WO2017006666A1

WO2017006666A1 - Negative electrode for iron-air secondary cell, iron-air secondary cell, and method for manufacturing negative electrode for iron-air secondary cell

Info

Publication number: WO2017006666A1
Application number: PCT/JP2016/066488
Authority: WO
Inventors: 和志林; 尚敏坂本; 厚範松田; 康孝前田; 翼鈴木
Original assignee: 株式会社神戸製鋼所; 国立大学法人豊橋技術科学大学
Priority date: 2015-07-06
Filing date: 2016-06-02
Publication date: 2017-01-12

Abstract

This negative electrode for an iron-air secondary cell is used in an iron-air secondary cell, wherein said negative electrode has a three-dimensional bond in which particles of a metal powder having iron or an iron alloy as the main component are joined to each other by metal bonding, and the porosity of the negative electrode is 30-70%. This method for manufacturing a negative electrode for an iron-air secondary cell is provided with a step for mixing a resin and a metal powder having iron or an iron alloy as the main component, a step for molding the mixture obtained in the mixing step, and a step for sintering the molded article obtained in the molding step.

Description

Negative electrode for iron-air secondary battery, iron-air secondary battery, and method for producing negative electrode for iron-air secondary battery

The present invention relates to a negative electrode for an iron-air secondary battery, an iron-air secondary battery, and a method for producing a negative electrode for an iron-air secondary battery.

Among the secondary batteries in practical use, the one having the highest energy density (the amount of electric power that can be discharged with respect to the battery mass) is a lithium ion battery. As a secondary battery exceeding the energy density of a lithium ion battery, a metal-air secondary battery has attracted attention. In the metal-air secondary battery, the reactant of the positive electrode is oxygen in the air, and the reactant of the negative electrode is a metal. The feature of this metal-air secondary battery is that the mass of the reactant in the positive electrode can theoretically be zero because oxygen in the atmosphere is utilized at the positive electrode. The mass of the battery occupies most of the mass of the reactant at the positive and negative electrodes and the mass of the electrolyte that mediates the reaction. For this reason, the energy density of a metal-air secondary battery capable of reducing the mass of the reactant on one electrode to zero can be dramatically improved.

As a metal-air secondary battery, a combination of a conductive material such as carbon powder and an oxygen reduction catalyst is used as a positive electrode (air electrode), and zinc, aluminum, iron, lithium, or the like is used as a negative electrode (metal electrode). Things are common. Among negative electrode materials, iron is excellent in terms of cost and the like. For example, a metal-air all solid secondary battery having a negative electrode in which iron oxide nanoparticles as a negative electrode active material are supported on the surface of a KOH-ZrO ₂ based solid electrolyte ( There is an iron-air secondary battery) (see JP 2012-74371 A). By using such a negative electrode, the characteristics of the iron-air secondary battery are improved as compared with the case of using a negative electrode made only of iron powder. However, the energy density and maximum discharge capacity of the iron-air secondary battery having the negative electrode are also insufficient for practical use, and the development of a more excellent negative electrode for iron-air secondary battery is desired.

JP 2012-74371 A

In view of the above circumstances, the present invention provides an iron-air secondary battery negative electrode capable of forming an iron-air secondary battery having a large energy density, an iron-air secondary battery having a large energy density, and an iron-air secondary having a large energy density. It aims at providing the manufacturing method of the negative electrode for iron-air secondary batteries which can form a battery.

The invention made in order to solve the above-mentioned problems is a negative electrode used in an iron-air secondary battery, in which a metal powder particle mainly composed of iron or an iron alloy is joined by metal bonding. This is a negative electrode for an iron-air secondary battery having a porosity of 30% or more and 70% or less.

The negative electrode for an iron-air secondary battery has a three-dimensional combination of metal powders mainly composed of iron or an iron alloy. Since the metal powder has a small particle diameter, ions serving as electron carriers are present on the particle surface. Most of the iron contained in the particles can react with the carrier ions when supplied to. In addition, since the negative electrode for the iron-air secondary battery has a porosity of 30% or more and 70% or less, carrier ions are supplied to the inside of the three-dimensional joined body, so the metal powder inside the three-dimensional joined body It can be used for battery reaction up to iron. For this reason, the energy density of an iron-air secondary battery becomes large by using the said negative electrode for iron-air secondary batteries.

The “porosity” is a value measured according to JIS-Z2501 (2000).

The three-dimensional bonded body may be a sintered body of metal powder. Thus, when the three-dimensional combination is a sintered body of metal powder, the three-dimensional combination can be formed easily and inexpensively.

The three-dimensional combination may have continuous pores. Thus, since the said three-dimensional conjugate | bonded_body has a continuous pore, since carrier ion can be more reliably supplied to the inside of a three-dimensional conjugate | bonded_body, the energy density of an iron-air secondary battery can be made larger.

Carbon may adhere to the surface of the three-dimensional combination. Thus, by adhering carbon to the surface of the three-dimensional bonded body, the conductivity of the negative electrode for the iron-air secondary battery can be improved, and the internal resistance of the iron-air secondary battery can be reduced. . Moreover, sulfur may adhere to the surface of the three-dimensional bonded body. As described above, sulfur adheres to the surface of the three-dimensional bonded body, thereby inhibiting the formation of an iron oxide film formed simultaneously with the reduction of iron on the surface of the iron-air secondary battery negative electrode during charging. In addition, iron can be sufficiently reduced to zero. The “surface of the three-dimensional conjugate” includes the inner surface of the pores of the three-dimensional conjugate.

The average particle size of the metal powder is preferably 10 μm or more and 100 μm or less. Thus, when the average particle diameter of the metal powder is within the above range, the energy density of the iron-air secondary battery can be increased. The “average particle diameter” means the average of equivalent circle diameters of particles measured by microscopic observation of the surface of the three-dimensional conjugate.

The metal powder may be water atomized powder. Thus, when the metal powder is a water atomized powder, the surface area of the metal powder and thus the negative electrode for the iron-air secondary battery is increased, the reactivity can be increased and the energy density can be further improved, and the water Since the atomized powder is suitable for mass production, the negative electrode for an iron-air secondary battery can be provided at low cost.

The iron-air secondary battery may use a solid electrolyte. As described above, since the iron-air secondary battery uses a solid electrolyte, the structure of the iron-air secondary battery is simplified. The degree of freedom in designing the secondary battery and thus the negative electrode for the iron-air secondary battery is increased.

Further, another invention made to solve the above-described problems is an iron-air secondary battery including the above-described negative electrode for an iron-air secondary battery.

Since the iron-air secondary battery uses the negative electrode for the iron-air secondary battery, the energy density can be increased.

Further, another invention made to solve the above problems includes a step of mixing a metal powder and a resin mainly composed of iron or an iron alloy, a step of forming a mixture obtained in the mixing step, It is a manufacturing method of the negative electrode for iron-air secondary batteries provided with the process of sintering the molded object obtained at a formation process.

Since the method for producing the negative electrode for an iron-air secondary battery sinters a mixture of a metal powder and a resin, pores (cavities) can be formed by thermal decomposition of the resin, and a three-dimensional bonded body having a large porosity is obtained. A negative electrode for an iron-air secondary battery can be formed. Therefore, the negative electrode for iron-air secondary batteries obtained by the method for producing the negative electrode for iron-air secondary batteries can be used for battery reactions up to the iron present in the three-dimensional combination. For this reason, the manufacturing method of the said negative electrode for iron air secondary batteries can manufacture the negative electrode for iron air secondary batteries which can enlarge the energy density of an iron air secondary battery.

The negative electrode for an iron-air secondary battery of the present invention and the negative electrode for an iron-air secondary battery obtained by the method for producing a negative electrode for an iron-air secondary battery of the present invention can form an iron-air secondary battery having a large energy density. Further, the iron-air secondary battery of the present invention has a large energy density.

It is a schematic diagram which shows the structure of the iron-air secondary battery of one Embodiment of this invention. It is a surface micrograph of the negative electrode for iron-air secondary batteries of Example 1 of this invention. It is a graph which shows the discharge characteristic of the iron air secondary battery using the negative electrode for iron air secondary batteries of Example 1 of this invention and a comparative example. It is a microscope picture of the cross section after discharge of the negative electrode for iron-air secondary batteries of Example 1 of this invention. It is a microscope picture of the cross section after the discharge of the negative electrode for iron-air secondary batteries of the comparative example of this invention. It is a scanning electron micrograph of the negative electrode for iron-air secondary batteries of Example 2 of this invention. It is a graph which shows the relationship between the discharge capacity of an iron-air secondary battery using the negative electrode for iron-air secondary batteries of Example 2, and a cycle. It is a graph which shows the charging / discharging curve of the iron air secondary battery using the negative electrode for iron air secondary batteries of Example 3. It is a scanning electron micrograph of the negative electrode for iron-air secondary batteries of Example 4 of this invention. It is a graph which shows the charging / discharging characteristic of the iron air secondary battery using the negative electrode for iron air secondary batteries of Example 4. It is a graph which expands and shows immediately after the discharge start of FIG. It is a typical exploded view which shows the structure of the iron-air secondary battery of Example 5 of this invention. It is a graph which shows the charging / discharging characteristic of the iron air secondary battery using the negative electrode for iron air secondary batteries of Example 5.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as appropriate.

[Iron-air secondary battery]
An iron-air secondary battery according to an embodiment of the present invention shown in FIG. 1 faces an iron negative electrode (a negative electrode for an iron-air secondary battery) 1 that is an embodiment of the present invention, and the iron negative electrode 1. An air electrode (positive electrode for an iron-air secondary battery) 2 and an electrolyte 3 filled between the iron negative electrode 1 and the air electrode 2 are provided. Further, in the iron-air secondary battery shown in FIG. 1, conductive wires are connected to the iron negative electrode 1 and the air electrode 2, respectively, and are electrically connected to a load X through the conductive wires.

The iron-air secondary battery is a storage battery that uses iron in the iron negative electrode 1 as the negative electrode active material and oxygen in the air as the positive electrode active material.

<Iron negative electrode>
The iron negative electrode 1 is a cathode using iron as an active material. The iron negative electrode 1 has a three-dimensional combination formed from a metal powder mainly composed of iron or an iron alloy. In this three-dimensional bonded body, the metal powder is bonded to each other by metal bonding. The metal powder forming the three-dimensional combination may contain an additive element. Further, the three-dimensional combined body may include a material other than the metal powder. As such a three-dimensional joined body, a sintered body of metal powder that is easy to form is suitable. Moreover, the iron negative electrode 1 may be formed only from the three-dimensional combination body of a metal powder, for example, may further have a current collection conductor or a structural material for reinforcement. The shape and dimensions of the iron negative electrode can be selected so as to obtain the discharge capacity required for the iron-air secondary battery in consideration of the energy density per weight of iron.

In this iron negative electrode 1, the electrolyte 3 is impregnated in the pores of the three-dimensional combination of metal powders, thereby increasing the contact area between the negative electrode active material (iron) and the electrolyte 3, thereby causing the reaction of the negative electrode active material. Facilitate. For this reason, it is preferable that the three-dimensional combined body of the iron negative electrode 1 has continuous pores so that the electrolyte 3 can be entirely impregnated up to the central portion.

The lower limit of the porosity of the iron negative electrode 1 is 30%, preferably 35%, and more preferably 40%. On the other hand, the upper limit of the porosity of the iron negative electrode 1 is 70%, preferably 65%, and more preferably 60%. When the porosity of the iron negative electrode 1 is less than the said minimum, the surface area of the iron negative electrode 1 is small, and there exists a possibility that the energy density of the said iron air secondary battery may become inadequate. On the other hand, when the porosity of the iron negative electrode 1 exceeds the above upper limit, the strength of the iron negative electrode 1 may be insufficient, or formation of the iron negative electrode 1 may be difficult.

Further, in the iron negative electrode 1, it is preferable that carbon is attached to the surface (including the pore inner surface) of the three-dimensional bonded body. Carbon assists the electrical conduction of the three-dimensional combination and reduces the internal resistance of the iron-air secondary battery. As will be described later, this carbon can be formed by carbonizing a resin used to form pores of a three-dimensional combination.

Further, in the iron negative electrode 1, it is preferable that at least one of chlorine and sulfur is attached to the surface of the three-dimensional bonded body. Chlorine and sulfur suppress the reaction of iron in the iron negative electrode 1 by decomposing a hydroxide other than iron, which is an active material formed on the surface of the three-dimensional bonded body, by reaction. In particular, since sulfur adheres to the surface of the three-dimensional combination, formation of an iron oxide film formed simultaneously with the reduction of iron on the surface of the iron negative electrode 1 during charging is inhibited, and the zero valence of iron is reduced. Can be sufficiently reduced. In addition, adhesion of sulfur can be performed by, for example, enclosing iron particles in a vacuum tube and vaporizing sulfur by heating to form iron sulfide on the surface of the iron particles.

The lower limit of the average particle diameter of the metal powder is preferably 10 μm, more preferably 20 μm, and further preferably 30 μm. On the other hand, the upper limit of the average particle diameter of the metal powder is preferably 100 μm, more preferably 90 μm, and still more preferably 80 μm. When the average particle diameter of the metal powder is less than the lower limit, handling may be difficult during the production of the negative electrode. In addition, pores of a sufficiently large size cannot be formed in the negative electrode, and it becomes difficult for the electrolyte 3 to be impregnated inside the three-dimensional bonded body, so that the energy density of the iron-air secondary battery may be insufficient. On the contrary, when the average particle diameter of the metal powder exceeds the upper limit, the central part of the metal powder does not react, and the energy density of the iron-air secondary battery may be insufficient.

Further, the lower limit of the average equivalent circle diameter of the joint (fusion) portion between the metal powder particles is preferably 3 μm, and more preferably 5 μm. On the other hand, the upper limit of the average equivalent circle diameter of the joint portion between the metal powder particles is preferably 50 μm, and more preferably 30 μm. If the average equivalent circle diameter of the joint portion between the particles of the metal powder is less than the above lower limit, the electrical continuity between the particles of the metal powder becomes insufficient, and there is a risk of limiting the charging / discharging of the iron-air secondary battery. is there. Conversely, if the average equivalent circle diameter of the joint portion between the particles of the metal powder exceeds the above upper limit, the surface area of the three-dimensional combination may be reduced, and the energy density of the iron-air secondary battery may be insufficient. Alternatively, it may be difficult to ensure the porosity.

The metal powder is not particularly limited, but water atomized powder is preferable. Water atomized powder is obtained by micronizing and solidifying molten metal by jetting high-pressure water. Such a water atomized powder has irregularities on the surface and a large specific surface area. Therefore, the contact area between the three-dimensional combination of the iron negative electrode 1 and the electrolyte 3 is increased, and the energy density of the iron-air secondary battery is increased. Can be bigger. Moreover, water atomized powder can be manufactured or purchased at low cost.

The contact area between the three-dimensional combination of the negative electrode 1 and the electrolyte 3 can be increased by etching. As the etching at this time, it is preferable to form micro facet pits of about several microns on the surface by an etch pit corrosion method. In such etching, two different kinds of etching liquids (A liquid: a mixture of HCL, H ₂ O ₂ and H ₂ O, B liquid: a mixed solution of FeCl ₃ .6H ₂ O, H ₂ O and HNO ₃ are mixed. Pit is distributed almost uniformly with the liquid A, and the inner surface of the pit is grown to a low index facet such as {100} or {110} by anisotropic etching with the liquid B. The pit size can be controlled by adjusting the hydrogen ratio. Increasing the ratio of hydrogen peroxide with solution A produces a large number of small pits of 1 to 2 μm, and conversely decreasing the number of small pits. Further, by using formic acid, facet pits can be enlarged.

Further, particles having a small particle size may be combined with metal powder. Examples of such particles include iron sponge, carbonyl iron particles, and iron oxide particles having an average particle diameter of 5 μm or less, more preferably 3 μm or less. Further, for the compounding, a method using a difference in surface potential such as an electrostatic adsorption method or a mechanical compounding method such as mechanochemical or mechanofusion can be used.

<Air electrode>
The air electrode 2 is formed of a conductive material in order to supply electrons used for the reaction of oxygen in the air, which is a positive electrode active material. The air electrode 2 preferably carries an oxygen reduction catalyst that promotes the decomposition reaction of hydrogen peroxide at the positive electrode described later. In addition, those having oxygen generation ability and durability are desirable.

As the conductive material, carbon is preferably used. For example, a carbon powder compact or carbon paper can be used. Examples of the oxygen reduction catalyst include platinum (platinum), manganese dioxide, and various perovskite oxides.

The air electrode 2 is preferably a sheet-like one. As a minimum of average thickness of air electrode 2, 0.05 mm is preferred and 0.1 mm is more preferred. On the other hand, the upper limit of the average thickness of the air electrode 2 is preferably 0.3 mm, and more preferably 0.2 mm. By setting the average thickness of the air electrode to the above lower limit or more, a sufficient reaction can be caused. If the air electrode becomes too thick, it tends to be difficult to efficiently form a three-phase interface of electrolyte, catalyst, and air.

<Electrolyte>
The electrolyte 3 provides a hydroxide ion (OH ⁻ ) serving as a carrier for transporting electric charge between the iron negative electrode 1 and the air electrode 2, and one that is usually used for a metal-air secondary battery is used. be able to. The electrolyte 3 may be a liquid electrolyte or a solid electrolyte, and a plurality of types of electrolytes may be used, or a plurality of electrolytes may be used in multiple layers. Further, the electrolyte 3 may be filled in a sealed space formed by a frame-shaped member that is sandwiched between the iron negative electrode 1 and the air electrode 2, for example. The electrolyte 3 is preferably a solid electrolyte that does not require a member for sealing the space filled with the electrolyte 3.

Examples of the liquid electrolyte include a solution in which a salt is dissolved in a solution or an ionic liquid. Examples of the liquid electrolyte in solution include an aqueous alkali solution such as an aqueous potassium hydroxide solution or an aqueous sodium hydroxide solution. The electrolyte may contain an additive such as potassium sulfide (K ₂ S).

When a solid electrolyte is used as an electrolyte, the iron-air secondary battery usually has a laminated structure in which a thin solid electrolyte is disposed between a plate-like iron negative electrode 1 and a plate-like air electrode 2. Composed. By using such a thin-layer solid electrolyte, the energy density of the iron-air secondary battery can be further increased.

Solid electrolyte refers to an electrolyte that does not have fluidity, and is composed of a polymer such as a polyethylene oxide polymer or an inorganic substance such as Li ₂ S—SiS ₂ , or a salt such as a basic hydroxide. The thing of the gel body hold | maintained at the gel can be mentioned. Examples of the salt in the gel solid electrolyte include basic hydroxides such as potassium hydroxide and sodium hydroxide, and examples of the gel include zirconia gel. A binder such as polyvinylidene fluoride (PVdF) may be mixed in the solid electrolyte.

When the solid electrolyte is layered, it is preferable that the average film thickness is 0.1 mm or more in order to exhibit the effect of conducting hydroxide ions and prevent short circuit. However, since the actual resistance (battery internal resistance) increases when the thickness is too large, the average film thickness is preferably set to 0.3 mm or less, for example.

<Charging and discharging of iron-air secondary batteries>
Here, the principle of discharging and charging of the iron-air secondary battery will be described.

In the iron negative electrode 1 during discharge of the iron-air secondary battery, as shown in the following reaction formula (1), iron in the three-dimensional combination of the iron negative electrode 1 reacts with hydroxide ions in the electrolyte 3. Electrons are generated by becoming iron hydroxide.
Fe + 2OH ⁻ → Fe (OH) ₂ + 2e ⁻ (1)

Further, the iron hydroxide generated in the above reaction formula (1) further reacts with hydroxide ions in the electrolyte 3 to generate iron tetroxide and water as shown in the following reaction formula (2). To generate electrons.
3Fe (OH) ₂ + 2OH ⁻ → Fe ₃ O ₄ + 4H ₂ O + 2e ⁻ (2)

Therefore, the above reaction formulas (1) and (2) in the iron negative electrode 1 can be collectively expressed as the following reaction formula (3).
3Fe + 8OH ⁻ → Fe ₃ O ₄ + 4H ₂ O + 8e ⁻ (3)

Further, when the iron-air secondary battery is charged, a reaction opposite to the reaction formula (3), that is, the reaction formulas (1) and (2) occurs in the iron negative electrode 1. That is, when electrons are supplied to iron tetroxide or iron hydroxide in the three-dimensional combination of the iron negative electrode 1, the iron is reduced and separated into iron and hydroxide ions.

Here, since the reaction in the iron negative electrode 1 is a solid-phase reaction that does not involve elution of iron ions into the electrolyte 3 and precipitation of iron from the electrolyte 3, dendride (dendritic crystals) associated with dissolution and precipitation of metal. There is no formation and the shape of the iron negative electrode 1 does not change. For this reason, even if the said iron air secondary battery repeats charging / discharging, an energy density does not fall easily.

Further, since the reaction in the iron negative electrode 1 is a solid-phase reaction, only iron existing within a range of several μm from the material surface is supplied from the electrolyte 3 as shown in the above reaction formulas (1) and (2). It cannot react with hydroxide ions to form iron hydroxide and thus iron tetroxide. However, since the iron negative electrode 1 of the iron-air secondary battery uses a three-dimensional bonded body in which the electrolyte 3 is impregnated as described above, most of the iron in the three-dimensional bonded body contacts the electrolyte 3. It exists in the vicinity of the material surface (including the inner surface of the pores) to be subjected to the above reaction. Therefore, the iron-air secondary battery has a high energy density. Further, since the particles are bonded to each other by metal bonds, even if iron hydroxide or iron tetroxide is formed on the surface, the current flow is not affected.

On the other hand, in the air electrode 2 at the time of discharge of the iron-air secondary battery, as shown in the following reaction formula (4), a circuit having a load X from oxygen in the air, water in the electrolyte 3, and the iron negative electrode 1 is provided. Hydrogen peroxide ions and hydroxide ions are generated from the electrons supplied through them.
O ₂ + H ₂ O + 2e ⁻ → O ₂ H ⁻ + OH ⁻ (4)

As shown in the following reaction formula (5), the hydrogen peroxide ions generated in the above reaction formula (4) are further decomposed by the catalytic reaction of the oxygen reduction catalyst to generate hydroxide ions and oxygen.
O ₂ H ⁻ → OH ⁻ + 1 / 2O ₂ (5)

Therefore, the reaction formulas (4) and (5) in the air electrode 2 can be collectively expressed as the following reaction formula (6).
1 / 2O ₂ + H ₂ O + 2e ⁻ → 2OH ⁻ (6)

Further, when the iron-air secondary battery is charged, a reaction opposite to the above reaction formula (6), that is, the reaction formulas (4) and (5) occurs in the air electrode 2.

<Iron negative electrode manufacturing method>
Here, the manufacturing method of the iron negative electrode 1 of the said iron air secondary battery is demonstrated.

The iron negative electrode 1 is obtained in a step of mixing a metal powder mainly composed of iron or an iron alloy and a resin (mixing step), a step of forming a mixture obtained in the mixing step (molding step), and this forming step. It can manufacture by the method provided with the process (sintering process) of sintering the molded object obtained.

(Mixing process)
In the mixing step, the metal powder that forms the three-dimensional combined body of the iron negative electrode 1 and the resin are mixed. When the fluidity of the resin is insufficient, a solution obtained by dissolving the resin in a solvent may be used. Moreover, you may form the paste-form mixture which disperse | distributed the metal powder and resin powder to the dispersion medium using powder-form resin. In addition to the metal powder and the resin, an additive may be blended.

The metal powder is as described above for the iron negative electrode 1.

The resin mixed with the metal powder is thermally decomposed in the sintering process to form pores in the resulting three-dimensional bonded body. In some cases, this resin functions as a binder for connecting metal powders in the molding process.

The resin mixed with the metal powder is not particularly limited as long as it does not deteriorate the moldability of the mixture with the metal powder and can be thermally decomposed in the sintering process. For example, water-soluble polyvinyl alcohol can be used.

The volume ratio between the metal powder and the resin is determined according to the porosity to be obtained. In determining the volume ratio between the metal powder and the resin, the volume of the solvent or dispersion medium contained in the mixture, or the volume of pores formed in the molded body according to the blending method and the molding method in the molding process is also taken into consideration. Is done.

(Molding process)
In the molding step, the mixture of the metal powder and the resin is molded into a desired iron negative electrode 1 shape. At this time, a current collecting conductor or a reinforcing structural member may be inserted and molded.

As a method for forming the mixture, for example, molding or the like can be applied when the mixture has fluidity, and for example, compression molding can be applied when the mixture does not have fluidity. Specific examples of the molding method of the mixture include powder press molding in which a powder obtained by pulverizing the dried mixture obtained in the mixing step is compressed with a mold.

When the solvent content in the mixture obtained in the mixing step is large, a drying step for volatilizing the solvent may be provided before the forming step or after the forming step.

(Sintering process)
In the sintering process, by heating the molded body obtained in the molding process, the metal powder in the molded body is sintered and the resin is thermally decomposed to form pores. From the viewpoint of improving the discharge capacity, it is possible to gradually raise the temperature to the sintering temperature at a constant rate so that the obtained iron negative electrode 1 is not completely oxidized (so that it has an unoxidized portion). preferable.

The heating temperature can be, for example, 900 ° C. or higher, more preferably 1000 ° C. or higher and 1300 ° C. or lower. Moreover, as heating time, it can be 15 minutes or more and 1 hour or less, for example.

If this sintering step is performed in an inert gas atmosphere, carbon in the resin can be carbonized and remain as carbon on the surface of the three-dimensional bonded body. For example, nitrogen gas can be used as the inert gas.

[Other Embodiments]
The said embodiment does not limit the structure of this invention. Therefore, in the above-described embodiment, the components of each part of the above-described embodiment can be omitted, replaced, or added based on the description and common general knowledge of the present specification, and they are all interpreted as belonging to the scope of the present invention. Should.

The iron-air secondary battery is not limited to a three-layer structure of an iron negative electrode, an electrolyte, and an air electrode. For example, an electrolyte layer is formed on both sides of the iron negative electrode, and an air electrode is provided on the outer sides of the electrolyte layers on both sides. It is good also as a 5 layer structure provided with. Further, the iron-air secondary battery may have a plurality of iron negative electrodes. Further, the iron negative electrode, the electrolyte, and the air electrode may be formed, for example, in a tubular shape or a spiral shape. That is, the shapes of the iron negative electrode, the electrolyte, and the air electrode are not particularly limited.

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not construed as being limited based on the description of the examples.

<Example 1>
First, negative electrodes for iron-air secondary batteries having different porosities were prepared, and the relationship between the porosity and the discharge performance was investigated by the three-electrode method.

(Negative electrode for iron-air secondary battery)
As the material for the negative electrode for the iron-air secondary battery, water atomized iron powder “Atomel 250M” having an average particle diameter of 70 μm from Kobe Steel was used as the metal powder, and polyvinyl alcohol was used as the resin mixed with the metal powder.

Specifically, first, 8 g of polyvinyl alcohol in 6 g of water was heated to 80 ° C. to dissolve the polyvinyl alcohol, and this polyvinyl alcohol aqueous solution was mixed with 80 g of metal powder.

Subsequently, the above mixture was filled into a disk-shaped cavity having a diameter of 2 cm and a height of 0.5 cm to form a disk-shaped molded body.

After the molded body was dried, it was sintered by heating in a nitrogen gas atmosphere at 1120 ° C. for 20 minutes, and was cut into a 5 mm × 5 mm × 15 mm column shape by wire electric discharge machining and used as Example 1 of an iron negative electrode did. Carbon adheres to the surface of the three-dimensionally bonded metal powder of the iron negative electrode obtained by this method.

FIG. 2 shows a micrograph of the surface of the prototype negative electrode for an iron-air secondary battery. In the figure, the bright part is iron particles, and the dark part corresponds to the gap. In addition, the porosity of this negative electrode for iron-air secondary batteries was about 50%.

<Comparative example>
For comparison, a comparative example of an iron negative electrode was prepared by sintering without mixing the resin and cutting out into a 5 mm × 5 mm × 15 mm columnar shape by wire electric discharge machining. The porosity of the comparative example of this iron negative electrode is about 18%, the communication between the internal pores is insufficient, and it is considered that the pores are not continuous.

Subsequently, the electrodes were evaluated. In order to compare only the characteristics of the iron negative electrode, the charge / discharge characteristics were evaluated by the three-electrode method. Specifically, an Hg / HgO (1M-NaOH) electrode was used as the reference electrode, and a Pt electrode was used as the counter electrode. An 8M-KOH aqueous solution was used as the electrolytic solution, and the tip of the iron negative electrode 5 mm was immersed in the electrolytic solution. Evaluation was performed with a charging current of 5 mA and a discharging current of 5 mA. The charging time was equally 48 hours.

(Charge / discharge characteristics)
FIG. 3 shows the change in voltage when the iron negative electrodes of Example 1 and Comparative Example were charged at 5 mA for 48 hours and then discharged at 5 mA. Here, the results up to the third cycle are shown.

As shown in the figure, charging / discharging was observed in any of the iron negative electrodes, indicating that these iron negative electrodes can operate as secondary batteries. However, the iron negative electrode of Example 1 having a porosity of 50% continued to discharge for about 13 hours as the initial discharge (discharge at the first cycle), and 10 hours after stabilization (discharge after the second cycle). In contrast, the iron electrode of the comparative example having a porosity of 18% had only a discharge time of about 4 hours. In addition, in the iron negative electrode of Example 1, flat portions corresponding to the respective oxidation reactions were clearly observed in the discharge characteristics, whereas in the iron negative electrode of the comparative example, only a few flat portions were confirmed. Further, the discharge density per weight of iron showed a high performance of 100 mAh / g or more in the iron negative electrode of Example 1, whereas it remained at about 25 mAh / g in the iron negative electrode of the comparative example. The effect of improving the density was confirmed.

Further, cross-sectional observation at the end of discharge of the iron electrodes of Example 1 and Comparative Example was performed. Specifically, the electrode was cut, embedded in resin, polished to obtain a cross section, and the cross section was observed. The micrographs are shown in FIGS. In the iron negative electrode of Example 1 (FIG. 4) having a porosity of 50%, many cavities (dark parts) were observed around the iron negative electrode observed as bright parts, and the formation of iron oxide could be confirmed on the surface. It was. That is, it turned out that the iron negative electrode of Example 1 has contributed to charging / discharging to the inside of an electrode. On the other hand, in the iron electrode of the comparative example having a porosity of 18% (FIG. 5), the existing cavities (dark parts) are isolated from each other, like the iron negative electrode of Example 1 having a porosity of 50%. The internal charge / discharge reaction could not be confirmed. From this, in the iron negative electrode of Example 1 whose porosity is 50%, it turned out that the cavity is connected to the exterior and contributes to the inside to charge / discharge.

<Example 2>
Next, in order to increase the contact area between the three-dimensionally bonded iron negative electrode and the electrolyte, iron particles were combined by an electrostatic adsorption method to produce a negative electrode.

As a specific procedure for preparing the negative electrode, using an electrostatic adsorption composite method, iron sponge (average particle size: about 5 μm) as a child particle, polydiallyldimethylammonium chloride (PDDA), polystyrene sulfonate sodium (PSS), and The treatment was performed in the order of PDDA and positively charged. On the other hand, iron particles (average particle size: about 45 μm) were used as mother particles, and the treatment was performed in the order of PSS, PDDA, and PSS to be negatively charged. Furthermore, iron sponge and iron particles were mixed to produce iron composite particles. The produced composite particles were formed and sintered by slip casting to produce a porous body. In the production of this porous body, the temperature was raised from room temperature to 800 ° C., heated at 800 ° C. for 1 hour and sintered (iron oxide porous body), and the temperature rising process was omitted and heated at 800 ° C. for 20 minutes for sintering. (Porous iron body) was obtained as a negative electrode material. The density estimated from the total volume of the negative electrode material is about 2.5 to 3 g / cm ³ , which is a value of about 30% to 38% of the density of iron, and the porosity is 62 to 70%. Equivalent to.

The structure of the produced porous negative electrode material was observed with a scanning electron microscope (SEM). In FIG. 6, the SEM observation result of the surface (a) and the inside (b) of an iron porous body is shown. From this, it was confirmed that the produced iron porous body had a structure in which there were child particles between the mother particles and the gap was made by the size of the child particles. Further, in this iron porous body, the surface portion was sintered but the inside was not sintered. From the XRD measurement results, the iron oxide porous body could not be confirmed except for the peak of iron oxide, and was completely oxidized, and the iron porous body was confirmed to have both peaks of iron and iron oxide.

Moreover, the redox behavior of the produced porous negative electrode material was evaluated by a cyclic voltammetry method in an aqueous potassium hydroxide solution. In this evaluation test, the working electrode was made of an iron oxide porous body and an iron porous body, a reference electrode was an Hg / HgO (1M-NaOH) electrode, a counter electrode was a Pt electrode, a charging rate of 10 mA, an iron oxide porous body and an iron porous body The discharge rates were 0.2 mA and 5 mA, respectively.

Fig. 7 shows the cycle characteristics of the above test. With the iron oxide porous body, a discharge capacity of 20 to 100 mAh / g was obtained in terms of Fe weight. On the other hand, the iron porous body obtained a discharge capacity of 300 to 500 mAh / g larger than that of the iron oxide porous body, and no cycle deterioration was confirmed. This revealed that the iron porous body can be used as a useful air battery negative electrode material. The reason for this is considered that iron remains in the iron porous body, so that many electron conductive paths are formed and the discharge capacity is improved.

<Example 3>
Next, using the iron negative electrode of Example 1, Example 3 of the negative electrode for an iron-air secondary battery according to the above embodiment was produced to produce an iron-air secondary battery, and the performance of this iron-air secondary battery It was confirmed.

(Air electrode)
As the air electrode, a commercially available carbon paper carrying a platinum catalyst (“EC-10-05-7” manufactured by Toray Industries, Inc.) was used.

As the electrolyte, an 8M aqueous potassium hydroxide solution was used. In some experiments, 0.05 M potassium sulfide (K ₂ S) was added.

(Charge / discharge characteristics)
FIG. 8 shows a change in voltage when a prototype of the iron-air secondary battery having the above configuration is charged at 5 mA for 48 hours (charge capacity 517 mAh / g) and then discharged at 5 mA. As shown in FIG. 8, two distinct flat portions corresponding to iron oxidation were observed during discharge. The initial discharge capacity was 91 mAh / g (Fe), the second cycle was 55 mAh / g (Fe), the third cycle was 54 mAh / g (Fe), and charge / discharge was confirmed, that is, the operation of the secondary battery was confirmed. . Further, when K ₂ S was added to the electrolyte, charging / discharging could be confirmed in the same manner, and the initial discharge capacity was 115 mAh / g (Fe).

<Example 4>
Next, Example 4 of the negative electrode for an iron-air secondary battery according to the above embodiment was produced to produce an iron-air secondary battery, and the performance of the iron-air secondary battery was confirmed.

(Negative electrode for iron-air secondary battery)
As a material for the negative electrode for the iron-air secondary battery, water atomized iron powder “Atomel 300M” with an average particle diameter of 70 μm from Kobe Steel was used as the metal powder. The manufacturing method is the same as in Example 1.

Subsequently, the mixture was filled into a cylindrical cavity having a diameter of 1 cm and a height of 1 cm to form a cylindrical molded body.

The dried product was dried and heated in a nitrogen gas atmosphere at 1120 ° C. for 20 minutes, and then sintered with hydrochloric acid, and then used as a negative electrode for an iron-air secondary battery. No carbon is attached to the surface of the three-dimensionally bonded body of the metal powder of the iron negative electrode of Example 4 obtained in this way.

FIG. 9 shows a scanning electron microscope (SEM) photograph of the surface of the prototype negative electrode for an iron-air secondary battery. The porosity of this negative electrode for iron-air secondary batteries was about 50%.

(Air electrode)
As the air electrode, water repellent carbon paper coated with electrolytic manganese dioxide as an oxygen reduction catalyst was used.

As the electrolyte, an 8M aqueous potassium hydroxide solution was used.

(Charge / discharge characteristics)
FIG. 10 shows a change in voltage when a prototype of the iron-air secondary battery having the above configuration is charged at 5 mA for 30 hours and then discharged at 0.2 mA.

As shown in the figure, the iron-air secondary battery prototype continued to discharge for more than 500 hours, although a slight decrease in voltage was observed after 200 hours, and finally confirmed the discharge for 900 hours. From this, it was confirmed that it has practically sufficient discharge characteristics.

Furthermore, as shown in FIG. 11, when the voltage change immediately after the start of discharge is examined in detail, the voltage decreases exponentially and rapidly from 6 hours after the start of discharge, but after 6 hours from the start of discharge, The voltage decreases approximately linearly and slowly. This is mainly a reaction in which iron (Fe) reacts with hydroxide ions (OH ⁻ ) to generate iron hydroxide (Fe (OH) ₂ ) in the early stage of discharge, and thereafter the generated iron hydroxide is Further, it is presumed that this is mainly due to a reaction that reacts with hydroxide ions (OH ⁻ ) to produce iron tetroxide (Fe ₃ O ₄ ) and water (H ₂ O).

<Example 5>
Next, Example 5 of the negative electrode for an iron-air secondary battery according to the above embodiment was produced using the iron negative electrode of Example 1. FIG. 12 shows a schematic diagram of the structure of the iron-air secondary battery. Such an all-solid iron-air secondary battery was prototyped and the performance of the all-solid iron-air secondary battery was confirmed.

(Air electrode)
As the air electrode 2, a commercially available carbon paper (“EC-10-05-7” manufactured by Toray Industries, Inc.) carrying 0.5 mg of a platinum catalyst was used.

As the electrolyte 3, a KOH—ZrO ₂ solid electrolyte in the form of powder pellets was used. The electrolyte 3 was disposed in an amount of 0.3 g per side so as to sandwich the iron negative electrode 1 from both sides, and a pair of air electrodes 2 was disposed outside the pair of electrolytes 3. The iron negative electrode 1 was sandwiched between a pair of glass slides 1a from a direction perpendicular to the electrode stacking direction. Moreover, while ensuring the passage of air, the periphery of the air electrode 2 was fixed using a pair of Teflon (registered trademark) ring-shaped guides 4 so that the respective members were in close contact with each other. The weight of the iron negative electrode 1 (a three-dimensional combination of metal powders) was 4.4256 g.

(Charge / discharge characteristics)
FIG. 13 shows changes in voltage when a prototype of the iron-air secondary battery having the above configuration is charged at 5 mA for 5 hours and then discharged at 0.2 mA. As shown in FIG. 12, charging / discharging of the all-solid-iron-air secondary battery using the negative electrode of Example 5, that is, the operation of the secondary battery was confirmed.

From the above results, it was confirmed that the iron-air secondary battery using the negative electrode for an iron-air secondary battery of the present invention has a large energy density.

The disclosure of the present specification includes the following aspects.
Aspect 1:
A negative electrode used for an iron-air secondary battery,
It has a three-dimensional bonded body in which particles of metal powder mainly composed of iron or iron alloy are bonded together by metal bonding,
A negative electrode for an iron-air secondary battery having a porosity of 30% to 70%.

Aspect 2:
The negative electrode for an iron-air secondary battery according to aspect 1, wherein the three-dimensional bonded body is a sintered body of metal powder.

Aspect 3:
The negative electrode for an iron-air secondary battery according to

aspect

1 or 2, wherein the three-dimensional combination has continuous pores.

Aspect 4:
The negative electrode for an iron-air secondary battery according to any one of aspects 1 to 3, wherein carbon or sulfur is attached to the surface of the three-dimensional bonded body.

Aspect 5:
The negative electrode for an iron-air secondary battery according to any one of embodiments 1 to 4, wherein the average particle diameter of the metal powder is 10 μm or more and 100 μm or less.

Aspect 6:
The negative electrode for an iron-air secondary battery according to any one of embodiments 1 to 5, wherein the metal powder is a water atomized powder.

Aspect 7:
The negative electrode for an iron-air secondary battery according to any one of embodiments 1 to 6, wherein the iron-air secondary battery uses a solid electrolyte.

Aspect 8:
An iron-air secondary battery comprising the negative electrode for an iron-air secondary battery according to any one of aspects 1 to 7.

Aspect 9:
A step of mixing metal powder and resin mainly composed of iron or iron alloy;
Forming the mixture obtained in the mixing step,
A method for producing a negative electrode for an iron-air secondary battery, comprising: a step of sintering a molded body obtained in the molding step.

This application is a Japanese patent application filed on July 6, 2015, Japanese Patent Application No. 2015-135656, a Japanese patent application filed on November 6, 2015, Japanese Patent Application No. 2015-218506. And a Japanese patent application filed on March 17, 2016, Japanese Patent Application No. 2016-053895 with a priority claim. Japanese Patent Application No. 2015-135656, Japanese Patent Application No. 2015-218506 and Japanese Patent Application No. 2016-053895 are incorporated herein by reference.

The iron-air secondary battery using the negative electrode for the iron-air secondary battery of the present invention can be widely used as a storage battery.

1 Iron negative electrode (negative electrode for iron-air secondary battery)
1a slide glass 2 air electrode (positive electrode for iron-air secondary battery)
3 Electrolyte 4 Guide X Load

Claims

A negative electrode used for an iron-air secondary battery,
It has a three-dimensional bonded body in which particles of metal powder mainly composed of iron or iron alloy are bonded together by metal bonding,
A negative electrode for an iron-air secondary battery having a porosity of 30% to 70%.
The negative electrode for an iron-air secondary battery according to claim 1, wherein the three-dimensional bonded body is a sintered body of metal powder.
The iron-air secondary battery negative electrode according to claim 1, wherein the three-dimensional combination has continuous pores.
The iron-air secondary battery negative electrode according to claim 1, wherein carbon or sulfur is attached to the surface of the three-dimensionally bonded body.
2. The negative electrode for an iron-air secondary battery according to claim 1, wherein the metal powder has an average particle size of 10 μm to 100 μm.
The iron-air secondary battery negative electrode according to claim 1, wherein the metal powder is water atomized powder.
The negative electrode for an iron-air secondary battery according to claim 1, wherein the iron-air secondary battery uses a solid electrolyte.
An iron-air secondary battery comprising the negative electrode for an iron-air secondary battery according to claim 1.
A step of mixing metal powder and resin mainly composed of iron or iron alloy;
Forming the mixture obtained in the mixing step,
A method for producing a negative electrode for an iron-air secondary battery, comprising: a step of sintering a molded body obtained in the molding step.