JP2013016474A - Positive electrode catalyst for air secondary battery and air secondary battery - Google Patents

Abstract

（式中、Ｚ^１は３価の有機基であり、複数のＺ^１は互いに同一でも異なっていてもよい。Ｅは酸素原子又は硫黄原子であり、複数のＥは互いに同一でも異なっていてもよい。Ｑ^１は少なくとも２つの窒素原子を有する２価の有機基である。Ｔ^１は水素原子又は有機基であり、複数のＴ^１は互いに同一でも異なっていてもよく、複数のＴ^１が有機基の場合、これらは互いに結合していてもよい。Ｍは遷移金属原子又は遷移金属イオンである。）
【選択図】なしProvided are a positive electrode catalyst for an air secondary battery excellent in both oxygen reduction activity and water oxidation activity, and an air secondary battery using the catalyst.
A positive electrode catalyst for an air secondary battery using a metal complex represented by the following general formula (1).

(In the formula, Z ¹ is a trivalent organic group, and a plurality of Z ¹ may be the same or different from each other. E is an oxygen atom or a sulfur atom, and a plurality of E may be the same or different from each other. good .Q ¹ is .T ¹ is a divalent organic group having at least two nitrogen atoms is a hydrogen atom or an organic group, a plurality of T ¹ may be the same or different from each other, a plurality of T ¹ In the case of an organic group, these may be bonded to each other, and M is a transition metal atom or a transition metal ion.)
[Selection figure] None

Description

  The present invention relates to a positive electrode catalyst for an air secondary battery and an air secondary battery using the catalyst.

An air battery using oxygen in the air as an active material is expected to be applied to various uses such as for an electric vehicle because it can achieve high energy density.
An air battery is a battery that uses a positive electrode catalyst having oxygen reducing ability and a negative electrode active material containing zinc, iron, aluminum, magnesium, lithium, hydrogen, or the like as an active material.
As a conventional air battery, a battery using manganese dioxide as a positive electrode catalyst has been disclosed (see Non-Patent Document 1).

Journal of Power Sources, Volume 91, 2000, Pages 83-85.

  Conventionally, batteries (secondary batteries, rechargeable batteries, storage batteries) that can store electricity by charging and can be used repeatedly are known. Development of batteries used as active materials 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.

  The positive electrode catalyst of the air secondary battery is required to have an oxidation activity of water during charging in addition to the oxygen reduction activity required for the positive electrode catalyst of an air battery (primary battery) that performs only discharge. From this point of view, when looking at the positive electrode catalyst of the conventional air battery, the above-mentioned manganese dioxide has an oxygen reduction activity, but has a low water oxidation activity.

  This invention is made | formed in view of such a situation, and makes it a subject to provide the positive electrode catalyst for air secondary batteries excellent in both the reduction activity of oxygen, and the oxidation activity of water. It is another object of the present invention to provide an air secondary battery using such a positive electrode catalyst for an air secondary battery.

To solve the above problem,
The present invention provides a positive electrode catalyst for an air secondary battery using a metal complex represented by the following general formula (1).

（式中、
Ｚ^１は３価の有機基であり、複数のＺ^１は互いに同一でも異なっていてもよい。
Ｅは酸素原子又は硫黄原子であり、複数のＥは互いに同一でも異なっていてもよい。
Ｑ^１は少なくとも２つの窒素原子を有する２価の有機基である。
Ｔ^１は水素原子又は有機基であり、複数のＴ^１は互いに同一でも異なっていてもよく、複数のＴ^１が有機基の場合、これらは互いに結合していてもよい。
Ｍは遷移金属原子又は遷移金属イオンである。
Ｘは対イオン又は中性分子であり、ｎは０以上の整数であり、ｎが２以上の場合、複数のＸは互いに同一でも異なっていてもよい。）

(Where
Z ¹ is a trivalent organic group, and a plurality of Z ¹ may be the same as or different from each other.
E is an oxygen atom or a sulfur atom, and a plurality of E may be the same as or different from each other.
Q ¹ is a divalent organic group having at least two nitrogen atoms.
T ¹ is a hydrogen atom or an organic group, and a plurality of T ¹ may be the same as or different from each other. When a plurality of T ¹ are an organic group, these may be bonded to each other.
M is a transition metal atom or a transition metal ion.
X is a counter ion or a neutral molecule, n is an integer of 0 or more, and when n is 2 or more, a plurality of X may be the same or different from each other. )

  The positive electrode catalyst for an air secondary battery of the present invention is preferably such that the metal complex represented by the general formula (1) is a metal complex represented by the following general formula (2).

（式中、
Ｒ^１は水素原子又は置換基であり、複数のＲ^１は互いに同一でも異なっていてもよく、隣り合うＲ^１同士は互いに結合して、それぞれが結合する炭素原子とともに環を形成してもよい。
Ｑ^２は少なくとも２つの窒素原子を有する２価の有機基である。
Ｔ^２は水素原子又は有機基であり、複数のＴ^２は互いに同一でも異なっていてもよく、複数のＴ^２が有機基の場合、これらは互いに結合していてもよい。
Ｍ、Ｘ及びｎは、前記と同じ意味を表す。）

(Where
R ¹ is a hydrogen atom or a substituent, and a plurality of R ¹ may be the same or different from each other, and adjacent R ¹ may be bonded to each other to form a ring together with the carbon atom to which each is bonded. .
Q ² is a divalent organic group having at least two nitrogen atoms.
T ² is a hydrogen atom or an organic group, and a plurality of T ² may be the same as or different from each other. When a plurality of T ² are an organic group, these may be bonded to each other.
M, X, and n represent the same meaning as described above. )

The positive electrode catalyst for an air secondary battery of the present invention is preferably such that T ¹ or T ² is an organic group having a nitrogen-containing aromatic heterocycle.
The positive electrode catalyst for an air secondary battery of the present invention is preferably such that the metal complex represented by the general formula (2) is a metal complex represented by the following general formula (3).

（式中、
Ｒ^２は水素原子又は置換基であり、複数のＲ^２は互いに同一でも異なっていてもよく、隣り合うＲ^２同士は互いに結合して、それぞれが結合する炭素原子とともに環を形成してもよい。
Ｑ^３及びＱ^４は、それぞれ独立に下記一般式（３−１）、（３−２）、（３−３）、（３−４）、（３−５）又は（３−６）で表される２価の基である。
Ｍ、Ｘ及びｎは、前記と同じ意味を表す。）

(Where
R ² is a hydrogen atom or a substituent, and a plurality of R ² may be the same or different from each other, and adjacent R ² may be bonded to each other to form a ring together with the carbon atom to which each is bonded. .
Q ³ and Q ⁴ are each independently represented by the following general formula (3-1), (3-2), (3-3), (3-4), (3-5) or (3-6). Divalent group.
M, X, and n represent the same meaning as described above. )

（式中、
Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、それぞれ独立に水素原子又は置換基であり、複数のＲ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、それぞれ互いに同一でも異なっていてもよく、複数のＲ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８が置換基である場合、これらはそれぞれ互いに結合して、それぞれが結合する炭素原子とともに環を形成してもよい。
Ａは、下記式（３−ａ）、（３−ｂ）又は下記一般式（３−ｃ）で表される２価の基であり、複数のＡは、互いに同一でも異なっていてもよい。）

(Where
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or a substituent, and a plurality of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are ^May be the same as or different from each other, and when a plurality of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are substituents, they are bonded to each other, and You may form a ring with an atom.
A is a divalent group represented by the following formula (3-a), (3-b) or the following general formula (3-c), and a plurality of A may be the same or different from each other. )

（式中、Ｒ^９は水素原子、又は置換基を有していてもよいヒドロカルビル基である。）

(In the formula, R ⁹ is a hydrogen atom or a hydrocarbyl group which may have a substituent.)

The positive electrode catalyst for an air secondary battery of the present invention is preferably such that M is one kind of atom selected from the group consisting of vanadium, chromium, manganese, iron, cobalt, nickel and copper, or an ion thereof.
The positive electrode catalyst for an air secondary battery of the present invention may be one using a composition containing the metal complex and carbon.
The positive electrode catalyst for an air secondary battery of the present invention may be obtained by heating the metal complex or a composition containing the metal complex and carbon at 300 to 1200 ° C.
In addition, the present invention includes the positive electrode catalyst for an air secondary battery of the present invention in the positive electrode catalyst layer, and includes at least one selected from the group consisting of zinc, iron, aluminum, magnesium, lithium, hydrogen, and these ions. An air secondary battery used as a negative electrode active material is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the positive electrode catalyst for air secondary batteries excellent in both the reduction activity of oxygen and the oxidation activity of water, and the air secondary battery using this catalyst can be provided.

1 is a schematic cross-sectional view illustrating an embodiment of an air secondary battery according to the invention. 10 is a graph showing the results of a charge / discharge cycle test of an air secondary battery in Example 7.

  Hereinafter, the present invention will be described in detail. In the present invention, “having a substituent” means “one or more hydrogen atoms are substituted with a group other than a hydrogen atom (substituent)” in the target group, unless otherwise specified. It means “the number and position of substituents are not limited, and all hydrogen atoms may be substituted with substituents”.

<Cathode catalyst for air secondary battery>
The positive electrode catalyst for an air secondary battery of the present invention (hereinafter sometimes simply referred to as “positive electrode catalyst”) uses a metal complex represented by the following general formula (1).

（式中、
Ｚ^１は３価の有機基であり、複数のＺ^１は互いに同一でも異なっていてもよい。
Ｅは酸素原子又は硫黄原子であり、複数のＥは互いに同一でも異なっていてもよい。
Ｑ^１は少なくとも２つの窒素原子を有する２価の有機基である。
Ｔ^１は水素原子又は有機基であり、複数のＴ^１は互いに同一でも異なっていてもよく、複数のＴ^１が有機基の場合、これらは互いに結合していてもよい。
Ｍは遷移金属原子又は遷移金属イオンである。
Ｘは対イオン又は中性分子であり、ｎは０以上の整数であり、ｎが２以上の場合、複数のＸは互いに同一でも異なっていてもよい。）

(Where
Z ¹ is a trivalent organic group, and a plurality of Z ¹ may be the same as or different from each other.
E is an oxygen atom or a sulfur atom, and a plurality of E may be the same as or different from each other.
Q ¹ is a divalent organic group having at least two nitrogen atoms.
T ¹ is a hydrogen atom or an organic group, and a plurality of T ¹ may be the same as or different from each other. When a plurality of T ¹ are an organic group, these may be bonded to each other.
M is a transition metal atom or a transition metal ion.
X is a counter ion or a neutral molecule, n is an integer of 0 or more, and when n is 2 or more, a plurality of X may be the same or different from each other. )

(Metal complex)
In the general formula (1), Z ¹ is a trivalent organic group, and a plurality (two) of Z ¹ may be the same as or different from each other.
Examples of the trivalent organic group include an aromatic group which may have a substituent.

The aromatic group in Z ¹ is a trivalent group generated by removing three hydrogen atoms from an aromatic compound (preferably from a carbon atom constituting the ring of the aromatic compound). Here, as the aromatic compound, for example, benzene, naphthalene, anthracene, tetracene, biphenyl, binaphthyl, phenanthrene, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyridine, pyrazine, pyrrole and the like preferably have 3 to 60 carbon atoms, More preferable examples include 3 to 40 aromatic compounds, which may be monocyclic or polycyclic.

The substituent that the aromatic group may have (hereinafter referred to as “substituent G”) is a group other than a hydrogen atom, and when there are a plurality of substituents G, the plurality of substituents G May be the same as or different from each other, and adjacent substituents G may be bonded to each other to form a ring together with the atoms to which they are bonded.
Examples of the substituent G include a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group, a formyl group, a hydroxysulfonyl group, a halogen atom, a hydrocarbyl group that may have a substituent, and a substituent. A good hydrocarbyloxy group, a hydrocarbyl mercapto group which may have a substituent, a hydrocarbylcarbonyl group which may have a substituent, a hydrocarbyloxycarbonyl group which may have a substituent, and a substituent An optionally substituted hydrocarbyloxysulfonyl group, and an amino group substituted with two optionally substituted hydrocarbyl groups (that is, an optionally substituted hydrocarbon disubstituted amino group. , Sometimes referred to as a “substituted amino group.”) An amino group substituted with two optionally substituted hydrocarbyl groups. Boniru group (i.e., may have a substituent group is a hydrocarbon-disubstituted amino carbonyl group. Hereinafter, sometimes referred to as "substituted amino group".) Are preferred.

Among these, the substituent G is substituted with a hydrocarbyl group which may have a substituent, a hydrocarbyloxy group which may have a substituent, and two hydrocarbyl groups which may have a substituent. More preferred are an amino group, an optionally substituted hydrocarbyl mercapto group, an optionally substituted hydrocarbylcarbonyl group, and an optionally substituted hydrocarbyloxycarbonyl group. More preferred are a hydrocarbyl group optionally having a substituent, a hydrocarbyloxy group optionally having a substituent, and an amino group substituted by two hydrocarbyl groups optionally having a substituent. A hydrocarbyl group which may be substituted and a hydrocarbyloxy group which may have a substituent are particularly preferred.
In the substituent G, when a nitrogen atom to which a hydrogen atom is bonded is present, the hydrogen atom is preferably substituted with a hydrocarbyl group. In addition, when the substituent G has a plurality of substituents, the plurality of substituents may be the same or different from each other, and adjacent substituents are bonded to each other so that each ring is bonded to the atom to which each is bonded. May be formed.

  Examples of the hydrocarbyl group in the substituent G include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, A linear or branched alkyl group having preferably 1 to 50, more preferably 1 to 20 carbon atoms, such as a nonyl group, a decyl group, an undecyl group, a dodecyl group, a pentadecyl group, an octadecyl group, a docosyl group; A cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclononyl group, a cyclododecyl group, a norbornyl group, an adamantyl group and the like, preferably having 3 to 50 carbon atoms, more preferably 3 to 20 monocyclic or Polycyclic cyclic alkyl group; ethenyl group, propenyl group, 3-butenyl group, 2-butenyl group, 2-pen Linear, branched or cyclic (in the case of cyclic), preferably 2 to 50, more preferably 2 to 20 carbon atoms, such as nyl, 2-hexenyl, 2-nonenyl, 2-dodecenyl, etc. Is monocyclic or polycyclic) alkenyl group; phenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-tert-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, 4-adamantylphenyl group, 4-phenylphenyl group A monocyclic or polycyclic aryl group having 6 to 50 carbon atoms, more preferably 6 to 20 carbon atoms, such as a phenylmethyl group, a 1-phenylethyl group, 2 Phenylethyl group, 1-phenyl-1-propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5 An aralkyl group having preferably 7 to 50 carbon atoms, more preferably 7 to 20 carbon atoms, such as a phenyl-1-pentyl group and a 6-phenyl-1-hexyl group, can be exemplified, and an alkyl group having 3 to 10 carbon atoms is preferable.

  The hydrocarbyl group in the substituent G preferably has 1 to 20 carbon atoms, more preferably has 2 to 12 carbon atoms, and still more preferably has 3 to 10 carbon atoms.

  In the substituent G, the hydrocarbyloxy group, hydrocarbyl mercapto group, hydrocarbylcarbonyl group, hydrocarbyloxycarbonyl group, and hydrocarbylsulfonyl group are the oxy group, mercapto group, carbonyl group, oxycarbonyl group, and sulfonyl group, respectively. It is a monovalent group formed by one bond.

  The substituted amino group and the substituted aminocarbonyl group in the substituent G are groups in which two hydrogen atoms in the amino group or aminocarbonyl group are substituted with the hydrocarbyl group, respectively. Here, the hydrocarbyl group is the same as the hydrocarbyl group as the substituent G.

Examples of the substituent that the hydrocarbyloxy group, hydrocarbyl mercapto group, hydrocarbylcarbonyl group, hydrocarbyloxycarbonyl group, hydrocarbylsulfonyl group, substituted amino group and substituted aminocarbonyl group in the substituent G may have include a halogen atom and a hydroxyl group , Amino group, nitro group, cyano group, hydrocarbyl group which may have a substituent, hydrocarbyloxy group which may have a substituent, hydrocarbyl mercapto group which may have a substituent, substituent And a hydrocarbylcarbonyl group which may have a substituent, a hydrocarbyloxycarbonyl group which may have a substituent, and a hydrocarbylsulfonyl group which may have a substituent.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The optionally substituted hydrocarbyl group, optionally substituted hydrocarbyloxy group, optionally substituted hydrocarbyl mercapto group, optionally substituted hydrocarbylcarbonyl The hydrocarbyloxycarbonyl group which may have a group and a substituent, and the hydrocarbylsulfonyl group which may have a substituent are the same as those exemplified as the substituent G.

  Among the above, the substituent G is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a phenyl group, a methylphenyl group, a 1-naphthyl group, 2- A naphthyl group and a pyridyl group are particularly preferable.

  When adjacent substituents G are bonded to each other to form a ring together with the atoms to which they are bonded, such a ring is preferably a benzene ring, a cyclohexane ring, a pyridine ring, or a naphthalene ring. Such a ring may have the substituent G described above as a substituent.

  Examples of the trivalent organic group include, in addition to the aromatic group, a trivalent group that does not correspond to the aromatic group and is generated by removing three hydrogen atoms from a hydrocarbon compound. A group formed by further removing two hydrogen atoms from the hydrocarbyl group is preferred.

In the general formula (1), E is an oxygen atom or a sulfur atom, and a plurality (two) of E may be the same as or different from each other.
The E is preferably an oxygen atom.

In the general formula (1), Q ¹ is a divalent organic group having at least two nitrogen atoms, and is represented by the following general formula (4-1), (4-2), or (4-3). Groups are preferred.

（式中、
Ｒ^１０及びＲ^１１は、それぞれ独立に水素原子又は置換基であり、複数のＲ^１０及びＲ^１１は、それぞれ互いに同一でも異なっていてもよい。
Ｒ^１２は水素原子、又は置換基を有していてもよい炭素数１〜１２のヒドロカルビル基であり、複数のＲ^１２は互いに同一でも異なっていてもよい。
Ｚ^２及びＺ^３は、それぞれ独立に２価の有機基である。
Ｙ^１及びＹ^２は、それぞれ独立に式「−Ｎ＝」又は「−ＮＨ−」で表される基である。
Ｐ^１は、Ｙ^１とＹ^１の隣接位の２つの炭素原子と一体となって複素環を形成する原子群である。
Ｐ^２は、Ｙ^２とＹ^２の隣接位の２つの炭素原子と一体となって複素環を形成する原子群である。
Ｄ^１は単結合、二重結合又は連結基である。）

(Where
R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a substituent, and the plurality of R ¹⁰ and R ¹¹ may be the same as or different from each other.
R ¹² is a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 12 carbon atoms, and a plurality of R ¹² may be the same as or different from each other.
Z ² and Z ³ are each independently a divalent organic group.
Y ¹ and Y ² are each independently a group represented by the formula “—N═” or “—NH—”.
P ¹ is an atomic group that forms a heterocyclic ring together with two carbon atoms adjacent to Y ¹ and Y ¹ .
P ² is an atomic group that forms a heterocyclic ring together with two carbon atoms adjacent to Y ² and Y ² .
D ¹ is a single bond, a double bond or a linking group. )

In the general formulas (4-1) and (4-2), R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a substituent, and the plurality of R ¹⁰ and R ¹¹ are the same as or different from each other. Also good.
Examples of the substituent represented by R ¹⁰ and R ¹¹ are the same as those of the substituent G.

In the general formula ^{(4-2), R 12} is hydrogen atom, or may have a substituent hydrocarbyl group having 1 to 12 carbon atoms. A plurality of R ¹² may be the same or different from each other.
The hydrocarbyl group in R ¹² is the same as the hydrocarbyl group in the substituent G except that it has 1 to 12 carbon atoms.

In the general formulas (4-1) and (4-2), Z ² and Z ³ are each independently a divalent organic group. Z ² and Z ³ are preferably an alkylene group which may be substituted with a substituent or a divalent aromatic group.

The alkylene group in Z ² and Z ³ is a divalent group generated by removing two hydrogen atoms from a saturated hydrocarbon, and may be linear, branched or cyclic. Specifically, methylene group, ethylene group, 1,1-propylene group, 1,2-propylene group, 1,3-propylene group, 2,4-butylene group, 2,4-dimethyl-2,4-butylene. Group, 1,2-cyclopentylene group, 1,2-cyclohexylene group, etc., preferably 1-20, more preferably 1-10, still more preferably 2-10 linear or branched chain And a cyclic alkylene group having preferably 3 to 20 carbon atoms.
The alkylene group in Z ² and Z ³ may have the same thing as the substituent G as a substituent.

The divalent aromatic group in Z ² and Z ³ is a divalent group generated by removing two hydrogen atoms from an aromatic compound (preferably from a carbon atom constituting the ring of the aromatic compound). , Either monocyclic or polycyclic. Here, the aromatic compound preferably has 3 to 60 carbon atoms, such as benzene, phenol, naphthalene, anthracene, tetracene, biphenyl, binaphthyl, phenanthrene, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyridine, and pyrazine. Preferably the thing of 3-40 can be illustrated.
The aromatic group in Z ² and Z ³ may have the same thing as the substituent G as a substituent.

As Q ¹ represented by the general formula (4-1), groups represented by the following formulas (4-1-1) to (4-1-11) are preferable, and the following formula (4-1-1) is preferable. ) To (4-1-6) are more preferred. Then, ^{Q 1} represented by the following formula (4-1-1) - (4-1-11) may have the same meanings as the substituent G as a substituent.

As Q ¹ represented by the general formula (4-2), groups represented by the following general formulas (4-2-1) to (4-2-11) are preferable, and the following general formula (4-2) The groups represented by -1) to (4-2-6) are more preferable. Q ¹ represented by the following general formulas (4-2-1) to (4-2-11) may have the same as the substituent G as a substituent.

（式中、Ｒ^４２は水素原子、又は置換基を有していてもよい炭素数１〜１２のヒドロカルビル基である。複数のＲ^４２は互いに同一でも異なっていてもよい。）

(In the formula, R ⁴² is a hydrogen atom or a hydrocarbyl group having 1 to 12 carbon atoms which may have a substituent. The plurality of R ⁴² may be the same as or different from each other.)

Wherein, R ⁴² is a hydrogen atom, or may have a substituent hydrocarbyl group having 1 to 12 carbon atoms, the hydrocarbyl groups are the same as the hydrocarbyl group in R ^12.
The plurality of R ⁴² may be the same as or different from each other.

In the general formula (4-3), Y ¹ and Y ² are each independently a group represented by the formula “—N═” or “—NH—”. And in the case of the group represented by the formula “—N =”, the double bond is located at the double bond position, that is, on either side of the two carbon atoms adjacent to each of Y ¹ and Y ^2. It is not limited.

In the general formula (4-3), P ¹ is an atomic group that forms a heterocycle together with two carbon atoms adjacent to Y ¹ and Y ¹ .
In the general formula (4-3), P ² is an atomic group forming a heterocyclic ring together with two carbon atoms adjacent Y ² and Y ^2.
The heterocyclic ring formed by P ^{1 and the} like and the heterocyclic ring formed by P ^{2 and the} like may be either monocyclic or polycyclic, but are preferably aromatic heterocyclic rings, and nitrogen-containing aromatics More preferably, it is a heterocyclic ring. Examples of the heterocyclic ring include pyrrole, pyridine, pyrazine, pyrimidine, pyridazine, thiazole, imidazole, oxazole, triazole, and indole, and pyrrole, pyridine, thiazole, imidazole, and oxazole are preferable.

The heterocyclic ring formed by P ^{1 and the} like and the heterocyclic ring formed by P ^{2 and the} like may have the same as the substituent G as a substituent. And when there are a plurality of substituents, adjacent substituents may be bonded to each other to form a ring together with the atoms to which they are bonded. When these substituents, P ¹ , P ² and D ¹ form a ring, preferred examples of such a ring include a benzene ring, a cyclohexane ring, a pyridine ring and a naphthalene ring. Moreover, such a ring may further have the substituent G described above as a substituent.

In the general formula (4-3), ^{D 1} is a single bond, a double bond or a linking group.
The linking group represented by D ¹ is an alkylene group, a group represented by the general formula “—C (G) ═”, or a group represented by the general formula “—N (G) —”. preferable. Examples of the alkylene group as the linking group include the same alkylene groups as those described above for Z ² and Z ³ , and the substituent may have the same as the substituent G. G has the same meaning as the substituent G described above.

The heterocyclic ring formed by P ^{1 and the} like and the heterocyclic ring formed by P ^{2 and the} like may be bonded to each other via a bond or linking group other than D ¹ to form a polycyclic heterocyclic ring. Good.

As Q ¹ represented by the general formula (4-3), groups represented by the following general formulas (4-3-1) to (4-3-14) are preferable, and the following general formula (4-3) The groups represented by -1) to (4-3-7) are more preferable. Q ¹ represented by the following general formulas (4-3-1) to (4-3-14) may have the same as the substituent G as a substituent.

（式中、Ｒ^４３は水素原子、又は置換基を有していてもよい炭素数１〜１２のヒドロカルビル基である。複数のＲ^４３は互いに同一でも異なっていてもよい。）

(In the formula, R ⁴³ is a hydrogen atom or a hydrocarbyl group having 1 to 12 carbon atoms which may have a substituent. The plurality of R ⁴³ may be the same as or different from each other.)

In the formula, R ⁴³ is the same as R ⁴² described above.

In the general formula (1), T ¹ is a hydrogen atom or an organic group, and a plurality (two) of T ¹ may be the same or different from each other. When a plurality of T ¹ are an organic group, T ¹ may be bonded to each other.
Examples of the organic group represented by T ¹ include groups exemplified as the substituent G, and organic groups having a nitrogen atom not corresponding to these exemplified groups.

  Examples of the organic group having a nitrogen atom include groups represented by the following general formula (5-a), (5-b) or (5-c).

（式中、
Ｒ^１３及びＲ^１４は、それぞれ独立に水素原子又は置換基であり、複数のＲ^１３及びＲ^１４は、それぞれ互いに同一でも異なっていてもよい。
Ｒ^１５は水素原子、又は置換基を有していてもよい炭素数１〜１２のヒドロカルビル基である。
Ｙ^３は式「−Ｎ＝」又は「−ＮＨ−」で表される基である。
Ｐ^３は、Ｙ^３とＹ^３の隣接位の２つの炭素原子と一体となって含窒素芳香族複素環を形成する原子群である。）

(Where
R ¹³ and R ¹⁴ are each independently a hydrogen atom or a substituent, and the plurality of R ¹³ and R ¹⁴ may be the same as or different from each other.
R ¹⁵ is a hydrogen atom or a hydrocarbyl group having 1 to 12 carbon atoms which may have a substituent.
Y ³ is a group represented by the formula “—N═” or “—NH—”.
P ³ is an atomic group that forms a nitrogen-containing aromatic heterocycle together with two carbon atoms adjacent to Y ³ and Y ³ . )

In the general formulas (5-a) and (5-b), R ¹³ and R ¹⁴ are each independently a hydrogen atom or a substituent, and examples of the substituent include the same as the substituent G. . The plurality of R ¹³ and R ¹⁴ may be the same as or different from each other.
In the general formula (5-b), R ¹⁵ is a hydrogen atom or a hydrocarbyl group having 1 to 12 carbon atoms which may have a substituent, and is the same as R ⁴² .

In the general formula (5-c), Y ³ is a group represented by the formula “—N═” or “—NH—”, and Y ¹ and Y ² in the general formula (4-3) The same. Therefore, when Y ³ is a group represented by the formula “—N =”, the position of the double bond, that is, on the side of the two carbon atoms adjacent to Y ³ , Is not limited.

The nitrogen-containing aromatic heterocycle formed by P ³ or the like may be monocyclic or polycyclic, and preferred examples include pyridine, pyrrole, pyrazine, pyrimidine, pyridazine, thiazole, imidazole, oxazole, triazole, and indole. , Benzimidazole, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, benzodiazine, pyridine, pyrrole, pyrazine, pyrimidine, pyridazine, thiazole, imidazole, oxazole, triazole, indole, benzimidazole, more preferably pyridine, pyrrole Further preferred are thiazole, imidazole and oxazole. The nitrogen-containing aromatic heterocyclic ring may have the same thing as the substituent G as a substituent.

Preferred examples of the divalent organic group formed by bonding a plurality of T ¹ to each other include those represented by the following formulas (5-1) to (5-35). The organic groups represented by the following formulas (5-1) to (5-35) may have the same thing as the substituent G as a substituent.

（式中、Ｒ^５１は水素原子、又は置換基を有していてもよい炭素数１〜１２のヒドロカルビル基である。複数のＲ^５１は互いに同一でも異なっていてもよい。）

(In the formula, R ⁵¹ is a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 12 carbon atoms. The plurality of R ⁵¹ may be the same or different from each other.)

（式中、Ｒ^５１は水素原子、又は置換基を有していてもよい炭素数１〜１２のヒドロカルビル基である。複数のＲ^５１は互いに同一でも異なっていてもよい。）

(In the formula, R ⁵¹ is a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 12 carbon atoms. The plurality of R ⁵¹ may be the same or different from each other.)

In the formula, R ⁵¹ is a hydrogen atom or a hydrocarbyl group having 1 to 12 carbon atoms which may have a substituent, and is the same as R ⁴² described above.

  In the general formula (1), M is a transition metal atom or a transition metal ion, and is coordinated or ionically bonded to at least E in the metal complex.

Examples of the transition metal atom include transition metals belonging to the fourth to sixth periods of the periodic table.
Transition metals belonging to the fourth to sixth periods of the periodic table include scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver Lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, scandium, Titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, silver, lanthanum, cerium, praseodymium, neodymium, summary , Europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten are preferred, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, Molybdenum, tantalum and tungsten are more preferred, vanadium, chromium, manganese, iron, cobalt, nickel and copper are more preferred, and iron and cobalt are particularly preferred.

  Examples of the transition metal ion include ions of the transition metal atom.

  In the general formula (1), X is a counter ion or a neutral molecule, and the counter ion electrically neutralizes the metal complex, and the neutral molecule is itself It is an electrically neutral molecule.

  Among X, neutral molecules (neutral compounds) include ammonia, pyridine, pyrrole, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, pyrazole, imidazole, 1,2,3-triazole, oxazole, Isoxazole, 1,3,4-oxadiazole, thiazole, isothiazole, indole, indazole, quinoline, isoquinoline, phenanthridine, cinnoline, phthalazine, quinazoline, quinoxaline, 1,8-naphthyridine, acridine, 2,2 ' -Bipyridine, 4,4'-bipyridine, 1,10-phenanthroline, ethylenediamine, propylenediamine, phenylenediamine, cyclohexanediamine, pyridine N-oxide, 2,2'-bipyridine N, N'-dioxide, oxamide, dimethyl Nitrogen atom-containing compounds such as glyoxime and o-aminophenol; water, methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, 2-methoxyethanol, Phenol, oxalic acid, catechol, salicylic acid, phthalic acid, 2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, hexafluoropentanedione, 1,3-diphenyl-1,3- Oxygen atom-containing compounds such as propanedione and 2,2′-binaphthol; Sulfur atom-containing compounds such as dimethyl sulfoxide and urea; 1,2-bis (dimethylphosphino) ethane, 1,2-phenylenebis (dimethylphosphine) and the like Examples of phosphorus atom-containing compounds

  Among these, the neutral molecule is preferably ammonia, pyridine, pyrrole, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, pyrazole, imidazole, 1,2,3-triazole, oxazole, isoxazole, 1,3,4-oxadiazole, indole, indazole, quinoline, isoquinoline, phenanthridine, cinnoline, phthalazine, quinazoline, quinoxaline, 1,8-naphthyridine, acridine, 2,2'-bipyridine, 4,4'- Bipyridine, 1,10-phenanthroline, ethylenediamine, propylenediamine, phenylenediamine, cyclohexanediamine, pyridine N-oxide, 2,2'-bipyridine N, N'-dioxide, oxamide, dimethylglyoxime, o-aminophen Nord, water, phenol, oxalic acid, catechol, salicylic acid, phthalic acid, 2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, hexafluoropentanedione, 1,3-diphenyl- 1,3-propanedione and 2,2′-binaphthol, more preferably ammonia, pyridine, pyrrole, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, pyrazole, imidazole, 1,2,3- Triazole, oxazole, isoxazole, 1,3,4-oxadiazole, indole, indazole, quinoline, isoquinoline, phenanthridine, cinnoline, phthalazine, quinazoline, quinoxaline, 1,8-naphthyridine, acridine, 2,2'- Bipyridine, 4,4′-bipyridine, 1 10-phenanthroline, ethylenediamine, propylenediamine, phenylenediamine, cyclohexanediamine, pyridine N-oxide, 2,2′-bipyridine N, N′-dioxide, o-aminophenol, phenol, catechol, salicylic acid, phthalic acid, 1,3 -Diphenyl-1,3-propanedione, 2,2'-binaphthol, more preferably pyridine, pyrrole, pyridazine, pyrimidine, pyrazine, pyrazole, imidazole, oxazole, indole, quinoline, isoquinoline, acridine, 2,2 '-Bipyridine, 4,4'-bipyridine, 1,10-phenanthroline, phenylenediamine, pyridine N-oxide, 2,2'-bipyridine N, N'-dioxide, o-aminophenol and phenol.

Among X, the counter ion may be either an anionic counter ion or a cationic counter ion.
Examples of counter ions having anionic property include hydroxide ions; peroxides; superoxides; cyanide ions; thiocyanate ions; halide ions such as fluoride ions, chloride ions, bromide ions, iodide ions; sulfate ions; Nitrate ion; carbonate ion, perchlorate ion; tetrafluoroborate ion; tetraarylborate ion such as tetraphenylborate ion; hexafluorophosphate ion; methanesulfonate ion; trifluoromethanesulfonate ion; p-toluenesulfonate ion Benzene sulfonate ion; phosphate ion; phosphite ion; acetate ion; trifluoroacetate ion; propionate ion; benzoate ion; metal oxide ion; methoxide ion; .
Among these, preferably, hydroxide ion, sulfate ion, nitrate ion, carbonate ion, perchlorate ion, tetrafluoroborate ion, tetraphenylborate ion, hexafluorophosphate ion, methanesulfonate ion, trifluoromethanesulfone Acid ion, p-toluenesulfonate ion, benzenesulfonate ion, phosphate ion, acetate ion, trifluoroacetate ion, more preferably hydroxide ion, sulfate ion, nitrate ion, carbonate ion, tetraphenylborate Ions, trifluoromethanesulfonate ions, p-toluenesulfonate ions, acetate ions, and trifluoroacetate ions.

Examples of the counter ion having a cationic property include alkali metal ions; alkaline earth metal ions; tetraalkylammonium ions such as tetra (n-butyl) ammonium ion and tetraethylammonium ion; and tetraarylphosphonium ions such as tetraphenylphosphonium ion. It can be illustrated.
Among these, Preferably, lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, magnesium ion, calcium ion, strontium ion, barium ion, tetra (n-butyl) ammonium ion, tetraethylammonium ion, tetraphenylphosphonium Ions, more preferably tetra (n-butyl) ammonium ions, tetraethylammonium ions, and tetraphenylphosphonium ions, and still more preferably tetra (n-butyl) ammonium ions and tetraethylammonium ions.

In the general formula (1), n is an integer of 0 or more, and represents the number of X constituting the metal complex.
And when n is two or more, several X may mutually be same or different. Further, the plurality of Xs may be only counter ions, only neutral molecules, or counter ions and neutral molecules may coexist.

  The metal complex represented by the general formula (1) is preferably a metal complex represented by the following general formula (2).

（式中、
Ｒ^１は水素原子又は置換基であり、複数のＲ^１は互いに同一でも異なっていてもよく、隣り合うＲ^１同士は互いに結合して、それぞれが結合する炭素原子とともに環を形成してもよい。
Ｑ^２は少なくとも２つの窒素原子を有する２価の有機基である。
Ｔ^２は水素原子又は有機基であり、複数のＴ^２は互いに同一でも異なっていてもよく、複数のＴ^２が有機基の場合、これらは互いに結合していてもよい。
Ｍ、Ｘ及びｎは、前記と同じ意味を表す）

(Where
R ¹ is a hydrogen atom or a substituent, and a plurality of R ¹ may be the same or different from each other, and adjacent R ¹ may be bonded to each other to form a ring together with the carbon atom to which each is bonded. .
Q ² is a divalent organic group having at least two nitrogen atoms.
T ² is a hydrogen atom or an organic group, and a plurality of T ² may be the same as or different from each other. When a plurality of T ² are an organic group, these may be bonded to each other.
M, X and n represent the same meaning as described above)

  In the general formula (2), M, X and n are the same as M, X and n in the general formula (1).

In the general formula (2), Q ² is a divalent organic group having at least two nitrogen atoms, and is the same as Q ¹ in the general formula (1).
In the general formula (2), T ² is a hydrogen atom or an organic group, and is the same as T ¹ in the general formula (1). Accordingly, the plurality of T ² may be the same as or different from each other, and the plurality of T ² may be bonded to each other.

In the general formula (2), R ¹ is a hydrogen atom or a substituent, a plurality of R ¹ may be the same or different, attached is R ¹ adjacent to each other, the carbon to which each is bound You may form a ring with an atom. R ¹ is the same as the substituent G except that R ¹ may be a hydrogen atom. That is, the substituent represented by R ¹ is the same as the substituent G.

R ¹ is hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, phenyl group, methylphenyl group, 1-naphthyl group, 2-naphthyl group. Or it is especially preferable that it is a pyridyl group.

  Preferred examples of the metal complex represented by the general formula (2) include a metal complex represented by the following general formula (3).

（式中、
Ｒ^２は水素原子又は置換基であり、複数のＲ^２は互いに同一でも異なっていてもよく、隣り合うＲ^２同士は互いに結合して、それぞれが結合する炭素原子とともに環を形成してもよい。
Ｑ^３及びＱ^４は、それぞれ独立に下記一般式（３−１）、（３−２）、（３−３）、（３−４）、（３−５）又は（３−６）で表される２価の基である。
Ｍ、Ｘ及びｎは、前記と同じ意味を表す。）

(Where
R ² is a hydrogen atom or a substituent, and a plurality of R ² may be the same or different from each other, and adjacent R ² may be bonded to each other to form a ring together with the carbon atom to which each is bonded. .
Q ³ and Q ⁴ are each independently represented by the following general formula (3-1), (3-2), (3-3), (3-4), (3-5) or (3-6). Divalent group.
M, X, and n represent the same meaning as described above. )

（式中、
Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、それぞれ独立に水素原子又は置換基であり、複数のＲ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、それぞれ互いに同一でも異なっていてもよく、複数のＲ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８が置換基である場合、これらはそれぞれ互いに結合して、それぞれが結合する炭素原子とともに環を形成してもよい。
Ａは、下記式（３−ａ）、（３−ｂ）又は下記一般式（３−ｃ）で表される２価の基であり、複数のＡは、互いに同一でも異なっていてもよい。）

(Where
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or a substituent, and a plurality of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are ^May be the same as or different from each other, and when a plurality of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are substituents, they are bonded to each other, and You may form a ring with an atom.
A is a divalent group represented by the following formula (3-a), (3-b) or the following general formula (3-c), and a plurality of A may be the same or different from each other. )

（式中、Ｒ^９は水素原子、又は置換基を有していてもよいヒドロカルビル基である。）

(In the formula, R ⁹ is a hydrogen atom or a hydrocarbyl group which may have a substituent.)

  In the general formula (3), M, X and n are the same as M, X and n in the general formula (1).

In the general formula (3), R ² is a hydrogen atom or a substituent, and is the same as R ¹ in the general formula (2). Therefore, several R < ² > may mutually be same or different and adjacent R < ² > may couple | bond together and may form a ring with the carbon atom to which each couple | bonds.

In the general formula (3), Q ³ and Q ⁴ are each independently the general formulas (3-1), (3-2), (3-3), (3-4), and (3-5). Or it is a bivalent group represented by (3-6).

In the general formulas (3-1) to (3-6), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or a substituent, and the general formula ( It is the same as R ^{1 in} 2). Accordingly, the plurality of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same as or different from each other, and the plurality of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and When R ⁸ is a substituent, they may be bonded to each other to form a ring together with the carbon atom to which each is bonded.
In the general formula (3-6), A is a divalent group represented by the formula (3-a), (3-b) or the general formula (3-c), and a plurality of A are These may be the same as or different from each other.

In the general formula (3-c), R ⁹ is a hydrogen atom or a hydrocarbyl group which may have a substituent.
The hydrocarbyl group in R ⁹ is the same as the hydrocarbyl group in the substituent G.

In the metal complex represented by the general formula (3), the ligand represented by the general formula including R ² , Q ³ and Q ⁴ is represented by the following formulas (6-7) to (6-11). The ligand represented by Formula (6-7)-(6-9) is more preferable.

  In the present invention, the ligands constituting the metal complex are preferably ligands represented by the following formulas (6-1) to (6-30), and among these, the formula (6 The ligands represented by -1) to (6-15) are more preferable. In the following formulas (6-1) to (6-30), the charge is omitted.

（式中、^ｔＢｕはｔｅｒｔ−ブチル基である。）

(In the formula, ^t Bu is a tert-butyl group.)

（式中、^ｔＢｕはｔｅｒｔ−ブチル基である。）

(In the formula, ^t Bu is a tert-butyl group.)

（式中、Ｍｅはメチル基であり、^ｔＢｕはｔｅｒｔ−ブチル基である。）

(In the formula, Me is a methyl group, and ^t Bu is a tert-butyl group.)

（式中、Ｍｅはメチル基であり、^ｔＢｕはｔｅｒｔ−ブチル基である。）

(In the formula, Me is a methyl group, and ^t Bu is a tert-butyl group.)

  In the present invention, examples of preferable metal complexes include metal complexes represented by the following general formulas (7-1) to (7-31). In the following general formulas (7-1) to (7-31), the charge, counter ion, and neutral molecule (X) are omitted.

（式中、Ｍは遷移金属原子又は遷移金属イオンであり、^ｔＢｕはｔｅｒｔ−ブチル基である。）

(In the formula, M is a transition metal atom or a transition metal ion, and ^t Bu is a tert-butyl group.)

（式中、Ｍは遷移金属原子又は遷移金属イオンであり、^ｔＢｕはｔｅｒｔ−ブチル基である。）

(In the formula, M is a transition metal atom or a transition metal ion, and ^t Bu is a tert-butyl group.)

（式中、Ｍは遷移金属原子又は遷移金属イオンであり、Ｍｅはメチル基であり、^ｔＢｕはｔｅｒｔ−ブチル基である。）

(In the formula, M is a transition metal atom or a transition metal ion, Me is a methyl group, and ^t Bu is a tert-butyl group.)

（式中、Ｍは遷移金属原子又は遷移金属イオンであり、Ｍｅはメチル基であり、^ｔＢｕはｔｅｒｔ−ブチル基である。）

(In the formula, M is a transition metal atom or a transition metal ion, Me is a methyl group, and ^t Bu is a tert-butyl group.)

  In the general formulas (7-1) to (7-31), M is a transition metal atom or a transition metal ion, and is the same as M in the general formula (1).

The metal complexes represented by the general formulas (7-1) to (7-31) are exemplified as a part of the preferred metal complexes in the present invention. For example, metals represented by general formulas (7-1) to (7-8), (7-10), (7-11), (7-16), (7-22), and (7-23) In the complex, the nitrogen atom to be coordinated with M becomes uncoordinated instead of those represented by these general formulas (the nitrogen atom of the group corresponding to Q ¹ in the general formula (1)). A metal complex that is a nitrogen atom (for example, a nitrogen atom in a pyridyl group corresponding to T ¹ in the general formula (1) in the case of the general formula (7-1)), or a general formula (7-30) In the metal complex represented by formula (1), the coordination object of M is replaced with a nitrogen atom represented by this general formula (a nitrogen atom of a group corresponding to Q ¹ in the general formula (1)), but not distributed. A metal complex that has become an oxygen atom is also a preferred metal complex.

(Method for producing metal complex)
For example, as shown below, the metal complex is obtained by organically synthesizing a ligand compound (hereinafter referred to as “ligand compound”), which is converted into a transition metal atom or a transition metal ion. It can manufacture by the method of having the process of mixing with the reaction agent (henceforth "a metal provision agent") to provide.

  The metal-imparting agent is, for example, a metal salt composed of a combination of M which is a transition metal atom in the general formulas (1) to (3) and X which is a counter ion, and preferable M and X are described above. As described above, a combination of M which is manganese, iron, cobalt, nickel or copper and X which is acetate ion, chloride ion or nitrate ion is preferable, and cobalt acetate and iron acetate are particularly preferable. The metal imparting agent may be an anhydride or a hydrate.

  For example, as described in “Journal of Organic Chemistry, 69, 5419 (2004)”, the ligand compound is obtained by combining a phenol compound having an aldehyde group and a compound having an amino group with a solvent such as alcohol. It can manufacture by the method which has the process made to react in. Further, for example, as described in “Australian Journal of Chemistry, 23, 2225 (1970)), a metal salt can be directly produced by adding a metal salt during the reaction. In addition, as described in “Tetrahedron., 1999, 55, 8377.”, an addition of an organometallic reagent to a heterocyclic ring and an oxidation reaction are performed, followed by a halogenation reaction, followed by cross-linking using a transition metal catalyst. It can manufacture by the method which has the process of performing a coupling reaction. It can also be produced by a method having a step of performing a cross-coupling reaction stepwise using a heterocyclic halide.

The step of mixing the ligand compound and the metal imparting agent is performed in the presence of an appropriate solvent.
Examples of the solvent include water, acetic acid, aqueous ammonia, methanol, ethanol, n-propanol, isopropyl alcohol, 2-methoxyethanol, 1-butanol, 1,1-dimethylethanol, ethylene glycol, diethyl ether, 1,2 -Dimethoxyethane, methyl ethyl ether, 1,4-dioxane, tetrahydrofuran, benzene, toluene, xylene, mesitylene, durene, decalin, dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, 1,2-dichlorobenzene, N, N'- Examples include dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, acetone, acetonitrile, benzonitrile, triethylamine, and pyridine. The solvent agent is soluble is preferred.
The said solvent may be used individually by 1 type, and may use 2 or more types together.

  The mixing temperature of the ligand compound and the metal imparting agent is preferably −10 to 200 ° C., more preferably 0 to 150 ° C., and particularly preferably 0 to 100 ° C. The mixing time is preferably 1 minute to 1 week, more preferably 5 minutes to 24 hours, and particularly preferably 1 hour to 12 hours. 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. In addition, depending on the kind of the solvent, the generated metal complex may be precipitated. In this case, the precipitated metal complex may be separated by filtration, and then washed, dried, or the like.

(Cathode catalyst for air secondary battery and method for producing the same)
The positive electrode catalyst for an air secondary battery of the present invention uses the metal complex. And the said metal complex may be used individually by 1 type, and may use 2 or more types together. In particular, since the catalytic activity is further improved, it is preferable that the positive electrode catalyst for an air secondary battery uses the metal complex in which M is a cobalt atom or a cobalt ion. The metal complex may be used alone or in combination with other components as a composition.

  An example of the other component is carbon. And the said other component may be used individually by 1 type, and may use 2 or more types together.

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 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.

A composition containing the metal complex and other components can be prepared by mixing these components.
In the composition, the content of the metal complex is 5 to 80 with respect to the total amount of the metal complex and other components (the sum of the content of the metal complex and the content of the other components). It is preferably mass%, more preferably 10 to 70 mass%, and particularly preferably 20 to 60 mass%.

Preferred positive electrode catalysts for air secondary batteries of the present invention include (1) those comprising the above metal complex, (2) those comprising a composition comprising the above metal complex and carbon, a metal complex, and a metal complex. A composition containing other components can be exemplified.
In addition, preferred positive electrode catalysts for air secondary batteries of the present invention include (3) those comprising a heat-treated product of the metal complex, and (4) those comprising a heat-treated product of a composition containing the metal complex and carbon. Examples of the heat treatment product of the metal complex and the heat treatment product of the composition containing the metal complex and other components (the heat treatment product of the above (1) or (2)) can be exemplified. The heat treatment is performed, for example, by heating an object.

  When performing the said heat processing, it is preferable to dry a process target object for 6 hours or more on the conditions which set temperature as 15-200 degreeC and pressure as 1333.22 Pa or less as the pretreatment. This pretreatment can be performed using, for example, a vacuum dryer.

The heat treatment is performed under a reducing gas atmosphere such as hydrogen or carbon monoxide; under an oxidizing gas atmosphere such as oxygen, carbon dioxide or water vapor; under an inert gas atmosphere such as nitrogen, helium, neon, argon, krypton or xenon; ammonia It is preferably carried out in a gas atmosphere such as a nitrogen-containing compound such as acetonitrile or its vapor; or a mixed gas atmosphere composed of two or more of these gases.
Among these, for example,
Under a reducing gas atmosphere, hydrogen or a mixed gas atmosphere of hydrogen and the inert gas;
In an oxidizing gas atmosphere, oxygen or a mixed gas atmosphere of oxygen and the inert gas;
In an inert gas atmosphere, nitrogen, neon, argon, or a mixed atmosphere composed of two or more of these gases is preferable.

  The pressure of the heat treatment is, for example, 50.7 to 152.0 kPa (0.5 to 1.5 atm), and normal pressure or a pressure in the vicinity thereof is preferable.

  The temperature of the heat treatment is preferably 250 ° C. or higher, more preferably 300 ° C. or higher, still more preferably 400 ° C. or higher, and particularly preferably 500 ° C. or higher. Moreover, this temperature becomes like this. Preferably it is 1500 degrees C or less, More preferably, it is 1200 degrees C or less, Most preferably, it is 1000 degrees C or less.

  The time for the heat treatment can be set according to the type of gas, temperature, and the like. For example, in an environment in which the gas is filled and sealed, or in an environment in which the gas is vented, the temperature may be lowered immediately after the temperature is gradually raised from room temperature to reach the target temperature. However, after reaching the target temperature, it is preferable to gradually heat by maintaining the temperature or the vicinity thereof for a predetermined time. By carrying out like this, durability of the catalyst obtained can be improved more. At this time, the time for maintaining the temperature is preferably 1 to 100 hours, more preferably 1 to 40 hours, still more preferably 2 to 10 hours, and particularly preferably 2 to 3 hours.

  Examples of the apparatus for performing the heat treatment include an oven, a furnace (such as a tubular furnace), and an IH hot plate.

  The heat treatment may be performed by adding an organic compound having a boiling point or melting point of 250 ° C. or higher, or an organic compound having a thermal polymerization start temperature of 250 ° C. or lower.

  Examples of the organic compound having a boiling point or melting point of 250 ° C. or higher include perylene-3,4,9,10-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic acid diimide, 5,8-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid diimide, 1,4,5,8-naphthalenetetracarboxylic acid, pyromellitic acid, dianhydropyromellitic acid, etc. And carboxylic acid derivatives of aromatic compounds. Examples of such compounds are given below.

  The organic compound having a thermal polymerization start temperature of 250 ° C. or lower is an organic compound having an aromatic ring and a double bond or triple bond, and examples thereof include acenaphthylene and derivatives thereof, vinyl naphthalene and derivatives thereof, and acenaphthylene and vinyl naphthalene. Is preferred.

<Air secondary battery>
The air secondary battery of the present invention includes the positive electrode catalyst for an air secondary battery of the present invention described above in the positive electrode catalyst layer, and is selected from the group consisting of zinc, iron, aluminum, magnesium, lithium, hydrogen, and ions thereof. One or more is used as the negative electrode active material, and one or more selected from the group consisting of zinc, iron, aluminum, magnesium, lithium and hydrogen is preferably used as the negative electrode active material.

  In the air secondary battery of the present invention, the positive electrode catalyst may be used alone or in combination of two or more.

FIG. 1 is a schematic cross-sectional view illustrating an embodiment of an air secondary battery according to the invention.
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, a negative electrode current collector 14, an electrolyte 15, and a container (not shown). ).
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.
In addition, the air secondary battery which concerns on this invention is not limited to what is shown here, A part structure may be changed as needed.

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.
The conductive material may be used in combination with a conductive polymer such as polypyrrole or polyaniline.

  The binder is for adhering the positive electrode catalyst, the conductive material and the like to the positive electrode current collector 12, and examples thereof include those that do not dissolve in the electrolytic solution used as the electrolyte 15, such as polytetrafluoroethylene (PTFE). , Tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, chlorotrifluoroethylene / ethylene A fluororesin such as a 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 content 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.

  The negative electrode active material in the negative electrode active material layer 13 is preferably zinc, iron, aluminum, magnesium, lithium, lithium ion, or hydrogen, more preferably zinc, iron, or hydrogen, and particularly preferably zinc.

  Negative electrodes using zinc, iron, aluminum, magnesium, and lithium as active materials include negative electrodes used in conventional zinc-air batteries, iron-air batteries, aluminum-air batteries, magnesium-air batteries, and lithium-air batteries. Can be illustrated. Moreover, as a negative electrode which uses hydrogen as an active material, the negative electrode which consists of a hydrogen storage alloy etc. which can occlude / release hydrogen can be illustrated.

  In the negative electrode active material layer 13, the constituent components such as the negative electrode active material may be used singly or in combination of two or more.

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

The electrolyte 15 is preferably used as an electrolytic solution by being dissolved in an aqueous solvent or a non-aqueous solvent.
The electrolyte for the aqueous solvent is preferably sodium hydroxide, potassium hydroxide, or ammonium chloride. In this case, the concentration of the electrolyte in the electrolytic solution is preferably 1 to 99% by mass, more preferably 5 to 60% by mass, and particularly preferably 5 to 40% by mass.

  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 electrolyte 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 15, and examples thereof include a resin nonwoven fabric or a porous film. Examples of the resin include polyolefins such as polyethylene and polypropylene; polytetrafluoroethylene, polyfluoride, and the like. Examples thereof include fluororesins such as vinylidene chloride. When the electrolyte 15 is used as an aqueous solution, it is preferable to use a hydrophilic resin as the resin.

  The air secondary battery of the present invention is useful as a small power source for mobile devices such as a power source for automobiles, a household power source, a mobile phone or a portable personal computer.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.
The compounds used in this example are as follows. In the following, the unit of concentration “M” represents “mol / L”.
Propionic acid: Wako, methanol anhydride and dichloromethane anhydride: Wako, cobalt acetate tetrahydrate: Aldrich, silica gel (Wakogel C300): Wako

<Synthesis of metal complexes>
[Synthesis Example 1]
(Synthesis of Compound (A))
According to the following reaction formula, the ligand compound (C) was synthesized via the compound (A) and the compound (B). And the metal complex (D) was synthesize | combined using the ligand compound (C) and the metal provision agent.

（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。）

(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 refine | purified using the silica gel column, and the compound (A) was obtained. Identification data for the obtained compound (A) 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 (B))

（式中、Ｂｏｃはｔｅｒｔ−ブトキシカルボニル基である。）

(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 the compound (A) 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 obtain compound (B). Identification data for the obtained compound (B) 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 (C))

  In the reaction vessel, 0.061 g of compound (B) 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 (C). Identification data for the obtained ligand compound (C) 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 (D))

（式中、Ａｃはアセチル基であり、Ｍｅはメチル基である。）

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

After making the inside of the reaction vessel a nitrogen gas atmosphere, 0.047 g of the ligand compound (C) and 3 mL of a mixed solution of 0.018 g of cobalt acetate tetrahydrate and 3 mL of chloroform were mixed. And stirred for 5 hours while heating to 80 ° C. The obtained solution was concentrated and dried to solidify to obtain a green solid. This was washed with water to obtain a metal complex (D). In addition, the metal complex (D) in the above reaction formula indicates that cobalt (Co) is coordinated to any position in the ligand compound (C) in an atomic or ionic state. Identification data for the obtained metal complex (D) are shown below.
ESI-MS [M + ·]: m / z = 749.0

[Synthesis Example 2]
(Synthesis of metal complex (E))
A metal complex (E) was synthesized according to the following reaction formula. The following ligand compounds as raw materials for the complex were synthesized based on the description of “Tetrahedron., 1999, 55, 8377”.

（式中、Ａｃはアセチル基であり、Ｅｔはエチル基である。）

(In the formula, Ac is an acetyl group, and Et is an ethyl group.)

After making the inside of the reaction vessel a nitrogen gas atmosphere, 4 ml of ethanol containing 0.300 g of the ligand compound and 0.149 g of cobalt acetate tetrahydrate was placed in a 25 ml eggplant flask and 1 at 80 ° C. Stir for hours. The produced brown precipitate was collected by filtration, washed with ethanol, and dried to obtain a metal complex (E) (yield 0.197 g). Identification data of the obtained metal complex (E) are shown below.
Elemental analysis value (%): As C ₃₂ H ₃₄ CoN ₂ O ₄
(Calculated value) C, 67.48; H, 6.02; N, 4.92.
(Measured value) C, 68.29; H, 5.83; N, 4.35.
ESI-MS [M + ·]: 533.1

[Synthesis Example 3]
(Synthesis of metal complex (F))
A metal complex (F) was synthesized according to the following reaction formula. The same ligand compound as used in Synthesis Example 2 was used as the starting material for the complex.

（式中、Ａｃはアセチル基であり、Ｅｔはエチル基である。）

(In the formula, Ac is an acetyl group, and Et is an ethyl group.)

  After making the inside of the reaction vessel a nitrogen gas atmosphere, 10 ml of ethanol containing 0.143 g (0.30 mmol) of the ligand compound and 0.0522 g (0.30 mmol) of iron (II) acetate was added to 25 ml of eggplant. It put in the flask and stirred at 80 degreeC for 2 hours. The resulting brown precipitate was collected by filtration, washed with ethanol, and dried to obtain a metal complex (F) (yield 0.12 g).

[Synthesis Example 4]
(Synthesis of metal complex (G))
A metal complex (G) was synthesized according to the following reaction formula. The following ligand compound as a raw material of the complex was synthesized based on the description of “A Chemistry, European Journal, 1999, 5, 1460”.

（式中、Ａｃはアセチル基であり、Ｅｔはエチル基である。）

(In the formula, Ac is an acetyl group, and Et is an ethyl group.)

To a 25 ml eggplant flask containing 3 ml of chloroform solution containing 0.214 g of the above ligand compound, 7 ml of ethanol containing 0.125 g of cobalt acetate tetrahydrate was added with stirring. Stir for hours. The precipitated brown precipitate was filtered, washed with ethanol, and then vacuum dried to obtain a metal complex (G) (yield 0.138 g). Identification data for the obtained metal complex (G) are shown below.
Elemental analysis value (%): C ₂₈ H ₃₄ CoN ₂ O ₄
(Calculated value) C, 64.49; H, 6.57; N, 5.37.
(Measured value) C, 64.92; H, 6.13; N, 5.06.
ESI-MS [M + ·]: 485.1

<Manufacture of cathode catalyst for air secondary battery>
[Example 1]
(Production of positive electrode catalyst (1))
The positive electrode catalyst (1) was produced by supporting the metal complex (D) on carbon. Specifically, 2 mg of the metal complex (D) and 8 mg of carbon (trade name: Ketjen Black EC600JD, manufactured by Lion Corporation) are mixed in methanol, irradiated with ultrasonic waves for 15 minutes, and then solvented with an evaporator. Was distilled off and dried under reduced pressure of 200 Pa overnight to obtain a positive electrode catalyst (1).

[Examples 2 to 4]
(Production of positive electrode catalysts (2) to (4))
Cathode catalyst (2), (3) or (4) in the same manner as in Example 1 except that metal complex (E), (F) or (G) was used instead of metal complex (D). ) Was manufactured.

[Examples 5 to 6]
(Production of positive electrode catalysts (5) to (6))
Instead of the metal complex (D), sarcomin (product code S0318, manufactured by Tokyo Chemical Industry Co., Ltd.) as the metal complex (H), or N, N′-bis (salicylidene) ethylenediamine iron (II) (as the metal complex (I)) A positive electrode catalyst (5) or (6) was produced in the same manner as in Example 1, except that product code D2571) manufactured by Tokyo Chemical Industry Co., Ltd. was used.

[Comparative Example 1]
(Production of positive electrode catalyst (R1))
Manganese dioxide (manufactured by Aldrich, product code 203750) and carbon (trade name: Ketjen Black EC600JD, manufactured by Lion) were mixed at a mass ratio of 1: 4 and stirred in ethanol at room temperature for 15 minutes. The positive electrode catalyst (R1) was obtained by drying at room temperature under reduced pressure of 200 Pa for 12 hours.

<Evaluation of cathode catalyst for air secondary battery>
(Evaluation of oxygen reduction activity)
About the positive electrode catalyst (positive electrode catalyst (1)-(6) and (R1)) obtained above, oxygen reduction activity was evaluated by the 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 positive electrode catalyst, ultrasonic waves were added. Was 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.
Using this measurement electrode, the current value of the oxygen reduction reaction was measured under the following measurement apparatus and measurement conditions. The current value is measured in a nitrogen-saturated state (under a nitrogen atmosphere) and an oxygen-saturated state (in an oxygen atmosphere). From the current values obtained in the measurement under an oxygen atmosphere, the current value is measured under a nitrogen atmosphere. The value obtained by subtracting the current value obtained by the measurement in was used as the current value of the oxygen reduction reaction. The current density was determined by dividing the current value by the surface area of the measurement electrode. The results are shown in Table 1. The current density is a value at −0.8 V with respect to the silver / silver chloride electrode.

(measuring device)
RRDE-1 rotating ring disk electrode device manufactured by Nisatsu Kogyo Co., Ltd. ALS model 701C dual electrochemical analyzer
Cell solution: 0.1 mol / L potassium hydroxide aqueous solution (oxygen saturation or nitrogen saturation)
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: 1600 rpm

(Evaluation of water oxidation activity)
About the positive electrode catalyst (positive electrode catalysts (1) to (6) and (R1)) obtained above, a measurement electrode similar to that in the case of the evaluation of the oxygen reduction activity was prepared, and using this, the following measurement device and Under the measurement conditions, the current value of the water oxidation reaction was measured. The current value was measured in a state where nitrogen was saturated, and the current density was determined by dividing the current value by the surface area of the measurement electrode. The results are shown in Table 1. The current density is a value at 1 V with respect to the silver / silver chloride electrode.

(measuring device)
RRDE-1 rotating ring disk electrode device manufactured by Nisatsu Kogyo Co., Ltd. ALS model 701C dual electrochemical analyzer
Cell solution: 1 mol / L sodium hydroxide aqueous solution (nitrogen saturation)
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

  As can be seen from Table 1, the positive electrode catalysts (1) to (6) of the present invention were remarkably excellent in both oxygen reduction activity and water oxidation activity, unlike the positive electrode catalyst (R1).

<Manufacture of air secondary battery>
[Example 7]
(Manufacture of positive electrode for air secondary battery (1))
In a menor mortar, metal complex (D) (1 part by mass) as a positive electrode catalyst, acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd.) (10 parts by mass) as a conductive material, PTFE powder (manufactured by Daikin) (1) Parts by mass) and ethanol (5 drops with a pipette) as a dispersion solution were mixed and then thinned to obtain a positive electrode catalyst layer (1).
Next, the obtained positive electrode catalyst layer (1) was sandwiched between a water-repellent PTFE sheet and a stainless mesh from both sides, and pressure-bonded with a press machine to obtain a positive electrode (1) for an air secondary battery.

(Manufacture of negative electrode (1))
The hydrogen storage alloy used as the negative electrode was taken out by the following method. An AA rechargeable nickel-metal hydride battery (ENELOOP (registered trademark), manufactured by Sanyo Electric Co., Ltd., HR-3UTGA) is connected to a charge / discharge tester (manufactured by Toyo System Co., Ltd., product name TOSCAT-3000U). It discharged until it became 0V. Next, the nickel metal hydride battery was disassembled, and the hydrogen storage alloy was taken out.
The hydrogen storage alloy was sandwiched between porous metal bodies (Celmet # 8, manufactured by Toyama Sumitomo Electric Co., Ltd.) and pressed with a press to obtain a negative electrode (1).

(Manufacture of air secondary battery (1))
After the positive electrode (1) and negative electrode (1) for an air secondary battery obtained above are installed in a container, a 8.0M potassium hydroxide aqueous solution is injected as an electrolytic solution, whereby the configuration shown in FIG. The air secondary battery (1) was obtained.

<Performance evaluation of air secondary battery>
(Charge / discharge cycle test)
The air secondary battery (1) obtained above was connected to a charge / discharge tester (manufactured by Toyo System Co., Ltd., product name TOSCAT-3000U), and a charge / discharge cycle test was performed. The charge / discharge cycle was performed by repeating the following steps 1 to 4 in this order 10 times. The voltage measurement results at this time are shown in FIG.
Step 1: Charge for 20 minutes at a constant current of 3 mA.
Step 2: Pause for 5 minutes.
Step 3: Discharge at a constant current of 3 mA. When the voltage reaches 0.5V, go to Step 4.
Step 4: Pause for 5 minutes.

  As shown in FIG. 2, the air secondary battery (1) had sufficient charge / discharge performance.

  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

  The present invention can be used in the energy field as an air secondary battery.

Claims (8)

A positive electrode catalyst for an air secondary battery using a metal complex represented by the following general formula (1).

(Where
Z ¹ is a trivalent organic group, and a plurality of Z ¹ may be the same as or different from each other.
E is an oxygen atom or a sulfur atom, and a plurality of E may be the same as or different from each other.
Q ¹ is a divalent organic group having at least two nitrogen atoms.
T ¹ is a hydrogen atom or an organic group, and a plurality of T ¹ may be the same as or different from each other. When a plurality of T ¹ are an organic group, these may be bonded to each other.
M is a transition metal atom or a transition metal ion.
X is a counter ion or a neutral molecule, n is an integer of 0 or more, and when n is 2 or more, a plurality of X may be the same or different from each other. ) The positive electrode catalyst for an air secondary battery according to claim 1, wherein the metal complex represented by the general formula (1) is a metal complex represented by the following general formula (2).

(Where
R ¹ is a hydrogen atom or a substituent, and a plurality of R ¹ may be the same or different from each other, and adjacent R ¹ may be bonded to each other to form a ring together with the carbon atom to which each is bonded. .
Q ² is a divalent organic group having at least two nitrogen atoms.
T ² is a hydrogen atom or an organic group, and a plurality of T ² may be the same as or different from each other. When a plurality of T ² are an organic group, these may be bonded to each other.
M, X, and n represent the same meaning as described above. ) Wherein T ¹ or T ² is, cathode catalyst for the air secondary battery according to claim 1 or 2 is an organic group having a nitrogen-containing aromatic heterocyclic ring. The positive electrode catalyst for an air secondary battery according to claim 2 or 3, wherein the metal complex represented by the general formula (2) is a metal complex represented by the following general formula (3).

(Where
R ² is a hydrogen atom or a substituent, and a plurality of R ² may be the same or different from each other, and adjacent R ² may be bonded to each other to form a ring together with the carbon atom to which each is bonded. .
Q ³ and Q ⁴ are each independently represented by the following general formula (3-1), (3-2), (3-3), (3-4), (3-5) or (3-6). Divalent group.
M, X, and n represent the same meaning as described above. )

(Where
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or a substituent, and a plurality of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are ^May be the same as or different from each other, and when a plurality of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are substituents, they are bonded to each other, and You may form a ring with an atom.
A is a divalent group represented by the following formula (3-a), (3-b) or the following general formula (3-c), and a plurality of A may be the same or different from each other. )

(In the formula, R ⁹ is a hydrogen atom or a hydrocarbyl group which may have a substituent.)   The positive electrode for an air secondary battery according to any one of claims 1 to 4, wherein the M is one kind of atom or ion thereof selected from the group consisting of vanadium, chromium, manganese, iron, cobalt, nickel, and copper. catalyst.   The positive electrode catalyst for an air secondary battery according to any one of claims 1 to 5, wherein a composition containing the metal complex and carbon is used.   The positive electrode catalyst for air secondary batteries as described in any one of Claims 1-6 obtained by heating the said metal complex or the composition containing the said metal complex and carbon at 300-1200 degreeC.   The positive electrode catalyst for an air secondary battery according to any one of claims 1 to 7 is included in a positive electrode catalyst layer, and is selected from the group consisting of zinc, iron, aluminum, magnesium, lithium, hydrogen, and ions thereof. Air secondary battery using one or more negative electrode active materials.

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