied. The above-described tank contains an electrolytic solution prepared in advance at a predetermined concentration, that is, an alkaline aqueous solution as described above, and water that is a solvent for the alkaline aqueous solution. When the electrolytic solution is stored in the tank before the use of the battery, the requirement for the components of the tank such as alkali resistance becomes severe, but an electrolytic solution having a uniform concentration can be supplied to the electrode structure from the beginning of the injection. There is an advantage. On the other hand, when only water is stored in the tank, it is necessary to previously arrange the electrolyte as described above in the electrode structure or the electrode storage portion.

[Coating layer]
In the injection type metal-air battery of this embodiment, a coating layer that is made of a material different from the negative electrode metal and suppresses the hydrogen generation reaction between the negative electrode and the electrolyte is formed on at least a part of the negative electrode surface. The By the coating layer, it is possible to avoid the entire contact between the negative electrode metal and the electrolytic solution for at least a certain period from the start of injection to the start of discharge. As a result, the amount of hydrogen generation and consumption due to corrosion of the negative electrode are reduced, and safety, capacity utilization of the battery, and energy density are improved. Further, by preventing wasteful consumption of the negative electrode, uneven discharge of the electrode at the start of discharge is improved. Furthermore, nonuniformity when such batteries are connected in series is eliminated, and variation in battery characteristics between cells due to uneven surface corrosion of the negative electrode is also improved.

As the material of the coating layer, even if a small amount is left from the start of injection of the electrolytic solution to the completion, it can remain on the negative electrode surface to prevent the entire contact between the negative electrode metal and the electrolytic solution. desirable. As long as it is such a material, a conventionally known material can be adopted. In particular, a material that does not react with the electrolytic solution to be used or a material that does not generate hydrogen even when reacted is preferable. From the above viewpoint, the thickness of the coating layer and the coating form can be adjusted according to the reactivity, solubility, and dispersibility of the coating layer material with respect to the electrolytic solution. By adjusting in this way, various materials can be applied except those that adversely affect the function as an electrolytic solution and those that are conductive materials that peel into a film and short-circuit both electrodes. Furthermore, a material having low reactivity with oxygen, water vapor, etc. in the atmosphere is preferable because it can be expected to protect the anode metal from oxidation during long-term storage and scratches on the surface during transportation.

When a material having high reactivity and easily dissolved in the electrolytic solution is used for the coating layer, the coating layer is thickened, and when a material difficult to dissolve in the electrolytic solution is used for the coating layer, depending on the solubility. What is necessary is just to make a coating layer thin. On the other hand, when a material that does not substantially react with the electrolytic solution is used for the coating layer, pinholes can be formed in the coating layer, or a discontinuous coating layer can be formed through gaps or grooves. If it does in this way, the elution to the electrolyte solution of a negative electrode component can be restrict | limited only from a discontinuous part, and the negative electrode consumption until discharge start can be suppressed. In this case, the elution from the discontinuous portion of the coating proceeds, so that the coating layer is detached from the electrode surface at the end of the injection, after the completion of the injection, and further at the start of discharge. Will be distributed. At this time, unevenness occurs due to local elution of the electrode from the discontinuous portion of the coating, and the reaction area of the negative electrode after the coating layer is peeled increases, so that a secondary effect of improving the output of the battery is obtained.

In the liquid-injection-type metal-air battery of this embodiment, the material of the coating layer formed on the negative electrode surface is not limited to a specific one as long as the above purpose is satisfied. However, typical examples thereof include metals, oxides, nitrides, and polymer materials. When these materials are employed, the dissolution time in the electrolytic solution can be increased by increasing the thickness of the coating layer, which is preferable from the viewpoint of easy operation of the dissolution rate in the electrolytic solution.

Examples of metal-based materials include zinc (Zn), tin (Sn), aluminum (Al), silicon (Si), gallium (Ga), germanium (Ge), indium (In), and bismuth (Bi), and these Alloys can be employed. When employing these, it is preferable from the viewpoint of suppressing the generation of hydrogen and protecting the negative electrode surface. Also, for example, magnesium (Mg), titanium (Ti), cobalt (Co), nickel (Ni), molybdenum (Mo), copper (Cu), silver (Ag), chromium (Cr), iron (Fe) and manganese (Mn) and alloys thereof can also be employed. These are preferable because they are insoluble in the electrolyte and can be applied to the coating layer to mechanically or chemically protect the negative electrode surface.

It should be noted that it is desirable that the metal material for forming the coating layer does not include the same type as the negative electrode. Moreover, the coating layer comprised from these metals can be formed on the negative electrode surface by sputtering, plating, or the like. In the case of coating with a metal, it is desirable to consider the difference in ionization tendency between the metal constituting the coating layer and the negative electrode metal which is the main component constituting the negative electrode. As the difference in ionization tendency increases, the coated surface becomes more stable. Here, it is desirable to increase the coverage of the coating layer as the difference in ionization tendency between the metal applied to the coating layer and the negative electrode metal increases. When a metal having a large difference in ionization tendency is applied to the coating layer, corrosion of a portion where the negative electrode surface is exposed tends to be accelerated. Therefore, it can be said that it is preferable to increase the coverage as described above from the viewpoint of preventing an increase in the amount of hydrogen generation. In addition, a coverage can be calculated | required from ratio of the surface area of the whole negative electrode surface by the side which contacts electrolyte solution, and the surface area of the said negative electrode surface coat | covered with the coating layer.

As the oxide-based material, an oxide that dissolves in an alkaline electrolyte can be used. For example, zinc oxide (ZnO), tin oxide (SnO _x ), aluminum oxide (AlO _x ), and the like can be given. An oxide that is insoluble in an alkaline electrolyte can also be used. For example, silicon oxide (SiO _x ), titanium oxide (TiO _x ), cobalt oxide (CoO _x ), nickel oxide (NiO _x ), molybdenum oxide (MoO _x ), manganese oxide (MnO _x ), chromium oxide (CrO _x ) Etc. Any of the oxides described above is hydrophilic. When an oxide soluble in the electrolytic solution is used, the oxide is eluted into the electrolytic solution, and almost all of the oxide is eventually peeled off from the negative electrode surface. On the other hand, when an oxide insoluble in the electrolyte is used, the negative electrode metal is eluted from the pinholes formed in the coating layer or the discontinuous portions described above, so that most of the oxide eventually peels from the negative electrode surface. Thus, when the reaction area of the negative electrode after peeling of a coating layer increases, since the output of a battery improves, it is preferable.

The coating layer composed of such an oxide can be formed on the negative electrode surface by sputtering, anodizing treatment, thermal oxidation treatment, or the like. It should be noted that, on the surface of the metal negative electrode, an oxide film due to oxygen in the air is naturally formed without any special treatment, but such a natural oxide film is subject to the occurrence of corrosion by the electrolyte. . Therefore, the natural oxide film formed on the negative electrode surface does not correspond to the coating layer in this embodiment.

Examples of the nitride material include nitrides such as silicon nitride (Si ₃ N ₄ ), aluminum nitride (AlN), chromium nitride (CrN), gallium nitride (GaN), titanium nitride (TiN), and iron nitride (FeN _x ). Can be mentioned. These nitrides are insoluble in the electrolytic solution and have a function of mechanically or chemically protecting the negative electrode surface. Moreover, such a coating layer can be formed on the negative electrode surface by sputtering, plasma nitriding, or the like.

And examples of the polymer material used as the coating layer include water-soluble starch, gelatin, cellulose, polyethylene glycol, polyvinyl alcohol (PVA), and the like. When such a material is used, the metal negative electrode can be protected until the material is gradually dissolved in the electrolytic solution and disappears from the negative electrode surface. Alternatively, a polymer material that is insoluble in the electrolytic solution and mechanically or chemically functions as a masking agent that protects the negative electrode surface can be used. For example, hydrophobic silicon, polyamide, polyacetal, epoxy resin, acrylic resin, natural rubber, chloroprene rubber, nitrile rubber, butyl rubber, ethylene propylene rubber, fluorine rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, and the like can be mentioned. . These polymer materials can be applied to the negative electrode surface by a dip method, a spin coating method, a spray method, a method using a roller or a brush, or the like. By the method as described above, the coating layer can be formed using the polymer material.

Note that the thickness of the coating layer can be determined in consideration of various factors. For example, the physical properties of the material used for the coating layer, the denseness based on the coating method, the reactivity with the electrolyte, the coating form, the type of electrolyte, the size (capacity) of the battery, and the injection time determined by the injection method Can be considered as. The thickness of the coating layer is preferably 0.1 to 10 μm. If the value of the thickness of the coating layer is within the above range, a particularly excellent hydrogen generation amount suppressing effect can be obtained while maintaining a high discharge capacity. Furthermore, the case of forming the layer thickness of the range, as the constituent components of the coating layer, a silicon oxide _(SiO x), zinc (Zn), aluminum oxide _(AlO x), aluminum nitride (AlN) or tin (Sn) It is preferable to contain as a main component. When the coating layer containing such a material is formed in a layer thickness within the above range, a more excellent hydrogen generation amount suppressing effect can be obtained while maintaining a high discharge capacity.

Hereinafter, the present invention will be described in more detail based on examples and comparative examples, but the present invention is not limited to only these examples.

(Example 1)
First, as a negative electrode substrate, an Al—Mn-based aluminum alloy sheet defined as A3003 in JISH4000 was prepared. The size of the substrate was 100 × 100 × 0.2 mm. Then, a SiO _x layer as a coating layer was formed on the surface of the substrate so as to have a thickness of 100 nm by reactive sputtering using SiO ₂ as a target. The sputtering was performed in a flow in which Ar gas was 61 sccm and O ₂ gas was 2.9 sccm. The deposition pressure was 0.3 Pa and the sputtering power was 200 W.

(Example 2)
The negative electrode substrate was subjected to constant current electrolytic plating using a general zincate bath. Thus, a zinc (Zn) layer as a coating layer was formed on the negative electrode substrate surface so as to have a thickness of 100 nm.

(Example 3)
The negative electrode substrate was immersed in an aqueous sulfuric acid solution and anodized. In this manner, the aluminum oxide (Al 2 _O ₃₎ layer with sulfuric anodized as a covering layer was formed to a thickness of 10 [mu] m.

(Example 4)
An AlN film having a thickness of 100 nm was formed on the negative electrode substrate surface by reactive sputtering using Al as a target. The sputtering was performed in a flow in which Ar gas was 41.5 sccm and N ₂ gas was 27.3 sccm, the film forming pressure was 0.3 Pa, and the sputtering power was 200 W. The thickness of the AlN layer was 0.1 μm.

(Example 5)
The negative electrode substrate was subjected to a zincate treatment using the beaker cell shown in FIG. As shown in FIG. 1, a PP (polypropylene) container 1 containing a predetermined mixed aqueous solution L was prepared, and an Hg / HgO reference electrode 2 and a cathode 3 were immersed therein. The cathode 3 is connected to the Hg / HgO reference electrode 2 by a current collecting nickel mesh 4. Further, the negative electrode substrate S was immersed in the mixed aqueous solution L. The negative electrode substrate S is attached with the masking agent M covering the side surface and the interface with the copper foil 5. First, the negative electrode substrate S was immersed in a zincate solution for 200 seconds. As the zincate solution, 100 ml of an aqueous solution in which 50 g of NaOH and 25 g of ZnO were dissolved was used. Next, the negative electrode substrate was washed with water and ethanol and then immersed in 50% nitric acid to dissolve the Zn layer on the surface of the negative electrode substrate S, thereby forming an oxide film on the Al surface. And after wash | cleaning the board | substrate S for negative electrodes with water and ethanol, it was immersed again in the zincate liquid of the same composition for 200 seconds, and the zinc layer as a coating layer was formed in the surface of the board | substrate S for negative electrodes. The thickness of the zinc layer was 0.1 μm.

(Example 6)
The negative electrode substrate was dip-coated using an aqueous solution containing 30% of commercially available polyvinyl alcohol. Subsequently, it heat-dried at 80 degreeC, and formed the polyvinyl alcohol layer as a coating layer on the said substrate surface.

(Example 7)
A masking agent was applied to the negative electrode substrate by dip coating. As a masking agent, a commercially available San-Econ Mask Ace S was used. Next, the masking agent on the surface was partially wiped using a spatula made of PFA so as to form a partial coating, thereby forming a masking layer.

(Example 8)
The negative electrode substrate was subjected to constant current electrolytic plating using a common stannate bath. Thus, a tin (Sn) layer as a coating layer was formed on the negative electrode substrate surface so as to have a thickness of 1 μm.

[Evaluation test]
(A) Hydrogen generation amount Eight types of negative electrode samples on which the coating layer was formed as described above were subjected to a hydrogen generation amount evaluation test. As an evaluation means, the measurement system shown in FIG. 2 was used. That is, the sealable container 11 was connected to the mass flow controller (MFC) 12 and the gas analyzer 14, and the measurement system was configured so that an air flow of 100 sccm was introduced into the sealable container 11. In addition, an electrolytic solution is introduced into a container installed in the sealable container 11 by a syringe 13 having a tube attached to the tip, and the negative electrode sample 16, the positive electrode 17, and the reference electrode 18 are immersed in the electrolytic solution. Yes. The negative electrode sample 16, the positive electrode 17, and the reference electrode 18 are connected to the discharge device 15 by a conductive wire. In addition, 8N KOH aqueous solution was used as electrolyte solution. As the gas analyzer 14 for analyzing the flow exhaust, a hydrogen generation amount was monitored using a quadrupole mass spectrometer (Omnistar) manufactured by Pfeiffer Vacuum. The hydrogen generation amount detected in each example was obtained by integrating the hydrogen generation amount detected during 600 seconds after the anode sample 16 was immersed in the KOH aqueous solution. On the other hand, a negative electrode sample 16 as it was was used as a comparative example. The hydrogen generation amounts of Examples 1 to 8 and Comparative Example are shown in Table 1. The accumulated hydrogen generation amount is shown as a percentage with the generation amount of the comparative example being “100”.

(B) Discharge capacity With respect to the negative electrode sample 16 corresponding to Examples 1 to 8 and Comparative Example, a commercially available air electrode having a general configuration is used as the positive electrode 17, and the Hg / HgO electrode is used as the reference electrode 18. A discharge cell as shown was prepared. In addition, the same electrolyte solution as the above (A) was used. Then, with the negative electrode sample 16, the positive electrode 17, and the reference electrode 18 immersed in the electrolyte, the discharge cell was left for 10 minutes. Thereafter, constant current discharge was performed at a current density of 100 mA / cm ² . When the negative electrode potential with respect to the reference electrode 18 reached 0 V, the discharge was terminated, and the discharge capacity of each example until the end of the discharge was determined. The results are also shown in Table 1.

As shown in Table 1, it was confirmed that the negative electrode samples of Examples 1 to 8 provided with the coating layer were significantly reduced in hydrogen generation compared to the comparative example in which the coating layer was not formed. It was also confirmed that even when the coating layer was formed, there was no tendency to decrease the discharge capacity of the battery. In Example 2 in which galvanization was applied as the coating layer, a higher discharge capacity was obtained than in the comparative example in which the coating layer was not formed. This is considered to be due to the fact that the zinc of the coating layer also functions as the negative electrode itself.

(C) Change over time of hydrogen generation amount A negative electrode sample 16 corresponding to Examples 1 and 2 provided with a coating layer was placed in a beaker cell in a sealable container 11 in the same manner as in (B) above. A commercially available air electrode was used as the positive electrode 17 serving as the counter electrode, and an Hg / HgO electrode was used as the reference electrode 18. Further, an 8N KOH aqueous solution was used as the electrolytic solution, and the electrolytic solution was injected into the cell with a syringe 13 having a tube attached to the tip. An air flow of 100 sccm was introduced into the sealable container 11. And a part of gas was extract | collected from the container upper surface, and the hydrogen analyzer contained in gas was monitored by the gas analyzer 14. The temporal change in the ratio of hydrogen gas contained in the exhaust gas was investigated from the time of injection, and compared with a case where a negative electrode sample of a comparative example in which a coating layer was not formed was immersed in an electrolytic solution. The result is shown in FIG.

From Figure 3, the following became clear. That is, in the comparative example in which the coating layer is not formed, the time until hydrogen detection is 100 seconds, whereas in the negative electrode samples of Examples 1 and 2 in which the coating layer is formed, the time until hydrogen is detected is It could be further delayed by 50 to 100 seconds. Thus, it was confirmed that the effect of suppressing initial hydrogen generation can be obtained by forming the coating layer on the negative electrode surface. It was also found that the total amount of hydrogen generated can be suppressed as a whole by forming a coating layer on the negative electrode surface.

As mentioned above, although the content of the present invention was explained along with the example, the present invention is not limited to these descriptions, and various modifications and improvements can be made within the scope of the paper of the present invention. It will be obvious to those skilled in the art.

The entire contents of Japanese Patent Application No. 2012-009117 (Application Date: January 19, 2012) and Japanese Patent Application No. 2013-003328 (Application Date: January 11, 2013) are cited here. Is done.

According to the present invention, the entire surface or a part of the negative electrode surface is a liquid injection type metal-air battery provided with a coating layer that suppresses the hydrogen generation reaction between the metal negative electrode and the electrolytic solution. In such a liquid injection type metal-air battery, corrosion or consumption of the negative electrode metal is suppressed during the liquid injection period from the start of injection of the electrolytic solution to the start of discharge. As a result, the capacity utilization rate and energy density of the liquid injection type air battery are improved.

S negative electrode substrate 16 negative electrode sample 20 electrode structure 21 negative electrode layer 25 coating layer

Claims

A negative electrode mainly composed of a metal having a higher ionization tendency than hydrogen;
A coating layer made of a material different from the metal, formed on at least a part of the negative electrode surface, and suppressing a hydrogen generation reaction between the negative electrode and an electrolyte;
A liquid-injection metal-air battery comprising:
The injection type metal-air battery according to claim 1, wherein the coating layer is formed discontinuously.
The injection type metal-air battery according to claim 1 or 2, wherein the coating layer is made of a metal, an oxide, a nitride, or a polymer material.
The coating layer is made of at least one metal selected from the group consisting of zinc, tin, aluminum, gallium, germanium, indium, bismuth, magnesium, titanium, cobalt, nickel, molybdenum, copper, silver, chromium, iron and manganese. 4. The injection type metal-air battery according to claim 3, wherein the injection-type metal-air battery is configured.
The injection type metal-air battery according to claim 3, wherein the coating layer is made of zinc formed by a double zincate process.
The coating layer is composed of at least one oxide selected from the group consisting of silicon oxide, aluminum oxide, chromium oxide, zinc oxide, tin oxide, titanium oxide, cobalt oxide, nickel oxide, molybdenum oxide, and manganese oxide. The liquid-injection metal-air battery according to claim 3.
The note according to claim 3, wherein the coating layer is made of at least one nitride selected from the group consisting of silicon nitride, aluminum nitride, chromium nitride, gallium nitride, titanium nitride, and iron nitride. Liquid metal-air battery.
The coating layer is starch, gelatin, cellulose, polyethylene glycol, polyvinyl alcohol, silicon, polyamide, polyacetal, epoxy resin, acrylic resin, natural rubber, chloroprene rubber, nitrile rubber, butyl rubber, ethylene propylene rubber, fluorine rubber, styrene-butadiene rubber. 4. The injection-type metal-air battery according to claim 3, wherein the injection-type metal-air battery is composed of at least one polymer material selected from the group consisting of acrylonitrile-butadiene rubber.