JP6142399B2 - Air secondary battery - Google Patents

Description

  The present invention relates to an air secondary battery.

  Since the air battery is supplied with oxygen, which is a positive electrode active material, from the outside of the battery, there is no need to store the positive electrode active material in the battery, and a large amount of the negative electrode active material can be filled in the battery. Expectations are high because high energy density can be achieved.

An air battery is a battery having a positive electrode including a positive electrode catalyst having oxygen reducing ability, a negative electrode using zinc, iron, aluminum, magnesium, lithium, hydrogen, or the like as a negative electrode active material, and an electrolytic solution. For example, when the negative electrode contains zinc, the discharge reaction of the air battery under alkaline conditions is represented by the following formula.
Positive electrode: O ₂ + 2H ₂ O + 4e ⁻ → 4OH ⁻
Negative electrode: Zn + 2OH ⁻ → ZnO + H ₂ O + 2e ⁻
Total reaction: 2Zn + O ₂ → 2ZnO

  Conventionally, batteries (secondary batteries, rechargeable batteries, storage batteries) that can store electricity by charging and can be used repeatedly are known. Development of batteries using oxygen as an active material is also underway. In the following description, a battery that uses oxygen in the air as an active material and can be repeatedly charged and discharged is referred to as an “air secondary battery” in order to distinguish it from the above-described air battery.

  As an air secondary battery, for example, Patent Document 1 discloses an air secondary battery using an electrolytic solution in which ammonium chloride is dissolved in water.

International Patent Publication WO2012-12558

  However, as described above, when an electrolytic solution in which ammonium chloride is dissolved in water is used for the air secondary battery, there is a problem that chlorine gas is generated during charging.

  The present invention has been made in view of such circumstances, and provides an air secondary battery in which generation of chlorine gas during charging is reduced.

That is, the present invention provides the following inventions.
An air secondary battery comprising: a positive electrode including a positive electrode catalyst having oxygen reduction activity and water oxidation activity; a negative electrode including at least one selected from the group consisting of zinc alone and a zinc compound; and an electrolyte. An air secondary battery in which the pH of the liquid is 1 to 13 and the concentration of chloride ions in the electrolytic solution is 1.0% by mass or less.

  According to the present invention, it is possible to provide a chargeable / dischargeable air secondary battery in which generation of chlorine gas during charging is reduced.

It is a schematic diagram which shows an example of the air secondary battery of this embodiment.

Hereinafter, this embodiment will be described in detail.

<Air secondary battery>
The air secondary battery of the present embodiment includes a positive electrode including a positive electrode catalyst having oxygen reduction activity and water oxidation activity, a negative electrode including one or more negative electrode active materials selected from the group consisting of zinc alone and a zinc compound, pH 1 to 13 and an electrolyte solution having a chloride ion concentration of 1.0% by mass or less.

FIG. 1 is a schematic cross-sectional view illustrating an embodiment of an air secondary battery according to this embodiment.
The air secondary battery 1 shown here includes a positive electrode catalyst layer 11 including the positive electrode catalyst, a positive electrode current collector 12, a negative electrode active material layer 13 including the negative electrode active material, a negative electrode current collector 14, an electrolyte solution 15, and the above. A container (not shown) is provided.
The positive electrode current collector 12 is disposed in contact with the positive electrode catalyst layer 11 to constitute a positive electrode. Further, the negative electrode current collector 14 is disposed in contact with the negative electrode active material layer 13, and these constitute a negative electrode. Further, a positive electrode terminal (lead wire) 120 is connected to the positive electrode current collector 12, and a negative electrode terminal (lead wire) 140 is connected to the negative electrode current collector 14.
The positive electrode catalyst layer 11 and the negative electrode active material layer 13 are disposed to face each other, and the electrolyte 15 is disposed so as to be in contact with them.
The air secondary battery according to the present embodiment is not limited to the one shown here, and a part of the configuration may be changed as necessary.

<Cathode catalyst>
In the air secondary battery of the present embodiment, the positive electrode catalyst is a catalyst having oxygen reduction activity and water oxidation activity, and preferably contains at least one selected from the group consisting of cobalt atoms and cobalt ions. .

  The positive electrode catalyst is preferably a mononuclear metal complex such as metal porphyrin or metal phthalocyanine; a polynuclear metal complex having a plurality of metal atoms or metal ions in one molecule; a metal cluster complex; a perovskite type, a spinel type, an olivine type. Inorganic oxides such as oxides; noble metals such as platinum and silver can be used.

  A mononuclear metal complex, a polynuclear metal complex, and an inorganic oxide are more preferable, and a mononuclear metal complex and a polynuclear metal complex are particularly preferable.

Specific structural formulas are exemplified for the mononuclear metal complex. M represents a metal atom or a metal ion. The hydrogen atom in the structural formula may be substituted.

Specific structural formulas are exemplified for the polynuclear metal complex. M represents a metal atom or a metal ion. A plurality of M may be the same or different. The hydrogen atom in the structural formula may be substituted. Note that the charge of the polynuclear metal complex is omitted.

(Method for producing metal complex)
Next, a method for synthesizing a metal complex suitably used in the present invention will be described.
In the metal complex of the present invention, for example, after the compound of the present invention is organically synthesized, the obtained compound is a reagent that gives a metal atom or metal ion (hereinafter referred to as “metal-imparting agent”). It is obtained by mixing with and reacting. The amount of the metal imparting agent to be reacted is not particularly limited, and the amount of the metal imparting agent may be adjusted according to the target metal complex. Usually, an excess amount of the metal imparting agent is reacted with the ligand. It is preferable to make it.

  Examples of the metal-imparting agent include acetate, fluoride, chloride, bromide, iodide, sulfate, carbonate, nitrate, hydroxide, perchlorate, trifluoroacetate, trifluoromethanesulfonic acid, tetrafluoro Examples thereof include borates, hexafluorophosphates, tetraphenyl borates and the like, and acetates are particularly preferable. Examples of the acetate include cobalt (II) acetate, iron (II) acetate, manganese (II) acetate, manganese (III) acetate, nickel (II) acetate, copper (II) acetate, and zinc (II) acetate. Preferably, it is cobalt acetate.

  The metal imparting agent may be a hydrate such as cobalt acetate (II) tetrahydrate, manganese acetate (II) tetrahydrate, manganese acetate (III) dihydrate, nickel acetate ( II) Tetrahydrate, copper acetate (II) monohydrate, zinc acetate (II) dihydrate.

  The step of mixing the ligand compound and the metal imparting agent is performed in the presence of a suitable solvent. As a solvent (reaction solvent) used in the reaction, water; organic acids such as acetic acid and propionic acid; amines such as aqueous ammonia and triethylamine; methanol, ethanol, n-propanol, isopropyl alcohol, 2-methoxyethanol, Alcohols such as 1-butanol and 1,1-dimethylethanol; ethylene glycol, diethyl ether, 1,2-dimethoxyethane, methyl ethyl ether, 1,4-dioxane, tetrahydrofuran (hereinafter referred to as “THF”), Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, durene, decalin; halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, 1,2-dichlorobenzene, N, N′-dimethylformamide (hereinafter, "DMF"), N, N'-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, acetone, acetonitrile, benzonitrile, triethylamine, pyridine and the like can be mentioned. In addition, these reaction solvents may be used individually by 1 type, or may use 2 or more types together. Moreover, as said solvent, the solvent in which the aromatic compound used as a ligand and a metal provision agent can melt | dissolve is preferable.

  The mixing temperature of the ligand compound and metal imparting agent is preferably −10 ° C. or higher and 250 ° C. or lower, more preferably 0 ° C. or higher and 200 ° C. or lower, and particularly preferably 0 ° C. or higher and 150 ° C. or lower.

  The mixing time of the ligand compound and the metal-imparting agent is preferably 1 minute or more and 1 week or less, more preferably 5 minutes or more and 24 hours or less, and particularly preferably 1 hour or more and 12 hours or less. In addition, it is preferable to adjust the said mixing temperature and mixing time in consideration of the kind of said ligand compound and a metal provision agent.

  The generated metal complex can be removed from the solvent by selecting and applying a suitable method from known recrystallization methods, reprecipitation methods, and chromatography methods. At this time, a plurality of the methods are combined. May be. Depending on the type of the solvent, the produced polynuclear metal complex may precipitate. In this case, the precipitated metal complex may be separated by filtration, and then washed, dried, or the like.

  The positive electrode catalyst layer 11 preferably includes a conductive material and a binder in addition to the positive electrode catalyst. The conductive material may be any material that can improve the conductivity of the positive electrode catalyst layer 11, but carbon is preferable.

Here, the carbon is the same as the carbon described and exemplified as the other components. Examples of the carbon include “NORIT” (manufactured by NORIT), “Ketjen Black” (manufactured by Lion), “Vulcan” (manufactured by Cabot), “Black Pearls” (manufactured by Cabot), “acetylene black” (electric) (Manufactured by Kagaku Kogyo Co., Ltd.) (all are trade names) carbon black; fullerenes such as C60 and C70; carbon fibers such as carbon nanotubes, multiwall carbon nanotubes, double wall carbon nanotubes, single wall carbon nanotubes, carbon nanohorns, graphene, Graphene oxide can be exemplified, and carbon black is preferable.
The carbon may be used in combination with a conductive polymer such as polypyrrole or polyaniline.

  Examples of the binder include those that adhere the positive electrode catalyst, the conductive material, and the like to the positive electrode current collector 12. Examples of the binder include those that do not dissolve in the electrolytic solution used as the electrolytic solution 15, and polytetrafluoroethylene (PTFE). ), Tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, chlorotrifluoroethylene / A fluororesin such as an ethylene copolymer is preferred.

  Content of the said positive electrode catalyst of the positive electrode catalyst layer 11, a electrically conductive material, and a binder is not limited. Since the catalytic activity of the positive electrode catalyst can be further improved, the blending amount of the conductive material is preferably 0.5 to 30 parts by mass, and 1 to 20 parts by mass with respect to 1 part by mass of the positive electrode catalyst. More preferably, the amount is 1 to 15 parts by mass, and the amount of the binder is preferably 0.1 to 10 parts by mass with respect to 1 part by mass of the positive electrode catalyst. More preferably, it is 5-5 mass parts, and it is especially preferable that it is 0.5-3 mass parts.

  In the positive electrode catalyst layer 11, each constituent component such as the positive electrode catalyst, the conductive material, and the binder may be used alone or in combination of two or more.

The material of the positive electrode current collector 12 may be conductive. Preferred examples of the positive electrode current collector 12 include a metal mesh, a metal sintered body, carbon paper, and carbon cloth.
Examples of the metal in the metal mesh and the metal sintered body include simple metals such as nickel, chromium, iron, and titanium; alloys including two or more of these metals can be exemplified, and nickel, stainless steel (iron-nickel-chromium alloy) Is preferred.

<Negative electrode>
As the negative electrode in the present embodiment, one or more selected from the group consisting of zinc alone and a zinc compound can be used as the negative electrode active material. Examples of the zinc compound include zinc oxide, zinc hydroxide, and zinc alloy.

  As the zinc alloy, an alloy with 1 ppm to 3000 ppm of bismuth, preferably 100 ppm to 1000 ppm of bismuth may be used. Alternatively, a zinc alloy of 1 ppm to 3000 ppm indium, preferably 100 to 1000 ppm indium, or 1 ppm to 3000 ppm indium and 1 ppm to 3000 ppm bismuth, preferably 100 ppm to 1000 ppm indium and 100 ppm to 1000 ppm bismuth may be used. Good. By using these zinc alloys, hydrogen overvoltage of zinc can be reduced and gas generation in the battery can be prevented.

  The negative electrode may be used in any shape of a plate shape, a granular shape, and a gel shape.

  The negative electrode current collector 14 may be the same as the positive electrode current collector 12.

<Electrolyte>
The electrolytic solution 15 is preferably used as an electrolytic solution in which an electrolyte is dissolved in a solvent. As the solvent, water is preferable. The pH of the electrolytic solution 15 is preferably 1 to 13, and more preferably 6 to 13. The pH can be measured using a glass electrode pH meter as defined in Japanese Industrial Standard JIS Z8802 “pH measurement method”.

  The concentration of chloride ions in the electrolytic solution is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.1% by mass or less.

  As an electrolyte in the electrolytic solution, an acid salt having an acid dissociation constant (pKa) in the range of 1 to 13 is preferably used. By using an acid salt having an acid dissociation constant in the range of 1 to 13, the buffer capacity of the electrolytic solution is increased and the pH stability is excellent. Therefore, the effect of stably charging and discharging the air secondary battery of the present invention is achieved. is there.

  Examples of the electrolyte include potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, sodium formate, potassium formate, sodium acetate, potassium acetate, tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, phosphoric acid Trisodium, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium borate, potassium sulfate, sodium sulfate, ammonium bicarbonate, ammonium formate, ammonium acetate, ammonium phosphate, ammonium dihydrogen phosphate, ammonium sulfate, ammonium hydrogen sulfate Is exemplified. More preferably, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, sodium formate, potassium formate, sodium acetate, potassium acetate, tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, phosphate triphosphate. Examples thereof include sodium, disodium hydrogen phosphate, and sodium dihydrogen phosphate. Preferably, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, sodium formate, potassium formate, sodium acetate, potassium acetate, triphosphate Potassium, dipotassium hydrogen phosphate, trisodium phosphate, and disodium hydrogen phosphate. The electrolyte may be an anhydride or a hydrate.

  Further, the electrolytes exemplified above may be mixed and used, and in addition to the electrolytes exemplified above, potassium hydroxide or sodium hydroxide may be used in combination.

  The concentration of the electrolyte in the electrolytic solution can be arbitrarily set depending on the use environment of the air secondary battery. The electrolyte may remain undissolved, but it is preferable that the concentration is not more than the saturation concentration of each electrolyte. The lower limit of the concentration is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more.

  Citric acid, succinic acid, tartaric acid or the like may be added as an additive to the electrolytic solution for the purpose of suppressing the generation of dendrites.

  Further, zinc oxide, zinc hydroxide, zinc sulfate, zinc formate, zinc acetate and the like may be added to the electrolytic solution for the purpose of suppressing dissolution of zinc ions in the electrolytic solution during discharge.

  Alternatively, the electrolyte may be used as a gel electrolyte in which a water-absorbing polymer such as polyacrylic acid is absorbed. In this case, the pH of the electrolyte before being absorbed into the water-absorbing polymer is handled as the pH of the electrolyte of the air secondary battery in the present invention. Further, the concentration of chloride ions in the electrolytic solution before absorption into the water-absorbing polymer is treated as the concentration of chloride ions in the electrolytic solution in the present invention.

<Other configurations>
The container accommodates the positive electrode catalyst layer 11, the positive electrode current collector 12, the negative electrode active material layer 13, the negative electrode current collector 14, and the electrolytic solution 15. Examples of the material of the container include resins such as polystyrene, polyethylene, polypropylene, polyvinyl chloride, and ABS resin, and metals that do not react with the contents such as the positive electrode catalyst layer 11.

In the air secondary battery 1, an oxygen diffusion film may be separately provided. The oxygen diffusion film is preferably provided outside the positive electrode current collector 12 (on the opposite side of the positive electrode catalyst layer 11). By doing so, oxygen (air) is preferentially supplied to the positive electrode catalyst layer 11 through the oxygen diffusion film.
The oxygen diffusion film may be a film that can suitably transmit oxygen (air), and examples thereof include a resin nonwoven fabric or a porous film. Examples of the resin include polyolefins such as polyethylene and polypropylene; polytetrafluoroethylene, A fluororesin such as polyvinylidene fluoride can be exemplified.

In the air secondary battery 1, a separator may be provided between them in order to prevent a short circuit due to contact between the positive electrode and the negative electrode.
The separator may be made of an insulating material that can move the electrolyte solution 15, and examples thereof include a resin nonwoven fabric or a porous membrane, and examples of the resin include polyolefins such as polyethylene and polypropylene; polytetrafluoroethylene, A fluororesin such as polyvinylidene fluoride can be exemplified. When the electrolytic solution 15 is used as an aqueous solution, it is preferable to use a hydrophilic resin as the resin.

  The shape of the secondary battery of the present invention is not particularly limited, and examples thereof include a coin type, a button type, a sheet type, a laminated type, a cylindrical type, a flat type, and a rectangular type.

  The air secondary battery according to the present embodiment is useful for, for example, a large power source such as an electric vehicle power source or a household power source, and is also useful as a small power source for mobile devices such as a mobile phone or a portable personal computer. .

  Hereinafter, the present invention will be described in more detail with reference to specific examples.

[Synthesis Example 1]
<Synthesis of Metal Complex MC1>
Compound 4 was synthesized via Compound 1, Compound 2, and Compound 3 according to the following reaction formulas (1) and (2). And according to following Reaction formula (3), the metal complex MC1 was synthesize | combined using the compound 4 and the metal provision agent.

(Synthesis of Compound 3)

…（１）

... (1)

First, compound 1 as a raw material was synthesized by the following method.
1,4-Dibromo-2,3-diaminobenzene was synthesized according to the method described in the literature (Journal of Organic Chemistry, 2006, 71, 3350). Next, 10 mL of acetic acid solution containing 0.600 g (2.256 mmol) of 1,4-dibromo-2,3-diaminobenzene was heated to 50 ° C. in the flask, and then the gas in the flask was allowed to flow for 1 hour. And replaced with argon. 0.234 g (0.752 mmol) of hexaketocyclohexane was added to the resulting solution, and then heated at 110 ° C. for 10 hours. After pouring the reaction solution into ice water, the reaction solution was made alkaline with aqueous sodium hydroxide. As a result, a light green product was obtained as a precipitate, and the precipitate was collected by filtration and washed in turn with water and dichloromethane to obtain 0.499 g of Compound 1.
In order to secure an amount necessary for the next step, the above operation was repeated several times. Identification data for the obtained compound 1 are shown below.

MS (FD, 8 kV) Found (m / z): 857.5 (M ⁺ ); 429.7 (M ²⁺ ), Theoretical: 857.57 (M ⁺ )
MS (Maldi-Tof, TCNQ): m / z 858 (M ⁺ )

Next, Compound 2 was synthesized using Compound 1 obtained above.
In a flask, 4.516 g (21.4 mmol) of 1-N-Boc-pyrrole-2-pyrrole was added to a mixed solution of 100 mL of THF containing 1.835 g (2.140 mmol) of Compound 1 and 40 mL of toluene. After boronic acid, 0.048 g of Aliquat 336 (trade name) and 14.88 g (0.107 mol) of potassium carbonate were added, the gas in the flask was replaced with argon over 1 hour.
After adding 0.890 g (0.771 mmol) of tetrakis (triphenylphosphine) palladium (0) to the reaction solution, the mixture was heated at 95 ° C. for 72 hours, then 12 mL of degassed water was added, and the mixture was further heated for 2 days. The crude product was obtained by continuing. This crude product was purified by a silica gel column (developing solvent: ethyl acetate / dichloromethane / hexane) to obtain 2.745 g of compound 2. Identification data for the obtained compound 2 are shown below.

  MS (FD, 8 kV) measured value (m / z): 1374.5, theoretical value: 1374.59

Then, the compound 2 obtained above was heated to deprotect the pyrrole group, thereby obtaining the compound 3.
Compound 3 was obtained by heating 0.340 g of Compound 2 at 180 ° C. for 30 minutes under a reduced pressure of 20 Pa. Identification data for the obtained compound 3 are shown below.

MS (FD, 8 kV) Found (m / z): 386.6 (M ²⁺ ); 774, 0 (M ⁺ ), Theoretical: 387.14 (M ²⁺ ); 774.27 (M ⁺ )
MS (Maldi-Tof, TCNQ) measured value (m / z): 775 (M ⁺ ); 1549 (2M ⁺ )

(Synthesis of Compound 4)

…（２）

... (2)

  In the flask, 0.207 g (0.267 mmol) of Compound 3 was added to a mixed solution of 1 mL of trifluoromethanesulfonic acid, 1.5 mL of pn-octylbenzaldehyde and 3 mL of dichloromethane, The gas was replaced with argon. The obtained solution was put into a microwave reactor and reacted at 50 W for 2 hours. Ammonium hydroxide was added to the reaction solution, the organic layer was washed with water, the obtained organic layer was dried with an evaporator, and further washed with water and hexane in order to obtain 0.349 g (0.254 mmol). ) Was obtained in a yield of 95%. Identification data for the obtained compound 4 are shown below.

MS (FD, 8 kV) Measured value (m / z): 1335.5 (M ⁺ ), Theoretical value: 1375.74 (M ⁺ )
MS (Maldi-Tof, TCNQ) measured value (m / z): 1373 (M ⁺ ); 2746 (2M ⁺ )

(Synthesis of metal complex MC1)
Metal complex MC1 was synthesized according to the following reaction formula (3).

…（３）

... (3)

  Place 0.125 g (0.091 mmol) of compound 4 and 0.079 g (0.318 mmol) of cobalt acetate tetrahydrate in a microwave test tube, add 5 mL of DMF to it, and The mixture was reacted at 200 ° C. and an output of 200 W for 2 hours. The reaction solution was poured into 25 mL of cold water, and the resulting precipitate was collected by filtration and washed in turn with water and hexane to obtain a polynuclear metal complex MC1. Identification data of the obtained metal complex MC1 are shown below.

MS (Maldi-Tof, TCNQ) Found (m / z): 1543 (M ⁺ ); 1569 (M ⁺ + CN ⁻ ); 1595 (M ⁺ + 2CN ⁻ ); 1621 (M ⁺ + 3CN ⁻ ), Theoretical value: 1543 .5 (M ⁺ )

[Synthesis Example 2]
<Synthesis of Metal Complex MC2>
Compound 7 was synthesized via Compound 5 and Compound 6 according to the following reaction formulas (4) to (6). And according to the following Reaction formula (7), the metal complex MC2 was synthesize | combined using the compound 7 and the metal provision agent.

(Synthesis of Compound (A))

…（４）
（式中、Ｂｏｃはｔｅｒｔ−ブトキシカルボニル基であり、ｄｂａはジベンジリデンアセトンである。）

... (4)
(In the formula, Boc is a tert-butoxycarbonyl group, and dba is dibenzylideneacetone.)

  After making the inside of the reaction vessel an argon gas atmosphere, 3.945 g of 2,9- (3′-bromo-5′-tert-butyl-2′-methoxyphenyl) -1,10-phenanthroline (Tetrahedron., 1999, 55, 8377.) 3.165 g of 1-N-Boc-pyrrole-2-boronic acid, 0.138 g of tris (benzylideneacetone) dipalladium, 0.247 g of 2-dicyclohexylphosphino -2 ′, 6′-dimethoxybiphenyl and 5.527 g of potassium phosphate were dissolved in a mixed solvent of 200 mL of dioxane and 20 mL of water, and the mixture was stirred at 60 ° C. for 6 hours. After completion of the reaction, the mixture was allowed to cool, distilled water and chloroform were added, and the organic layer was extracted. The resulting organic layer was concentrated to give a black residue. This was purified using a silica gel column to obtain Compound 5. Identification data for the obtained compound 5 are shown below.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 1.34 (s, 18H), 1.37 (s, 18H), 3.30 (s, 6H), 6.21 (m, 2H) ), 6.27 (m, 2H), 7.37 (m, 2H), 7.41 (s, 2H), 7.82 (s, 2H), 8.00 (s, 2H), 8.19 (D, J = 8.6 Hz, 2H), 8.27 (d, J = 8.6 Hz, 2H).

(Synthesis of Compound 6)

…（５）
（式中、Ｂｏｃはｔｅｒｔ−ブトキシカルボニル基である。）

... (5)
(In the formula, Boc is a tert-butoxycarbonyl group.)

  After making the inside of the reaction vessel a nitrogen gas atmosphere, 0.904 g of compound 5 was dissolved in 10 mL of anhydrous dichloromethane. While the obtained dichloromethane solution was cooled to −78 ° C., 8.8 mL of boron tribromide (1.0 M dichloromethane solution) was slowly added dropwise thereto. After dropping, the mixture was stirred as it was for 10 minutes, and was left with further stirring until it reached room temperature. After 3 hours, the reaction solution was cooled to 0 ° C., a saturated aqueous sodium hydrogen carbonate solution was added, and extracted by adding chloroform, and the organic layer was concentrated. The resulting brown residue was purified with a silica gel column to give compound 6. Identification data for the obtained compound 6 are shown below.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 1.40 (s, 18H), 6.25 (m, 2H), 6.44 (m, 2H), 6.74 (m, 2H) ), 7.84 (s, 2H), 7.89 (s, 2H), 7.92 (s, 2H), 8.35 (d, J = 8.4 Hz, 2H), 8.46 (d, J = 8.4 Hz, 2H), 10.61 (s, 2H), 15.88 (s, 2H).

(Synthesis of Ligand Compound 7)

…（６）

(6)

  In a reaction vessel, 0.061 g of compound 6 and 0.012 g of benzaldehyde were dissolved in 5 mL of propionic acid and heated at 140 ° C. for 7 hours. Thereafter, propionic acid was distilled off from the obtained reaction solution, and the resulting black residue was purified with a silica gel column to obtain a ligand compound 7. Identification data for the obtained ligand compound 7 are shown below.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 1.49 (s, 18H), 6.69 (d, J = 4.8 Hz, 2H), 7.01 (d, J = 4. 8 Hz, 2H), 7.57 (m, 5H), 7.90 (s, 4H), 8.02 (s, 2H), 8.31 (d, J = 8.1 Hz, 2H), 8.47 (D, J = 8.1 Hz, 2H).

(Synthesis of metal complex MC2)

…（７）
（式中、Ａｃはアセチル基であり、Ｍｅはメチル基である。）

... (7)
(In the formula, Ac is an acetyl group, and Me is a methyl group.)

After making the inside of the reaction vessel into a nitrogen gas atmosphere, 0.045 g of compound 7 and 3 mL of a mixed solution of 0.040 g of cobalt acetate tetrahydrate and 3 mL of chloroform were mixed, and the mixture was heated to 80 ° C. The mixture was stirred for 5 hours while heating. The resulting solution was concentrated to dryness to give a blue solid. This was washed with water to obtain a metal complex MC2. In the metal complex MC2 in the above reaction formula, “(OAc)” indicates that 1 equivalent of acetate ion is present as a counter ion. Identification data for the obtained metal complex MC2 are shown below.
ESI-MS [M + ·]: m / z = 866.0

<Chlorine generation>
[Reference Example 1]
The metal complex MC1 obtained above was used as a positive electrode catalyst, and a water oxidation reaction was performed with a rotating disk electrode. Specifically, it is as follows.
As the electrode, a disk electrode having a disk portion made of glassy carbon (diameter 6.0 mm) was used.
After adding 1 mL of a 0.5% by mass Nafion (registered trademark) solution (a solution obtained by diluting a 5% by mass Nafion (registered trademark) solution 10 times with ethanol) to a sample bottle containing 1 mg of the metal complex MC1, The sound wave was irradiated and dispersed for 15 minutes. After 7.2 μL of the obtained suspension was dropped on the disk portion of the electrode and dried, the electrode for measurement was obtained by drying in a dryer heated to 80 ° C. for 3 hours. A 20 mass% potassium carbonate aqueous solution was prepared using potassium carbonate (product code 162-03495, manufactured by Wako Pure Chemical Industries, Ltd.) as an electrolyte. The pH of the solution was 11.4. A voltage of 2 V was applied to the silver / silver chloride electrode, and water was oxidized for 10 minutes. The reaction was carried out using the following reaction apparatus and reaction conditions.

(Reactor)
RRDE-1 rotating ring disk electrode device manufactured by Nisatsu Keiki Co., Ltd. ALS model 701C dual electrochemical analyzer (reaction conditions)
Solution temperature: 25 ° C
Reference electrode: Silver / silver chloride electrode (saturated potassium chloride)
Counter electrode: platinum wire Sweep speed: 10 mV / sec Electrode rotation speed: 900 rpm

  Residual chlorine test paper (manufactured by Nissan Chemical Industries, Ltd., Aqua Check LC) was immersed in the electrolytic solution for 60 seconds. No color was seen and no chlorine was generated.

[Reference Example 2]
In Reference Example 1, the metal complex MC1 was changed to the metal complex MC2 and used as the positive electrode catalyst. After adding 1 mL of a 0.5% by mass Nafion (registered trademark) solution (a solution obtained by diluting a 5% by mass Nafion (registered trademark) solution 10 times with ethanol) to a sample bottle containing 1 mg of the metal complex MC2, The sound wave was irradiated and dispersed for 15 minutes. After 7.2 μL of the obtained suspension was dropped on the disk portion of the electrode and dried, the electrode for measurement was obtained by drying in a dryer heated to 80 ° C. for 3 hours. A 20 mass% potassium phosphate aqueous solution was prepared using tripotassium phosphate monohydrate (product code 60492, manufactured by Fluka) as an electrolyte. The pH of the solution was 13.0. A voltage of 2 V was applied to the silver / silver chloride electrode, and water was oxidized for 10 minutes. The reaction was carried out in the same reaction apparatus and reaction conditions as in Reference Example 1. Residual chlorine test paper (manufactured by Nissan Chemical Industries, Ltd., Aqua Check LC) was immersed in the electrolytic solution for 60 seconds. No color was seen and no chlorine was generated.

[Reference Example 3]
A 20% by mass ammonium chloride aqueous solution was prepared using ammonium chloride as an electrolyte. The pH of the electrolytic solution was 4.7. A water oxidation reaction was carried out in the same manner as in Reference Example 1. When the chlorine concentration of the electrolytic solution was measured with a residual chlorine test paper (manufactured by Nissan Chemical Industries, Ltd., Aqua Check LC), 0.3 ppm of chlorine was generated.

[Charge / discharge test with air secondary battery]
[Example 1]
Metal complex MC1 as a positive electrode catalyst, acetylene black as a conductive material, and PTFE powder as a binder are mixed in a metal complex MC1: acetylene black: PTFE = 1: 10: 1 (mass ratio), After adding 5 drops of ethanol to the sample with a pipette, these were mixed in a menor mortar, and then thinned to obtain the positive electrode catalyst layer 1. The positive electrode catalyst layer 1 is sandwiched between a water-repellent PTFE sheet and a stainless mesh from both sides, and is subjected to pressure bonding with a press machine, whereby the positive electrode 1 for an air secondary battery is obtained.

A zinc plate (manufactured by Aldrich) serving as a negative electrode is sandwiched between porous metal bodies (Celmet # 8, manufactured by Toyama Sumitomo Electric Co., Ltd.) and pressed with a press. An air secondary battery is assembled together with the produced positive electrode 1 for an air secondary battery, and a 20 mass% potassium carbonate aqueous solution (pH = 11.4) is filled as an electrolytic solution. Connect to a charge / discharge tester (manufactured by Toyo System Co., Ltd., product name: TOSCAT-3000U) and perform a charge / discharge cycle test.
In the charge / discharge cycle test, the following steps 1 to 4 are repeated 10 times.
Step 1: Charge for 20 minutes at a constant current of 10 mA Step 2: Stop for 5 minutes Step 3: Discharge at a constant current of 10 mA. When the voltage reaches 0.5V, go to Step 4.
Step 4: Pause for 5 minutes

After 10 charge / discharge cycles, a residual chlorine test paper (manufactured by Nissan Chemical Industries, Ltd., Aqua Check LC) is immersed in the electrolytic solution for 60 seconds. Color development is not seen and generation of chlorine is not confirmed.
[Example 2]
A charge / discharge cycle test is performed in the same manner as in Example 1 using the metal complex MC2 as the positive electrode catalyst and the 20% by mass tripotassium phosphate aqueous solution (pH = 13.0) as the electrolytic solution. After 10 charge / discharge cycles, a residual chlorine test paper (manufactured by Nissan Chemical Industries, Ltd., Aqua Check LC) is immersed in the electrolytic solution for 60 seconds. Color development is not seen and generation of chlorine is not confirmed.
[Comparative Example 1]
A charge / discharge cycle test is performed in the same manner as in Example 1 using the metal complex MC1 as the positive electrode catalyst and the 20% by mass ammonium chloride aqueous solution (pH = 4.7) as the electrolytic solution. After 10 charge / discharge cycles, a residual chlorine test paper (manufactured by Nissan Chemical Industries, Ltd., Aqua Check LC) is immersed in the electrolytic solution for 60 seconds. Color development is observed in the test, and generation of chlorine is confirmed.

  The air secondary battery of the present invention does not generate harmful chlorine gas during charging and can be used in the energy field.

  DESCRIPTION OF SYMBOLS 1 ... Air secondary battery, 11 ... Positive electrode catalyst layer, 12 ... Positive electrode collector, 120 ... Positive electrode terminal, 13 ... Negative electrode active material layer, 14 ... Negative electrode collector, 140 ... Negative electrode terminal, 15 ... Electrolyte

Claims (3)

An air secondary battery comprising a positive electrode including a positive electrode catalyst having oxygen reduction activity and water oxidation activity, a negative electrode including at least one selected from the group consisting of zinc alone and a zinc compound, and an electrolyte solution,
The pH of the electrolyte is 6 a to 13,
Wherein Ri der concentration of chloride ions is 1.0 mass% or less in the electrolytic solution,
The electrolytic solution is an electrolytic solution in which potassium carbonate is dissolved in a solvent,
The positive electrode catalyst is at least one selected from the group consisting of a mononuclear metal complex having a cobalt atom, a mononuclear metal complex having a cobalt ion, and a polynuclear metal complex containing either or both of a cobalt atom and a cobalt ion. An air secondary battery which is a positive electrode catalyst .   The air secondary battery according to claim 1, wherein a concentration of chloride ions in the electrolytic solution is 0.1% by mass or less. Air secondary cell according to claim 1 or 2 concentration of electrolytic substance of the electrolyte solution is not more than 1 mass% or more saturation concentration.

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