CN108140920A

CN108140920A - Magnesium air electrode for cell and magnesium air battery and aromatic compound and metal complex

Info

Publication number: CN108140920A
Application number: CN201680062219.1A
Authority: CN
Inventors: 古志野伸能; 小林宪史; 栗林浩
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2015-10-27
Filing date: 2016-10-21
Publication date: 2018-06-08

Abstract

A kind of magnesium air electrode for cell and magnesium cell that can inhibit hydrogen peroxide generation is provided.A kind of magnesium air electrode for cell, it includes the metal complexes selected from one or more of the group being made of cobalt complex and iron complex.A kind of magnesium air electrode for cell, wherein, above-mentioned metal complex is cobalt complex.A kind of magnesium air electrode for cell, wherein, it is nitrogen-atoms or oxygen atom that above-mentioned cobalt complex, which has at least one of coordination atom, the coordination atom,.A kind of magnesium air electrode for cell, wherein, above-mentioned metal complex is iron complex.A kind of magnesium air battery, with above-mentioned magnesium air electrode for cell.In addition, a kind of aromatic compound, forms above-mentioned complex compound；And above-mentioned complex compound.

Description

Magnesium air electrode for cell and magnesium air battery and aromatic compound and metal Complex compound

Technical field

The present invention relates to magnesium air electrode for cell and magnesium air battery and aromatic compound and metal complex.

Background technology

Magnesium air battery supplies oxygen as a positive electrode active material from the outside batteries, therefore does not need to receive in cell contents Positive active material.Therefore, it is possible to fill a large amount of negative electrode active material in battery, it is close that very high energy can be reached Degree.So expectation is expressed to magnesium air battery.

Magnesium air battery is the battery for having anode, cathode and electrolyte, the reducing power for just having oxygen, described Cathode is using magnesium or magnesium alloy as negative electrode active material.The exoelectrical reaction of battery is expressed from the next.

Anode：O₂+2H₂O+4e^-→4OH^-

Cathode：2Mg+4OH^-→2Mg(OH)₂+4e^-

Overall reaction：2Mg+O₂+2H₂O→2Mg(OH)₂

For example, Patent Document 1 discloses a kind of magnesium air battery, uses carbon (carbon fiber sheet) as anode.

Existing technical literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2011-181382 bulletins

Invention content

The subject that the invention solves

But there are a large amount of generation peroxidating in the carbon that is used only described in patent document 1 as the magnesium air battery of anode The subject of hydrogen.

The present invention is to carry out in light of this situation, provides the magnesium air electrode for cell that can inhibit hydrogen peroxide generation With magnesium air battery.In addition, the present invention provide as the magnesium air electrode for cell raw material and useful ligand and metal network Close object.

That is, the present invention provides following [1]~[19].

[1] a kind of magnesium air electrode for cell, it includes one in the group being made of cobalt complex and iron complex Kind or more metal complex.

[2] the magnesium air electrode for cell according to [1], wherein, above-mentioned metal complex is cobalt complex.

[3] the magnesium air electrode for cell according to [2], wherein, above-mentioned cobalt complex has coordination atom, the coordination At least one of atom is nitrogen-atoms or oxygen atom.

[4] the magnesium air electrode for cell according to [2] or [3], wherein, above-mentioned cobalt complex has more than two Coordination atom, the coordination atom are nitrogen-atoms and oxygen atom.

[5] the magnesium air electrode for cell according to any one of [2]~[4], wherein, above-mentioned cobalt complex is multinuclear Complex compound.

[6] the magnesium air electrode for cell according to [1], wherein, above-mentioned metal complex is iron complex.

[7] the magnesium air electrode for cell according to [6], wherein, above-mentioned iron complex has coordination atom, the coordination The all nitrogen-atoms of atom.

[8] the magnesium air electrode for cell according to any one of [1]~[7], further includes conductive carbon.

[9] the magnesium air electrode for cell according to [1], wherein, above-mentioned metal complex meets following conditions.

The energy variation amount associated with the absorption of oxygen molecule being obtained using density functional theory (B3LYP/LANL2DZ) For -50kJ/mol~-230kJ/mol.

[10] the magnesium air electrode for cell according to [9], wherein, above-mentioned metal complex further meets following Part.

It is being obtained using density functional theory (B3LYP/LANL2DZ) to be with hydrone associated energy variation amount of adsorbing 0kJ/mol~-80kJ/mol.

[11] according to the magnesium air electrode for cell described in [9] or [10], wherein, selected from being made of nitrogen-atoms and oxygen atom The atom of one or more of group be coordinated with the element selected from one or more of the group being made of iron and cobalt.

[12] the magnesium air electrode for cell according to any one of [9]~[11], wherein, above-mentioned metal complex is Iron complex, all nitrogen-atoms of coordination atom being coordinated to iron.

[13] the magnesium air electrode for cell according to any one of [9]~[11], wherein, above-mentioned metal complex is Cobalt complex, is two or more to the coordination atom that cobalt is coordinated, which is nitrogen-atoms and oxygen atom.

[14] the magnesium air electrode for cell according to any one of [9]~[13], further includes conductive carbon And binding material.

[15] the magnesium air electrode for cell according to [1], wherein, above-mentioned metal complex has shown in formula (1) Aromatic compound is as ligand.

(in formula (1), Q¹、R¹、R²And R³It is each independently hydrogen atom or monovalent substituent.Multiple Q¹、R¹、R²And R³Respectively It is identical or different.)

[16] the magnesium air electrode for cell according to [15], wherein, above-mentioned Q¹It is former for monovalence nitrogen heterocycle or halogen Son.

[17] a kind of magnesium air battery has the magnesium air electrode for cell described in any one of [1]~[16].

[18] a kind of aromatic compound is represented by formula (2).

(in formula (2), Q²For monovalence nitrogen heterocycle or halogen atom.R⁴、R⁵And R⁶It is each independently hydrogen atom or monovalence Substituent group.Multiple Q²、R⁴、R⁵And R⁶It is identical or different respectively.)

[19] a kind of metal complex is the metal complex with ligand and metal,

The ligand is the aromatic compound shown in formula (3),

The metal is the element selected from one or more of the group being made of iron and cobalt.

(in formula (3), Q³For monovalence nitrogen heterocycle or halogen atom.R⁷、R⁸And R⁹It is each independently hydrogen atom or monovalence Substituent group.Multiple Q³、R⁷、R⁸And R⁹It is identical or different respectively.)

The effect of invention

According to the present invention, when making magnesium air cell power generation, the yield of hydrogen peroxide can be inhibited.In addition, according to this Invention, is capable of providing as the raw material of the magnesium air electrode for cell and useful ligand and metal complex.

Description of the drawings

Fig. 1 is the schematic diagram of an example for the magnesium air battery for showing present embodiment.

Specific embodiment

In the following, present embodiment is described in detail.

The magnesium air electrode for cell of the present invention includes one kind in the group being made of cobalt complex and iron complex Above metal complex.

(cobalt complex)

Cobalt complex has metal centered on cobalt atom or cobalt ions, and with organic ligand.The organic ligand has There is the coordination atom being coordinated with central metal, preferably at least one of coordination atom is nitrogen-atoms or oxygen atom, is more preferably matched The all nitrogen-atoms of position atom and/or oxygen atom, all nitrogen-atoms of further preferred coordination atom and oxygen atom.Cobalt complex It is preferred that the reducing power with oxygen.Herein, the reducing power of oxygen is to refer to hydrogen reduction be hydroxide ion.

As the cobalt complex of the reducing power with oxygen, Cob altporphyrin, cobalt benzoporphyrin, cobalt phthalocyanine, cobalt porphin can be exemplified The cobalts mononuclear complexes such as quinoline alkene (Porphycene), salicil amine ethyl cobalt (SALCOMINE)；One intramolecular has multiple The cobalt polynuclear complex of cobalt atom or cobalt ions, preferably cobalt polynuclear complex.

About cobalt mononuclear complex, specific structural formula is exemplified.Hydrogen atom in structural formula can be substituted base and be taken Generation.It should be noted that the record of charge and counter ion counterionsl gegenions is omitted in the structural formula.

About cobalt polynuclear complex, specific structural formula is exemplified.Hydrogen atom in structural formula can be substituted base and be taken Generation.It should be noted that the record of charge and counter ion counterionsl gegenions is omitted in the structural formula.In addition, the part in the structural formula Cobalt can be replaced by other metallic atoms or metal ion.

As the substituent group that cobalt complex can have, can exemplify：The halogeno-groups such as fluorine-based, chloro, bromo, iodo；Hydroxyl Base；Carboxyl；Sulfydryl；Sulfonic group；Nitro；Phosphonic acid base；Silicyl with the alkyl that carbon atom number is 1~4；Methyl, ethyl, Propyl, isopropyl, cyclopropyl, butyl, isobutyl group, tertiary butyl, amyl, cyclopenta, hexyl, cyclohexyl, norborny, nonyl, Cyclononyl, decyl, 3,7- dimethyl octyl group, adamantyl, dodecyl, cyclo-dodecyl, pentadecyl, octadecyl, two The total carbon atom numbers such as dodecyl are 1~50 straight chain, branch or cricoid saturated hydrocarbyl；Methoxyl group, ethyoxyl, propoxyl group, The total carbon atom numbers such as butoxy, amoxy, cyclohexyloxy, norborneol oxygroup, decyloxy, dodecyloxy be 1~50 straight chain, Branch or cricoid alkoxy；The total carbon atom numbers such as phenyl, 4- aminomethyl phenyls, 1- naphthalenes, 2- naphthalenes, 9- anthryls are 6~60 Monovalence aromatic group, preferably halogeno-group, sulfydryl, hydroxyl, carboxyl, the saturated hydrocarbyl that carbon atom number is 1~20, entire carbon atom The monovalence aromatic group that number is 6~30 for alkoxy, the total carbon atom number of 1~10 linear chain or branch chain, more preferably chloro, Bromo, hydroxyl, carboxyl, methyl, ethyl, tertiary butyl, cyclohexyl, norborny, adamantyl, methoxyl group, ethyoxyl, phenyl.

(iron complex)

Iron complex has metal centered on iron atom or iron ion, and with organic ligand.The organic ligand has There is the coordination atom being coordinated with central metal, preferably at least one of coordination atom is nitrogen-atoms or oxygen atom, is more preferably matched The position all nitrogen-atoms of atom.Iron complex preferably has the reducing power of oxygen.

As the iron complex of the reducing power with oxygen, the iron mononuclear complexes such as iron-phthalocyanine, iron naphthalene phthalocyanine can be exemplified； There is the iron polynuclear complex of multiple iron atoms or iron ion in an intramolecular.

About iron mononuclear complex, specific structural formula is exemplified.Hydrogen atom in structural formula can be substituted base and be taken Generation.It should be noted that the record of charge and counter ion counterionsl gegenions is omitted in the structural formula.

About iron polynuclear complex, specific structural formula is exemplified.Hydrogen atom in structural formula can be substituted base and be taken Generation.It should be noted that the record of charge and counter ion counterionsl gegenions is omitted in the structural formula.In addition, the part in the structural formula Iron can be replaced by other metallic atoms, metal ion.

As the substituent group that iron complex can have, can enumerate identical with the substituent group that cobalt complex can have Substituent group.

The metal complex used in the magnesium air electrode for cell of the present invention is preferably, and utilizes density functional theory (B3LYP/LANL2DZ), it is -50kJ/mol~-230kJ/mol to calculate the energy variation amount associated with absorption oxygen molecule.It is logical Crossing makes energy variation amount can obtain the excellent magnesium air electrode for cell of hydrogen reduction in the range.

(explanation of density functional theory (B3LYP/LANL2DZ))

The metal complex used in the magnesium air electrode for cell of the present invention is preferably, and utilizes density functional theory (B3LYP/LANL2DZ), it is -50kJ/mol~-230kJ/mol to calculate the energy variation amount associated with absorption oxygen molecule.Make For with the associated energy variation amount of absorption oxygen molecule, more preferably -55kJ/mol~-200kJ/mol, further preferably - 60kJ/mol~-180kJ/mol.The program for carrying out above-mentioned energy balane is the GAUSSIAN09 of GAUSSIANINC.Carrying out energy When amount calculates, metal complex carries out most stable of under each state in cationic state, neutral state and anionic state Structure optimization under rotation status calculates, using the energy value of most stable state.In addition, when carrying out above-mentioned energy balane, In metal complex, made energy calculation with removing the structure after the substituent group that is considered occurring to be hydrated and be detached from.

About the structure of metal complex absorption oxygen molecule, also in cationic state, neutral state and anionic state Each state under carry out structure optimization under most stable of rotation status and calculate, using the energy value of most stable state.By being adopted Energy value subtracts the energy value of metal complex and the individual energy value of oxygen molecule before adsorbing oxygen molecule, thus calculates Energy variation amount.As the selection method of metal complex, such as the energy variation amount of well known metal complex can be calculated, So as to which suitably selection includes metal complex within the above range.

About by the way that such metal complex is empty to obtain the excellent magnesium of hydrogen reduction for magnesium air electrode for cell The reasons why gas electrode for cell, the inventors of the present invention are presumed as follows.

It is believed that：In the catalysis reaction for having used metal complex, in order to which the molecule with reactivity is made easily to be coordinated And produce the undersaturated position of coordination.In metal complex, for big with physics such as halogen atom, alkoxy, carboxylic acid groups For the metal complex of small and high water solubility ligand, ligand is detached from water, it is believed that is that oxygen molecule is easy With the environment of central metal coordination.It is believed that：In metal complex used in magnesium air battery in the present invention, also with generation The structure at above-mentioned coordination undersaturated position carries out reduction reaction.In addition, it can be said that above-mentioned oxygen molecule reduction reaction is just Occur at pole, electronics comes anode from cathode by electric conductor, and therefore, which becomes the possibility of anionic state It is high.It is believed that：Oxygen molecule needs steadily to be adsorbed in the structure for producing the undersaturated position of above-mentioned coordination and as the moon The metal complex of ionic condition.But if metal complex excessively stabilizes, it is likely that simple metal is caused to aoxidize etc. Undesirable reaction, it can thus be assumed that it is preferred that metal complex is moderately stabilized.Therefore, in this specification, pass through quantization Learn the oxygen molecule adsorption capacity calculated to calculate metal complex.

In addition, the metal complex included in the magnesium air electrode for cell of the present invention is preferably, in anionic state Under, using density functional theory (B3LYP/LANL2DZ), the energy variation amount associated with adsorbed water molecule is calculated as 0kJ/ Mol~-80kJ/mol.As the energy variation amount associated with the absorption of hydrone, more preferably -20kJ/mol~-75kJ/ Mol, further preferably -40kJ/mol~-70kJ/mol.The program use of above-mentioned energy balane is carried out with above-mentioned (with absorption The calculating of the associated energy variation amount of oxygen atom) same program, will be above-mentioned in oxygen molecule replace with hydrone to count It calculates.

The metal network for being -50kJ/mol~-230kJ/mol about the energy variation amount calculated and absorption oxygen molecule is associated Object is closed, exemplifies preferred structural formula.Hydrogen atom in structural formula can be substituted base and be replaced.It should be noted that the knot The record of charge and counter ion counterionsl gegenions is omitted in structure formula.

(herein, M is iron or cobalt.)

The metal network for being -50kJ/mol~-230kJ/mol as the energy variation amount calculated and absorption oxygen molecule is associated The substituent group that object can have is closed, can be exemplified：The halogeno-groups such as fluorine-based, chloro, bromo, iodo；Hydroxyl；Carboxyl；Sulfydryl；Sulfonic acid Base；Nitro；Phosphonic acid base；Silicyl with the alkyl that carbon atom number is 1~4；Methyl, ethyl, propyl, isopropyl, ring third Base, butyl, isobutyl group, tertiary butyl, amyl, cyclopenta, hexyl, cyclohexyl, norborny, nonyl, cyclononyl, decyl, 3,7- The total carbons such as dimethyl octyl group, adamantyl, dodecyl, cyclo-dodecyl, pentadecyl, octadecyl, docosyl are former Subnumber is 1~50 straight chain, branch or cricoid saturated hydrocarbyl；Methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, ring The total carbon atom numbers such as hexyloxy, norborneol oxygroup, decyloxy, dodecyloxy are 1~50 straight chain, branch or cricoid alcoxyl Base；The total carbon atom numbers such as phenyl, 4- aminomethyl phenyls, 1- naphthalenes, 2- naphthalenes, 9- anthryls are 6~60 monovalence aromatic group, excellent Be selected as straight chain that saturated hydrocarbyl, total carbon atom number that halogeno-group, sulfydryl, hydroxyl, carboxyl, carbon atom number are 1~20 are 1~10 or The alkoxy of branch, more preferably the monovalence aromatic group that total carbon atom number is 6~30, chloro, bromo, hydroxyl, carboxyl, first Base, ethyl, tertiary butyl, cyclohexyl, norborny, adamantyl, methoxyl group, ethyoxyl, phenyl.

The metal complex used in the magnesium air electrode for cell of the present invention preferably has the aromatic series shown in formula (1) Object is closed as ligand.By using the metal complex, the excellent magnesium air electrode for cell of hydrogen reduction can obtain.

In the aromatic compound shown in formula (1), the record of charge is omitted.It can be on N (nitrogen-atoms) in formula (1) Proton is bonded with, phenol structure can be formed with bonding protons on the phenates in formula (1).

R¹、R²And R³It is each independently hydrogen atom or monovalent substituent.As R¹、R²And R³Shown monovalent substituent, It is 1~18 that halogen atom, hydroxyl, carboxyl, sulfydryl, sulfonic group, nitro, phosphonic acid base, the total carbon atom number with alkyl, which can be exemplified, Silicyl, total carbon atom number be 1~50 straight chain, branch or cricoid saturated hydrocarbyl, total carbon atom number be 1~50 it is straight Chain, branch or cricoid alkoxy, the monovalence aromatic group that total carbon atom number is 6~60.

As above-mentioned halogen atom, fluorine atom, chlorine atom can be exemplified.

As the above-mentioned total carbon atom number with alkyl be 1~18 silicyl, can exemplify trimethyl silyl, T-butyldimethylsilyl.

As straight chain, branch or the cricoid saturated hydrocarbyl that above-mentioned total carbon atom number is 1~50, methyl, second can be exemplified Base, propyl, isopropyl, cyclopropyl, butyl, isobutyl group, tertiary butyl, amyl, cyclopenta, hexyl, cyclohexyl, norborny, nonyl Base, cyclononyl, decyl, 3,7- dimethyl octyl group, adamantyl, dodecyl, cyclo-dodecyl, pentadecyl, octadecyl, Docosyl.

As straight chain, branch or the cricoid alkoxy that above-mentioned total carbon atom number is 1~50, methoxyl group, second can be exemplified Oxygroup, propoxyl group, butoxy, amoxy, butoxy, amoxy, cyclohexyloxy, norborneol oxygroup, decyloxy, dodecane oxygen Base.

As the monovalence aromatic group that above-mentioned total carbon atom number is 6~60, phenyl, 4- aminomethyl phenyls, 4- can be exemplified Octyl phenyl, 1- naphthalenes, 2- naphthalenes, 9- anthryls.

R¹The straight chain, branch or cricoid saturated hydrocarbyl, entire carbon atom that preferably hydrogen atom, total carbon atom number are 1~50 Number is 6~60 monovalence aromatic group, more preferably hydrogen atom, the straight chain that total carbon atom number is 1~18, branch or cricoid Saturated hydrocarbyl, the monovalence aromatic group that total carbon atom number is 6~36, further preferably total carbon atom number are the one of 6~18 Valency aromatic group, particularly preferably phenyl.The phenyl can be with the alkyl that carbon atom number is 1~16 as substituent group.

R²Preferably hydrogen atom, straight chain, branch or cricoid saturated hydrocarbyl that total carbon atom number is 1~50, more preferably The saturated hydrocarbyl of hydrogen atom, the straight chain that total carbon atom number is 1~18, further preferably hydrogen atom.

Four R having²It can be the same or different, it is preferably identical.

R³Preferably hydrogen atom, halogen atom, hydroxyl, straight chain, branch or the cricoid saturated hydrocarbons that total carbon atom number is 1~50 Base, straight chain, branch or the cricoid alkoxy that total carbon atom number is 1~50, more preferably hydrogen atom, total carbon atom number for 1~ The alkoxy of 18 linear or branched saturated hydrocarbon base, the linear chain or branch chain that total carbon atom number is 1~18, further preferably hydrogen Atom, the linear or branched saturated hydrocarbon base that total carbon atom number is 1~18.

Six R having³It can be the same or different, it is preferably different.With six R³In, from R³Benzene From the point of view of the position of the substituent group O (oxygen atom) of ring, positioned at the R of meta position³Particularly preferably hydrogen atom.From with R³Phenyl ring O From the point of view of the position of (oxygen atom), positioned at the R of contraposition³Preferably total carbon atom number is 1~18 linear or branched saturated hydrocarbon base.

Q¹For hydrogen atom or monovalent substituent.As Q¹Shown monovalent substituent, can exemplify and R¹、R²And R³Shown The same monovalent substituent of monovalent substituent, can exemplify furan nucleus, thiphene ring, pyrrole ring, pyridine ring, pyrazine in addition to this The total carbon atom numbers such as ring, pyrimidine ring, pyridazine ring, imidazole ring, phospha phenyl ring are 3~60 monovalence aromatic heterocycle.These rings Can have the alkyl that halogen atom, carbon atom number are 1~18 or the oxyl that carbon atom number is 1~18 as substituent group.In addition, Can further be condensed on these rings has aromatic rings.Wherein, which can not produce the oxygen reduction activity of metal complex It is raw influence in the range of, imported for the purpose of increasing dissolubility of the metal complex in general solvent, improving operability. Therefore, as Q¹, alkyl that few carbon atom number be 1~18 is preferably contributed the electronics of the central metal of metal complex.It needs It is noted that since these rings are monovalent substituent, Q¹It is the group formed from these rings one hydrogen atom of removing. If for example, ring be pyridine ring, Q¹For pyridyl group.

Two Q having¹At least one of preferably monovalent substituent, more preferable two are monovalent substituent.

As Q¹Shown monovalent substituent, preferably halogen atom, hydroxyl, carboxyl, sulfydryl, sulfonic group, nitro, phosphonic acid base, It is monovalence aromatic group that linear or branched saturated hydrocarbon base that total carbon atom number is 1~18, total carbon atom number are 6~18, total Carbon atom number be 3~18 monovalence aromatic heterocycle, more preferable halogen atom, total carbon atom number be 3~18 monovalence aromatic series Heterocycle.As the monovalence aromatic heterocycle, since the oxygen reduction activity of metal complex increases, thus preferably monovalence contains Azacyclyl.As the ring for forming the monovalence nitrogen heterocycle, pyridine ring, pyridazine ring, pyrimidine ring, pyridine ring, three can be enumerated Piperazine ring, phenanthroline ring, bipyridyl ring, dipyrryl methylene basic ring, quinoline ring, isoquinolin ring, imidazole ring, pyrazole ring, oxazole ring, Thiazole ring, oxadiazole rings, Thiadiazole, azepine diazole ring, acridine ring, N- alkyl pyrrole rings etc., preferably pyridine ring, pyridazine ring, Pyrimidine ring, phenanthroline ring, bipyridyl ring, imidazole ring, more preferable pyridine ring, pyridazine ring, pyrimidine ring.As Q¹Shown halogen is former Son, preferably chlorine atom or bromine atoms.

Q¹During substituent group for large volume, due to two Q having¹Mutual steric hindrance is repelled, the aromatic series shown in formula (1) The molecular structure of compound (ligand) can damage flatness, and the oxygen reduction activity of metal complex reduces.Therefore, Q¹Preferably body The molecular structure of aromatic compound of the product as low as shown in formula (1) can keep the substituent group of this degree of flatness.

Two Q having¹It can be the same or different, as described above, in order not to make have two Q¹Position occurs each other Resistance is repelled, in a Q¹During substituent group for large volume, preferably another Q¹For compact substituent group.For example, in a Q¹It serves as reasons In the case of the monovalence nitrogen heterocycle that phenanthroline ring, bipyridyl ring are formed, preferably another Q¹For hydrogen atom or halogen atom.

From the viewpoint of the ease of manufacturing of the aromatic compound shown in formula (1), two Q having¹It is it is preferred that identical.

As the concrete example of the aromatic compound shown in formula (1), the aromatic series shown in formula (A1)~(A30) can be enumerated Compound.

In the aromatic compound shown in formula (A1)~(A30), the record of charge is omitted.In formula (A1)~(A30) In, Me is methyl, and Et is ethyl, and nBu is normal-butyl, and tBu is tertiary butyl, and nOct is n-octyl, and tOct is t-octyl.In formula (A1) in~(A30), R is hydrogen atom or carbon atom number is 1~18 alkyl.When R is hydrogen atom, it can be taken off as proton It falls.

In the metal complex shown in formula (A1)~(A30), from two Q in the aromatic compound shown in formula (1)¹ Steric hindrance it is few from the viewpoint of, preferably formula (A1)~(A3), (A5)~(A13), (A15), (A16), (A18), (A20), (A22), (A24)~(A30), from two Q in the aromatic compound shown in formula (1)¹At least one of be halogen From the viewpoint of atom or monovalence nitrogen heterocycle, more preferably formula (A5)~(A13), (A15), (A20), (A22), (A24) ~(A29), from two Q in the aromatic compound shown in formula (1)¹From the viewpoint of identical, further preferably formula (A5) ~(A13), (A15), (A20), (A22).

For with metal complex of the aromatic compound shown in formula (1) as ligand, according to central metal Quantity and charge, can have counter anion in a manner of generally neutral.As the example of counter anion, Ke Yiju Go out the anionicsite of aftermentioned metal salt.That is, metal complex for example can have acetato-, halide ion to be used as and contend with Anion.In metal complex, from the viewpoint of handling easiness when being used as magnesium air electrode for cell, preferred phase For 1 molecule of complex compound, counter anion is 0~1.

As the concrete example using the aromatic compound shown in formula (1) as the metal complex of ligand, formula can be enumerated (Co-A5)、(Co-A6)、(Co-A7)、(Co-A8)、(Fe-A5)、(Fe-A6)、(Fe-A7)、(Fe-A8)、(Co2-A9)、 (Co2-A10)、(Fe2-A1)1、(FeCo-A12)、(Co-A9)、(Co-A10)、(Fe-A11)、(Co-A12)、(Co-A20)、 (Fe-A20)、(Co2-A22)、(Fe2-A22)、(Co2-A24)、(Co2-A25)、(Co2-A26)、(Co2-A27)、(Co2- A28), the metal complex shown in (Co2-A29).

In the metal complex shown in above formula, the record of charge and counter anion is omitted.In above formula, R is hydrogen Atom or the alkyl that carbon atom number is 1~18.

Formula (Co-A5), (Co-A6), (Co-A7), (Co-A8), (Fe-A5), (Fe-A6), (Fe-A7), (Fe-A8), (Co2-A9)、(Co2-A10)、(Fe2-A11)、(FeCo-A12)、(Co-A9)、(Co-A10)、(Fe-A11)、(Co-A12)、 (Co-A20)、(Fe-A20)、(Co2-A22)、(Fe2-A22)、(Co2-A24)、(Co2-A25)、(Co2-A26)、(Co2- A27), in (Co2-A28), the metal complex shown in (Co2-A29), from the aromatic compound (ligand) shown in formula (1) Two Q¹From the viewpoint of identical, preferably formula (Co-A5), (Co-A6), (Co-A7), (Co-A8), (Fe-A5), (Fe- A6)、(Fe-A7)、(Fe-A8)、(Co2-A9)、(Co2-A10)、(Fe2-A11)、(FeCo-A12)、(Co-A9)、(Co-A10)、 (Fe-A11)、(Co-A12)、(Co-A20)、(Fe-A20)、(Co2-A22)、(Fe2-A22).From the viewpoint that central metal is cobalt From the point of view of, more preferably formula (Co-A5), (Co-A6), (Co-A7), (Co-A8), (Co2-A9), (Co2-A10), (FeCo-A12), (Co-A9)、(Co-A10)、(Co-A12)、(Co-A20)、(Co2-A22)。

(manufacturing method of metal complex)

Then, the manufacturing method of metal complex used in the magnesium air electrode for cell of the present invention is illustrated.

The manufacturing method of metal complex is not particularly limited, is suitable for the magnesium air electrode for cell of the present invention Metal complex with oxygen reducing ability is for example obtained as below：In a manner of organic chemistry after synthetic ligands compound, by gained The ligand compound arrived is mixed with assigning the reactant (hereinafter referred to as " metal imparting agent ") of metallic atom or metal ion, makes it Reaction, thus obtains metal complex.The amount of metal imparting agent reacted with ligand compound is not particularly limited, according to target Metal complex adjusts the amount of metal imparting agent, in general, make excessive metal imparting agent anti-relative to ligand compound It should.

About ligand compound, specific structural formula is exemplified.Hydrogen atom in structural formula can be substituted base and be replaced.

As metal imparting agent, make central metal in the case of cobalt, can enumerate cobalt acetate (II), cobalt acetate (III), Cobalt chloride (II), cobaltous fluoride (II), cobaltous fluoride (III), cobaltous bromide (II), cobaltous iodide (II), cobaltous sulfate (II), cobalt carbonate (II), cobalt nitrate (II), cobalt hydroxide (II), cobalt phosphate (II), cobaltous perchlorate (II), trifluoroacetic acid cobalt (II), fluoroform Sulfonic acid cobalt (II), cobalt (II), hexafluorophosphoric acid cobalt (II), tetraphenylboronic acid cobalt (II), cobaltous octadecanate (II), benzoic acid Cobalt (II) etc., preferably cobalt acetate (II), cobalt chloride (II).

Metal imparting agent may be hydrate, for example, cobalt acetate (II) tetrahydrate, cobalt chloride (II) six Hydrate.

As metal imparting agent, make central metal in the case of iron, can enumerate ferric acetate (II), iron chloride (II), Iron chloride (III), ferric bromide (II), ferric bromide (III), ferric flouride (II), ferric flouride (III), ferric sulfate (II), ferric sulfate (III), ferric nitrate (III), ferric phosphate (III), ferric perchlorate (II), ferric perchlorate (III), trifluoroacetic acid iron (II), trifluoro Loprazolam iron (II), tetrafluoro boric acid iron (II), tetraphenylboronic acid iron (II), ferric stearate (II), ferric stearate (III) etc., Preferably ferric acetate (II), iron chloride (II), iron chloride (III).

Metal imparting agent may be hydrate, for example, iron chloride (II) tetrahydrate, iron chloride (III) six Hydrate.

The process mixed to ligand compound and metal imparting agent carries out in the presence of appropriate solvent.As reaction Used in solvent (reaction dissolvent), water can be enumerated；The organic acids such as acetic acid, propionic acid；The amines such as ammonium hydroxide, triethylamine；Methanol, The alcohols such as ethyl alcohol, normal propyl alcohol, isopropanol, 2-methyl cellosolve, n-butyl alcohol, 1,1- dimethyl ethanols；Ethylene glycol, diethyl ether, 1, 2- dimethoxy-ethanes, methyl ethyl ether, 1,4- dioxanes, tetrahydrofuran, benzene,toluene,xylene, mesitylene, equal tetramethyl The aromatic hydrocarbons such as benzene, decahydronaphthalene；Halogen systems solvent, the N such as dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, 1,2- dichloro-benzenes, N '-two Methylformamide, N, N '-dimethyl acetamide, n-methyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), acetone, acetonitrile, benzonitrile, three Ethamine, pyridine etc..It should be noted that these reaction dissolvents can be used alone, can also share two or more.Separately Outside, as solvent, it is preferably able to the solvent of dissolving ligand compound and metal imparting agent.

The mixing temperature of ligand compound and metal imparting agent is preferably -10 DEG C or more and 250 DEG C hereinafter, more preferably 0 DEG C or more and 200 DEG C hereinafter, further preferably 0 DEG C or more and less than 150 DEG C.

The incorporation time of ligand compound and metal imparting agent is preferably 1 minute or more and 1 week hereinafter, more preferably 5 Minute or more and 24 hours hereinafter, further preferably 1 hour or more and less than 12 hours.

It should be noted that mixing temperature and incorporation time preferably consider the type of ligand compound and metal imparting agent and It is adjusted.

For the metal complex generated, the selection application conjunction from well known recrystallization method, reprecipitation method, chromatography etc. Suitable method thus, it is possible to be taken out from solvent, can combine a variety of methods at this time.It should be noted that the kind according to solvent Class, the metal complex generated are precipitated sometimes, in this case, by after filtering out etc. and detaching the metal complex of precipitation, It cleaned, dried.

In the magnesium air electrode for cell of the present invention, metal complex can be used alone, can also be by two kinds Use mixed above.

In the magnesium air electrode for cell of the present invention, metal complex can be mixed using well known any means It closes, for example, the method mixed using the mortar of agate.

Then, the manufacturing method of the aromatic compound shown in formula (1) is illustrated.

Aromatic compound shown in formula (1) can be manufactured by combining generally known reaction, therefore without special It limits, for example, can be manufactured according to the scheme of formula (4).

One mode of the scheme of formula (4) is shown.

It is synthesized in a manner of organic chemistry with Q¹After the compound of pyrrole ring, and with R¹Aldehyde compound mixing, thus Pyrrole ring position can be attached to.Obtained intermediate product has methine structure between two pyrrole rings.Therefore, pass through The hydrogen of methine is converted into methylene matrix using appropriate oxidant, the aromatic compound shown in formula (1) can be obtained.

As oxidant, it can suitably select oxygen, 2,3-, bis- chloro- 5,6- dicyanos -1,4-benzoquinone (DDQ) in air etc. logical Normal oxidant uses.

It is usually used general in cyclization etc. when can be applicable in synthesis derivatives of porphyrin in the scheme of formula (4) Method.

In the scheme of formula (4), general protecting group can be pre-set respectively at OH positions, NH positions.The H positions of OH Such as can be the state for having carried out methoxy protection, methyl protection etc., the H positions of NH for example can be to have carried out tertiary fourth The state of Epoxide carbonyl protection etc..In this case, deprotection reaction is carried out after the scheme of the formula that carried out (4), it is possible thereby to To the aromatic compound shown in formula (1).

In the scheme of formula (4), Q¹Or Q can be converted into aftermentioned reaction²Substituent group.For example, in formula (4) in scheme, Q¹For halogen atom, suzuki reaction is carried out after the scheme of the formula that carried out (4), Yamamoto reaction, Hui Shan reactions, is applied The cross-coupling reactions such as Di Le reactions, thus, it is possible to be converted to monovalence nitrogen heterocycle.

Then, to being carried out with manufacturing method of the aromatic compound shown in formula (1) as the metal complex of ligand Explanation.

The manufacturing method of metal complex is not particularly limited, the fragrance shown in formula (1) is synthesized in a manner of organic chemistry After compounds of group, the aromatic compound shown in formula (1) and the metal salt containing metal target kind are mixed and are made in a solvent It is reacted, and thus obtains metal complex.The amount of metal salt reacted with the aromatic compound shown in formula (1) does not limit especially It is fixed, the amount of metal salt is adjusted according to metal target complex compound, generally, it is preferred to the aromatic series shown in relative to formula (1) It closes object and uses slightly excessive metal salt.

As metal salt, ferric acetyl acetonade (II), ferric acetyl acetonade (III), ferric sulfate (II), ferric acetate can be enumerated (II), trifluoromethayl sulfonic acid iron (II), iron chloride (II), iron chloride (III), ferric nitrate (III), methanol iron (II), ethyl alcohol iron (II), cobalt acetate (II), cobalt acetate (III), cobalt chloride (II), cobaltous fluoride (II), cobaltous fluoride (III), cobaltous bromide (II), iodate Cobalt (II), cobaltous sulfate (II), cobalt carbonate (II), cobalt nitrate (II), cobalt hydroxide (II), cobalt phosphate (II), cobaltous perchlorate (II), Trifluoroacetic acid cobalt (II), trifluoromethayl sulfonic acid cobalt (II), cobalt (II), hexafluorophosphoric acid cobalt (II), tetraphenylboronic acid cobalt (II), cobaltous octadecanate (II), cobalt benzoate (II) etc., preferably ferric acetate (II), iron chloride (II), cobalt acetate (II), chlorination Cobalt (II).

Metal salt may be hydrate, for example, iron chloride (II) tetrahydrate, cobalt acetate (II) four are hydrated Object, cobalt chloride (II) hexahydrate.

The process mixed to aromatic compound and metal salt carries out in the presence of appropriate solvent.As in reaction Solvent (reaction dissolvent) used, can enumerate water；The organic acids such as acetic acid, propionic acid；The amines such as ammonium hydroxide, triethylamine；Methanol, second The alcohols such as alcohol, normal propyl alcohol, isopropanol, 2-methyl cellosolve, n-butyl alcohol, 1,1- dimethyl ethanols；Ethylene glycol, diethyl ether, 1,2- Dimethoxy-ethane, methyl ethyl ether, 1,4- dioxanes, tetrahydrofuran, benzene,toluene,xylene, mesitylene, durol, The aromatic hydrocarbons such as decahydronaphthalene；Halogen systems solvent, the N such as dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, 1,2- dichloro-benzenes, N '-dimethyl Formamide, N, N '-dimethyl acetamide, n-methyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), acetone, acetonitrile, benzonitrile, three second Amine, pyridine etc..It should be noted that these reaction dissolvents can be used alone, can also share two or more.In addition, As solvent, the aromatic compound and the solvent of metal salt being preferably able to shown in dissolution type (1).

The mixing temperature of aromatic compound and metal salt shown in formula (1) is not particularly limited, preferably -10 DEG C or more And 250 DEG C hereinafter, more preferably 0 DEG C or more and 200 DEG C hereinafter, further preferably 0 DEG C or more and less than 150 DEG C.

The incorporation time of aromatic compound and metal salt shown in formula (1) is not particularly limited, preferably 1 minute or more And 1 week hereinafter, more preferably 3 minutes or more and 24 hours hereinafter, further preferably 10 minutes or more and less than 12 hours.

It should be noted that mixing temperature and incorporation time preferably consider the aromatic compound and metal shown in formula (1) The type of salt and be adjusted.

For the metal complex generated, the selection application conjunction from well known recrystallization method, reprecipitation method, chromatography etc. Suitable method thus, it is possible to be taken out from solvent, can combine two or more methods at this time.It should be noted that according to molten The type of agent, the metal complex generated are precipitated sometimes, in this case, by filtering out the metal complex of precipitation point etc. From rear, cleaned, dried.

Then, the aromatic compound shown in formula (2) is illustrated.The magnesium air gold used in electrode of the present invention Belonging to complex compound has ligand and a metal, which is the aromatic compound shown in formula (2), the metal be preferably selected from by iron and The element of one or more of the group of cobalt composition.

R in formula (2)⁴、R⁵And R⁶Concrete example and preference respectively with the R in formula (1)¹、R²And R³Concrete example and excellent Select example identical.

Q in formula (2)²Concrete example and preference and formula (1) in Q¹Shown monovalence nitrogen heterocycle or halogen atom Concrete example is identical with preference.

That is, Q²For fluorine atom, chlorine atom, bromine atoms, iodine atom or monovalence nitrogen heterocycle.As forming, the monovalence is nitrogenous The ring of heterocycle can enumerate pyridine ring, pyridazine ring, pyrimidine ring, pyridine ring, triazine ring, phenanthroline ring, bipyridyl ring, two pyrroles Cough up methylene ring, quinoline ring, isoquinolin ring, imidazole ring, pyrazole ring, oxazole rings, thiazole ring, oxadiazole rings, Thiadiazole, nitrogen Miscellaneous diazole ring, acridine ring, N- alkyl pyrrole rings etc., preferably pyridine ring, pyridazine ring, pyrimidine ring, phenanthroline ring, bipyridyl ring, miaow Azoles ring, more preferable pyridine ring, pyridazine ring, pyrimidine ring.As Q²Shown halogen atom, preferably chlorine atom or bromine atoms.

The preferred embodiment of aromatic compound shown in formula (2) for above-mentioned formula (A5)~(A13), (A15), (A20), (A22), the aromatic compound shown in (A24)~(A26).

Aromatic compound shown in formula (2) can be manufactured by combining commonly known reaction, therefore without special It limits, for example, can be manufactured according to the scheme of formula (5).

One mode of the scheme of formula (5) and the Q in the scheme of formula (4)²One for monovalence nitrogen heterocycle or halogen atom A mode is identical.

Then, the metal complex with ligand and metal is illustrated, in the metal complex, which is formula (3) aromatic compound shown in, the metal are the element selected from one or more of the group being made of iron and cobalt.The present invention's Magnesium air electrode for cell preferably comprises metal complex, which has ligand and metal, which is formula (3) institute The aromatic compound shown, the metal are the element selected from one or more of the group being made of iron and cobalt.

In the aromatic compound shown in formula (3), charge is omitted in the same manner as the aromatic compound shown in formula (1) Record.Proton can be bonded on N (nitrogen-atoms) in formula (3), can be formed on the phenates in formula (3) with bonding protons Phenol structure.

R in formula (3)⁷、R⁸And R⁹Concrete example and preference respectively with the R in formula (1)¹、R²And R³Concrete example and excellent Select example identical.Q in formula (3)³Concrete example and preference and formula (2) in Q²Concrete example it is identical with preference.

About with structure and concrete example of the aromatic compound shown in formula (3) as the metal complex of ligand, with With the aromatic compound shown in formula (1) as among the metal complex of ligand by the Q in formula (1)¹It is defined to monovalence The structure of nitrogen heterocycle or halogen atom is identical with concrete example.

With the aromatic compound shown in formula (3) as the metal complex of ligand preferred embodiment be above-mentioned formula (Co- A5)、(Co-A6)、(Co-A7)、(Co-A8)、(Fe-A5)、(Fe-A6)、(Fe-A7)、(Fe-A8)、(Co2-A9)、(Co2- A10)、(Fe2-A11)、(FeCo-A12)、(Co-A9)、(Co-A10)、(Fe-A11)、(Co-A12)、(Co-A20)、(Fe- A20), (Co2-A22), (Fe2-A22), (Co2-A24), (Co2-A25), the metal complex shown in (Co2-A26).

It can be utilized with above-mentioned with formula (1) as the metal complex of ligand with the aromatic compound shown in formula (3) The shown aromatic compound method identical for the metal complex of ligand is manufactured.

(magnesium air battery)

The magnesium air battery of present embodiment has the magnesium air electrode for cell of the present invention as anode, and with negative Pole and electrolyte, the cathode include be selected from by magnesium simple substance and group of magnesium alloys into one or more of group negative electrode active material.

Fig. 1 is the schematic sectional view of an embodiment of the magnesium air battery for exemplifying present embodiment.

Magnesium air battery 1 shown in FIG. 1 has：Anode catalytic oxidant layer 11 comprising electrode catalyst；Positive electrode collector 12； Negative electrode active material layer 13 comprising negative electrode active material；Negative electrode collector 14；Electrolyte 15；It (is saved with the container for accommodating them Sketch map shows).

Positive electrode collector 12 is contiguously configured with anode catalytic oxidant layer 11, they constitute anode.In addition, negative electrode collector 14 are contiguously configured with negative electrode active material layer 13, they constitute cathode.In addition, it is connected with positive terminal in positive electrode collector 12 Sub (lead) 120, negative terminal (lead) 140 is connected in negative electrode collector 14.Anode catalytic oxidant layer 11 and negative electrode active material Matter layer 13 is configured opposite to each other, is configured with electrolyte 15 in a manner of being contacted with them between them.

It should be noted that the magnesium air open battery of present embodiment schedules mode shown in FIG. 1, it can be as needed Change part is formed.

(anode catalytic oxidant layer)

Anode catalytic oxidant layer includes metal complex as electrode catalyst, but other than metal complex, can also Include other electrode catalysts.In addition, metal complex, conductive material and binding material are preferably comprised in anode catalytic oxidant layer. As long as conductive material can improve the electric conductivity of electrode, preferably conductive carbon.

As conductive carbon, can exemplify " Norit " (manufacture of NORIT companies), " Ketjen black " (manufacture of Lion companies), (electrochemically industry is public for " VULCAN " (manufacture of Cabot companies), " BLACKPEARLS " (manufacture of Cabot companies), " acetylene black " Department's manufacture) carbon blacks such as (being trade name)；The fullerenes such as C60, C70；Carbon nanotube, multi-walled carbon nanotube, double-walled carbon nano-tube, The carbon fibers such as single-walled carbon nanotube, carbon nanohorn, graphene, graphene oxide, preferably carbon black.

Conductive carbon can be applied in combination with electroconductive polymers such as polypyrrole, polyanilines.

Electrode catalyst and conductive material are mutually bonded by binding material, can exemplify polytetrafluoroethylene (PTFE) (PTFE), polycyclic Oxidative ethane (PEO), polyethylene glycol (PEG), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-H), carboxymethyl cellulose (CMC), SBR styrene butadiene rubbers (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyacrylonitrile (PAN), polyimides (PI), Nafion (registered trademark) etc., preferably polytetrafluoroethylene (PTFE) gather partially Difluoroethylene (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-H), Nafion (registered trademark).

It is excellent as upper limit value about metal complex relative to metal complex and the blend amount of the total amount of conductive material It is selected as 90 weight %, more preferably 50 weight %, further preferably 30 weight %, particularly preferably 20 weight %.As under Limit value, preferably 0.1 weight %, more preferably 0.5 weight %, further preferably 1.0 weight %, particularly preferably 2.0 weights Measure %.

About the blend amount of binding material, relative to 1 mass parts of electrode catalyst, as upper limit value, preferably 300 mass Part, more preferably 200 mass parts, particularly preferably 150 mass parts.As lower limiting value, preferably 0.1 mass parts, more preferably 0.5 mass parts.

In anode catalytic oxidant layer, each constituent such as other electrode catalysts, conductive material, binding material respectively can be with One kind is used alone, can also share two or more.

(positive electrode collector)

Positive electrode collector has the function of to supply electric current to electrode catalyst, therefore, as long as the material of positive electrode collector is Electric conductivity.As preferred positive electrode collector, can exemplify metallic plate, metal foil, metal mesh, metal sinter, carbon paper, Carbon cloth.

As the metal in metal mesh and metal sinter, the simple substance of the metals such as nickel, copper, chromium, iron, titanium can be exemplified；Packet Containing the two or more alloys in these metals, preferably nickel, copper, stainless steel (Fe-Ni-Cr alloy).

(anode)

Just having anode catalyst layer and positive electrode collector.It can be pressed from both sides between anode catalytic oxidant layer and positive electrode collector Hold gas diffusion layers.About anode, the mixture can be configured for the mixing such as electrode catalyst, conductive material, binding material In on positive electrode collector, hot pressing is then carried out, anode catalytic oxidant layer is thus formed on positive electrode collector.The temperature of hot pressing does not have Especially limitation, can arbitrarily set, but be preferably set near the glass transition temperature of used binding material.In addition, Anode can be formed：Said mixture is made to be scattered in solvent, is then applied on positive electrode collector and dry, thus shape Into anode.It, can be used as the solvent illustrated in above-mentioned reaction dissolvent as solvent.

(cathode)

As cathode, it can use and live selected from one or more of group being made of magnesium simple substance and magnesium compound as cathode Property substance.As magnesium compound, magnesium alloy etc. can be exemplified.

Magnesium alloy is with magnesium alloy as main component, can exemplify magnesium-aluminum series alloy, magnesium-aluminum-zinc series alloy, magnesium-zirconium Be alloy, magnesium-zinc-zirconium alloy, magnesium-rare earth element system alloy and in above-mentioned alloy added with several % calcium it is fire-retardant Property magnesium alloy.

The shape of cathode is not particularly limited, and can be used with any shape in plate, granular, powder shaped, gel.

The form of negative electrode collector 14 can be with the homomorphosis of positive electrode collector 12.

(electrolyte)

Electrolyte can use the electrolyte for forming electrolyte dissolution in solvent.As solvent, since ion is easy Ionization, thus preferred water.

As electrolyte, sodium chloride, potassium chloride, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, carbon can be exemplified Sour potassium, saleratus, 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, Boratex, potassium sulfate, sodium sulphate, preferably sodium chloride, potassium chloride, sodium hydroxide, Potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, saleratus, more preferably sodium chloride, sodium carbonate, sodium bicarbonate.It needs Illustrate, electrolyte can be anhydride, or hydrate.

Electrolyte can be used alone, and can also be shared two or more.

The concentration of electrolyte in electrolyte can be according to the use environment of magnesium air battery come arbitrary setting, preferably 1 ~99 mass %, more preferably 5~60 mass %, further preferably 5~40 mass %.

The polycarboxylates such as citrate, succinate, tartrate can be added in the electrolytic solution.

Make in the form of the gel-like electrolyte that can form electrolyte to be absorbed into the water absorbent polymers such as polyacrylic acid With.

Container accommodates anode catalytic oxidant layer 11, positive electrode collector 12, negative electrode active material layer 13, negative electrode collector 14 and electricity Solve liquid 15.As the material of container, can exemplify the resins such as polystyrene, polyethylene, polypropylene, polyvinyl chloride, ABS resin, The metal not reacted with 11 grade contents of anode catalytic oxidant layer.

Oxygen diffusion membrane can be separately set in magnesium air battery 1.Oxygen diffusion membrane is preferably disposed on positive electrode collector 12 Outside (opposite side of anode catalytic oxidant layer 11).It, can be by by the way that oxygen diffusion membrane to be set to the outside of electrode aggregate 12 Oxygen diffusion membrane is preferentially to anode catalytic oxidant layer 11 for oxygen supply (air).

As long as oxygen diffusion membrane can suitably penetrate the film of oxygen (air), can exemplify resin non-woven fabrics, Perforated membrane.As resin, the polyolefin such as polyethylene, polypropylene can be exemplified；The fluorine tree such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride Fat.

It is short-circuit caused by the contact of positive electrode and negative electrode in order to prevent in magnesium air battery 1, can positive electrode and negative electrode it Between partition board is set.

As long as partition board is formed by the insulating materials that electrolyte 15 can move, can exemplify resin non-woven fabrics or Perforated membrane.As resin, the polyolefin such as polyethylene, polypropylene can be exemplified；The fluorine tree such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride Fat.When using electrolyte 15 in form of an aqueous solutions, as resin, it is preferable to use hydrophilized resin.

The shape of the magnesium air battery of present embodiment is not particularly limited, for example, coin-shaped, button-type, Piece shape is laminated shape, is cylindrical shape, pancake, rectangular.

The magnesium air battery of present embodiment large-scale power supply such as power supply used for electric vehicle, domestic power supply has With in addition, also useful with Miniature Power Unit as the mobile equipment such as mobile electricity Words, pocket pc.

Embodiment

In the following, by specific embodiment, the present invention will be described in more detail.

[synthesis example 1]

As shown in following reaction equations, after synthesizing compound 3 via compound 1 and compound 2, compound 3 and metal are used Imparting agent synthesizes cobalt complex MC1.

(synthesis of compound 1)

(in formula, Boc is tert-butoxycarbonyl, and dba is dibenzalacetone.)

Make in reaction vessel for after argon gas atmosphere, by 2, the 9- of 3.94g (6.00mmol) (3 '-bromo- 5 '-tertiary butyl -2 ' - Methoxyphenyl) -1,10- phenanthroline (according to Tetrahedron., 1999,55,8377. record is synthesized), 3.17g 1-N-Boc- pyrroles -2- the boric acid of (15.0mmol), three (BENZYLIDENE ACETONE) two palladium, the 0.25g of 0.14g (0.15mmol) The potassium phosphate of the 2- dicyclohexylphosphontetrafluoroborates -2 ' of (0.60mmol), 6 '-dimethoxy-biphenyl and 5.53g (26.0mmol) are added to The in the mixed solvent of the water of 200mL dioxanes and 20mL, makes its dissolving, is stirred 6 hours at 60 DEG C.After reaction, make institute Obtained reaction solution natural cooling adds in distilled water and chloroform, organic layer is extracted.Obtained organic layer is concentrated, is obtained To black residue.For obtained black residue, purified by using chloroform as molten silicagel column is unfolded, by This obtains compound 1.The appraising datum of obtained compound 1 described below.

¹H-NMR(300MHz,CDCl₃)：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= 8.6Hz, 2H), 8.27 (d, J=8.6Hz, 2H)

(synthesis of compound 2)

(in formula, Boc is tert-butoxycarbonyl.)

Make in reaction vessel for after nitrogen atmosphere, the compound 1 of 0.904g (1.08mmol) is dissolved in the anhydrous of 10mL In dichloromethane.Obtained dichloromethane solution is cooled to -78 DEG C on one side, Boron tribromide is slowly added dropwise thereto on one side 1.0M dichloromethane solutions 8.8mL (8.8mmol).After completion of dropwise addition, obtained reaction solution is cooled to -78 DEG C on one side, Stirring 10 minutes on one side, are followed by stirring for until room temperature is reached, are further stirred at room temperature.It, will be obtained anti-after 3 hours Liquid is answered to be cooled to 0 DEG C, after adding in saturated sodium bicarbonate aqueous solution, chloroform is added in and extracts, concentrate obtained organic layer.It is right In the residue of obtained brown, purified by using silicagel column of the chloroform as developing solvent, thus obtain chemical combination Object 2.The appraising datum of obtained compound 2 described below.

¹H-NMR(300MHz,CDCl₃)：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=8.4Hz, 2H), 8.46 (d, J=8.4Hz, 2H), 10.61(s,2H),15.88(s,2H).

(synthesis of compound 3)

It is in reaction vessel, the benzaldehyde of the compound 2 of 0.061g (0.10mmol) and 0.012g (0.11mmol) is molten Solution heats 7 hours in the propionic acid of 5mL at 140 DEG C.Propionic acid is distilled off from obtained reaction solution, for obtained Black residue is purified by silicagel column, thus obtains compound 3, which has used chloroform and methanol with 10：1 The solvent that mixes of volume ratio as developing solvent.The appraising datum of obtained compound 3 described below.

¹H-NMR(300MHz,CDCl₃)：δ (ppm)=1.49 (s, 18H), 6.69 (d, J=4.8Hz, 2H), 7.01 (d, J =4.8Hz, 2H), 7.57 (m, 5H), 7.90 (s, 4H), 8.02 (s, 2H), 8.31 (d, J=8.1Hz, 2H), 8.47 (d, J= 8.1Hz,2H).

(synthesis of cobalt complex MC1)

(in formula, Ac is acetyl group, and Me is methyl.)

Make in reaction vessel for after nitrogen atmosphere, the 3mL of the cobalt acetate tetrahydrate of 0.040g (0.16mmol) will be included The mixed solution of methanol and 3mL chloroforms is mixed with the compound 3 of 0.045g (0.065mmol), is stirred on one side be heated to 80 DEG C while It mixes 5 hours.Make obtained solution concentration solid, obtain blue solid.Obtained blue solid is washed with water, is thus obtained Cobalt complex MC1.It should be noted that in cobalt complex MC1 in above-mentioned reaction equation, " OAc " represent the acetic acid of 1 equivalent from Son exists as counter ion counterionsl gegenions.The appraising datum of obtained cobalt complex MC1 described below.

ESI-MS[M·]⁺：M/z=866.0

[synthesis example 2]

As shown in following reaction equations, after synthesizing compound (F) via compound (D) and compound (E), compound is used (F) and metal imparting agent has synthesized cobalt complex MC2.

In reaction vessel, by 2,6-, the bis- bromo- 4- tert-butyl benzenes methyl ethers of 0.547g, 0.844g 1-N-Boc- pyrroles- 2- boric acid, three (BENZYLIDENE ACETONE) two palladium of 0.138g, 0.247g 2- dicyclohexylphosphontetrafluoroborates -2 ', 6 '-dimethoxy-biphenyl and The potassium phosphate of 5.527g is dissolved in the in the mixed solvent of 200mL dioxanes and the water of 20mL, is stirred 9 hours at 60 DEG C.Reaction After, make obtained reaction solution natural cooling, add in distilled water, chloroform, organic layer is extracted.It concentrates obtained Organic layer obtains black residue.It for obtained black residue, is purified using silicagel column, thus obtains compound (D).The appraising datum of obtained compound (D) described below.

¹H-NMR(300MHz,CDCl₃)δ1.30(s,18H),1.31(s,9H),3.19(s,3H),6.19(m,2H),6.25 (m,2H),7.22(s,2H),7.38(m,2H).

According to following reaction equation synthesis compound (E).

Make in reaction vessel for after nitrogen atmosphere, the compound (D) of 0.453g is dissolved in the anhydrous methylene chloride of 15mL In.Using dry ice/acetone batch, obtained dichloromethane solution is cooled to -78 DEG C on one side, 5.4mL is slowly added dropwise on one side Boron tribromide (1.0M dichloromethane solutions).After completion of dropwise addition, by obtained reaction solution stir 10 minutes, remove dry ice/ After acetone bath, stir to room temperature is reached, be further stirred at room temperature.After 1 hour, saturation is added in into obtained reaction solution NaHCO₃Aqueous solution is neutralized, and is added in chloroform later and is carried out 3 extractions, concentrates obtained organic layer.For obtained Black residue is purified using silica gel, thus obtains compound (E).The identification number of obtained compound (E) described below According to.

¹H-NMR(300MHz,CDCl₃)δ1.34(s,9H),6.35(m,2H),6.40(s,1H),6.55(m,2H),6.93 (m,2H),7.36(s,2H),9.15(s,2H).

According to following reaction equation synthesis Macrocyclic compound (F).

In reaction vessel, by the compound (E) of 0.051g and the dissolution of benzaldehyde of 0.019g in the propionic acid of 20mL, 140 DEG C are heated 7 hours.Propionic acid is distilled off from obtained reaction solution, with the obtained black residue of silica gel purification, thus Obtain compound (F).The appraising datum of obtained compound (F) described below.

¹H-NMR(300MHz,CDCl₃) δ 1.38 (s, 18H), 6.58 (d, J=3.8Hz, 4H), 6.92 (d, J=3.8Hz, 4H),7.49(m,10H),7.71(s,4H),12.75(br,4H).

According to following reaction equation synthesis cobalt complex MC2.

Make in reaction vessel for after nitrogen atmosphere, on one side by methanol 4ml and chlorine comprising 0.047g cobalt acetate tetrahydrates The mixed solution of imitative 6ml and the Macrocyclic compound (F) of 0.057g are heated to 80 DEG C, on one side stirring 5 hours.It will be obtained molten Liquid concentration is solid, obtains violet solid.Obtained violet solid is washed with water, thus obtains cobalt complex MC2.It is described below The appraising datum of obtained cobalt complex MC2.

ESI-MS[M·]+：M/z=846.0

[synthesis example 3]

According to following reaction equation synthesis cobalt complex MC3.

Make in reaction vessel for after nitrogen atmosphere, by the tertiary fourths of the 4- of the cobalt chloride hexahydrate comprising 0.476g and 0.412g The 10ml ethanol solutions of bis- formyl phenol of base -2,6- are added in the eggplant type flask of 50ml, are stirred at room temperature.To obtained The 5ml ethanol solutions for including 0.216g o-phenylenediamines are slowly added dropwise in solution.Obtained mixture is flowed back 2 hours, by This generation dark brown precipitation.It filters obtained dark brown to precipitate and dry, thus obtains cobalt complex MC3 (receipts amount 0.465g； Yield 63%).

[synthesis example 4]

Make in reaction vessel after nitrogen atmosphere, to add in 3, the 5- bis- comprising 0.476g cobalt chloride hexahydrates and 0.469g The 10ml ethanol solutions of tertiary butyl-Benzaldehyde,2-hydroxy, are stirred at room temperature.It is slowly added dropwise and includes into obtained solution The 10ml ethanol solutions of 0.216g o-phenylenediamines.Obtained mixture is flowed back 2 hours, thus generates dark brown precipitation.It crosses It filters obtained dark brown to precipitate and dry, thus obtains cobalt complex MC4 (receipts amount 0.08g；Yield 7%).

[synthesis example 5]

As shown in following reaction equations, after synthesizing compound 10 via 4~compound of compound 9, compound 10 and gold are used Belong to imparting agent synthesis cobalt complex MC5.

(synthesis of compound 4)

Make in the reaction vessel through shading under argon stream, then add in 4-TBP 250g (1.664mol), Chloroform 420ml and carbon tetrachloride 420ml, next, within 8 ± 2 DEG C of 1 hour used times of temperature bromine/chloroformic solution [bromine 240g are added dropwise (0.9) equivalent, chloroform 270ml].After completion of dropwise addition, after obtained reaction solution is stirred at room temperature a Dinner, depressurize dense Thus contracting obtains (the receipts amount 372g of compound 4 of oily；Yield 97.5%).

(synthesis of compound 5)

Make in reaction vessel under argon stream, then to add in compound 4 (371g), Anhydrous potassium carbonate (335g) and acetone 5L, next, 30 minutes used times dropwise addition iodomethane 435g.After completion of dropwise addition, within temperature 40 DEG C stirring one Dinner.It filters obtained Reaction solution, and be evaporated under reduced pressure, thus obtain (the receipts amount 355.8g of compound 5；Yield 90.3%).

(synthesis of compound 6)

Make in reaction vessel under argon stream, lithium 10g and dehydration diethyl ether 102ml then to be added in, next, the used time 30 Diethyl ether solution [the compound 5 of compound 5 is added dropwise in minute：158g, dehydration diethyl ether：1L], flow back within 1 hour.By gained To reaction solution be cooled to room temperature, thus obtain lithiumation liquid.Make in reaction vessel under argon stream, then to add in 2,2 '-connection Pyridine 12.52g (0.08mol) and dehydrated toluene 1L next, obtained lithiumation liquid was added dropwise in 40 minutes used times, is carried out later It flows back within 45 hours.After interior temperature is cooled to 5 DEG C, water 300ml is added dropwise and carries out liquid separation, organic layer and water layer are thus separated into, with two Chloromethanes extracts obtained water layer, thus obtains organic layer.After the organic layer that the organic layer first obtained is obtained with after is merged, Manganese dioxide 50g is added, stirs a Dinner.Obtained mixture is filtered, after being dehydrated with anhydrous sodium sulfate, is concentrated under reduced pressure, Thus crude product is obtained.Column purification is carried out to obtained crude product, thus obtains (the receipts amount 6.245g of compound 6；Yield 16.2%).

(synthesis of compound 7)

Make the reaction vessel through shading under argon stream, then to add in compound 6 (6.145g, 12.79mmol) and taking off Water dichloromethane 400ml next, after adding in bromine 6.2g, flow back within 20 hours.It is remaining in obtained reaction mixture There are single bromine body, therefore additional bromine, further reflux 20 hours.After reaction, obtained reaction mixture is neutralized and divided After liquid, column purification is carried out, thus obtains (the receipts amount 7.334g of compound 7；Yield 89.8%).

(synthesis of compound 8)

(in formula, Boc is tert-butoxycarbonyl, and dba is dibenzalacetone.)

Make in reaction vessel for after argon gas atmosphere, by the compound 7 of 0.50g (0.77mmol), 0.41g (1.9mmol) 1-N-Boc- pyrroles -2- boric acid, three (BENZYLIDENE ACETONE) two palladium of 0.018g (0.02mmol), 0.032g (0.08mmol) 2- The potassium phosphate of dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyl and 0.72g (3.1mmol) be added to 25mL dioxanes and The in the mixed solvent of the water of 2.5mL makes its dissolving, is stirred 6 hours at 60 DEG C.After reaction, make obtained reaction solution certainly So cooling after adding in distilled water and chloroform, extracts organic layer.Obtained organic layer is concentrated, obtains black residue. For obtained black residue, purified by using silicagel column of the chloroform as developing solvent, thus obtain chemical combination Object 8.The appraising datum of obtained compound 8 described below.

(synthesis of compound 9)

(in formula, Boc is tert-butoxycarbonyl.)

Make in reaction vessel for after nitrogen atmosphere, the compound 8 of 0.28g (0.43mmol) is dissolved in anhydrous the two of 10mL In chloromethanes.Obtained dichloromethane solution is cooled to -20 DEG C on one side, Boron tribromide is slowly added dropwise on one side 1.0mol/L dichloromethane solutions 3.46mL (3.46mmol).After completion of dropwise addition, obtained reaction solution is cooled to -20 on one side DEG C, stirring 10 minutes, next, stirring to room temperature is reached, are further stirred at room temperature on one side.It, will be obtained after 3 hours Reaction solution is cooled to 0 DEG C, after adding in saturated sodium bicarbonate aqueous solution, adds in chloroform and extracts, concentrate obtained organic layer. For obtained brown residue, purified by using silicagel column of the chloroform as developing solvent, thus obtain chemical combination Object 9.The appraising datum of obtained compound 9 described below.

(synthesis of compound 10)

In reaction vessel, the compound 9 of 80mg (0.13mmol) is dissolved in the propionic acid of 150mL, is heated to 90 DEG C. The 25mL propionic acid dissolved with 14mg (0.13mmol) benzaldehyde is added dropwise into obtained solution, is heated to 140 DEG C later, stirring 3 hours.Propionic acid is distilled off from obtained reaction solution, for obtained black residue, using used by chloroform with Methanol is with 10：The solvent that 1 volume ratio mixes is purified as the silicagel column of developing solvent, thus obtains compound 10.The appraising datum of obtained compound 10 described below.

(synthesis of cobalt complex MC5)

(in formula, Ac is acetyl group, and Me is methyl.)

Make in reaction vessel for after nitrogen atmosphere, the 2mL first of the cobalt acetate tetrahydrate of 1.3mg (5.2 μm of ol) will be included The mixed solution of alcohol and 2mL chloroforms is mixed with the compound 10 of 8.7mg (1.3 μm of ol), is stirred on one side be heated to 60 DEG C while It mixes 2 hours.Make obtained solution concentration solid, obtain blue solid.Obtained blue solid is washed with water, is thus obtained Cobalt complex MC5.It should be noted that in cobalt complex MC5 in above-mentioned reaction equation, " OAc " represent the acetic acid of 1 equivalent from Son exists as counter ion counterionsl gegenions.

[synthesis example 6]

Make in reaction vessel after argon gas atmosphere, to add in 4- tert-butyl benzene methyl ether 10.1g (61.2mmol) and dehydration dichloro Methane 85mL next, after bromine 7.48mL (153mmol) was added dropwise in 10 minutes used times, is stirred at room temperature 11 hours.To acquired Reaction solution in add in Na₂SO₃After aqueous solution, extracted with chloroform.Obtained organic layer is cleaned with water and saturated brine, Obtained organic layer is dried with sodium sulphate, filters, concentrate later, thus obtain 1, the 3- bis- as colourless liquid Bromo- 5- tertiary butyls -2- methoxybenzenes (receipts amount 19.8g；Yield 100%).

(in formula, Boc is tert-butoxycarbonyl.)

Make in reaction vessel after argon gas atmosphere, to add in 1- tert-butoxycarbonyl -2- pyrrol boronic acids 1.88g (8.72mmol), sodium carbonate 2.77g (26.2mmol) and tetrakis triphenylphosphine palladium (0) 504mg (0.436mmol).Make other anti- It answers in container after argon gas atmosphere, to add in 1,3-, bis- bromo- 5- tertiary butyls -2- methoxybenzenes 3.01g (8.72mmol),-two Evil of Isosorbide-5-Nitrae Alkane 80mL and water 5mL.Obtained mixed liquor is added at room temperature in previous reaction vessel, later within temperature 60 DEG C stir Mix 4 hours, next, within temperature 100 DEG C stir 1 hour.Filter obtained reaction solution and concentrate, using developing solvent oneself Alkane：Chloroform=4：1 carries out silica gel column chromatography, thus obtains (the receipts amount 1.80g of compound 14 as colourless liquid；Yield 49.6%).The appraising datum of obtained compound 14 described below.

¹H NMR(400MHz,CDCl₃) δ 7.48 (d, J=2.8,1H), 7.41-7.40 (m, 1H), 7.23 (d, J=2.8, 1H),6.25-6.20(m,2H),3.40(s,3H),1.30(s,9H),1.26(s,9H)；¹³C NMR(100MHz,CDCl₃)δ 152.5,149.6,148.2,129.9,129.7,129.4,126.8,122.5,116.6,114.3,110.3,83.6,59.9, 34.6,31.4,27.4.

Make in reaction vessel after argon gas atmosphere, 14 1.00g of compound (2.46mmol) and propionic acid 9g to be added in, at 100 DEG C Stirring 4 hours.Obtained reaction solution is cooled to room temperature.It is added in into reaction solution after cooling by benzaldehyde 129.5mg (1.23mmol) is dissolved in solution obtained from propionic acid 1g, flows back 5 hours.Obtained reaction solution is cooled down It to room temperature, is concentrated, utilizes developing solvent hexane：Chloroform=3：1 carries out silica gel column chromatography, thus obtains as orange solid (the receipts amount 790mg of compound 15 of body；Yield 91.8%).The appraising datum of obtained compound 15 described below.

¹H NMR(400MHz,CDCl₃) δ 9.41 (s, 2H), 7.51 (d, J=2.0,2H), 7.38-7.28 (m, 7H), 6.53 (t, J=3.2,2H), 6.07 (t, J=3.2,2H), 5.56 (s, 1H), 3.50 (s, 6H), 1.31 (s, 18H)；¹³C NMR (100MHz,CDCl₃)δ149.5,149.2,142.0,133.8,129.0,128.44,128.37,127.9,127.4,126.3, 117.8,108.3,107.5,60.3,44.6,34.6,31.3.

Make in reaction vessel after argon gas atmosphere, to add in 15 220mg of compound (0.312mmol), tetrakis triphenylphosphine palladium (0) 54.1mg (0.468mmol), be dehydrated THF3mL and 2- pyridinyl zinc bromides 0.5mol/L THF solution 1.87mL (0.937mmol) is stirred at room temperature 2 hours, flows back.After 13 hours, four are added in into obtained reaction mixture (triphenylphosphine) palladium (0) 27.0mg (0.234mmol), the THF for the 0.5mol/L for being dehydrated THF2mL and 2- pyridinyl zinc bromides are molten Liquid 0.94mL (0.47mmol) flows back 12 hours.Obtained reaction solution is cooled down, after adding in saturated sodium bicarbonate aqueous solution It is filtered.Obtained filtrate is concentrated, is extracted with chloroform, obtained organic layer is cleaned with water and saturated brine, is used After sodium sulphate is dried, filtering, concentration, with developing solvent hexane：Chloroform=3：1 carries out 2 alumina gel column chromatographys, by This obtains red solid (217mg).After obtained red solid is dried in vacuo, it is dissolved in dichloromethane 2mL.Make gained After open system, to stir on one side, 5 minutes one side used times were added dropwise 2,3-, bis- chloro- 5,6- dicyanos the dichloromethane solution arrived 1,4-benzoquinone (DDQ) 86.6mg (0.343mmol) is dissolved in solution obtained from dichloromethane 7mL.It is molten for obtained reaction Liquid utilizes developing solvent chloroform：Ethyl acetate=4：1 carries out silica gel column chromatography, thus obtains blue solid 85.6mg.Use dichloro Methane extracts obtained blue solid, cleans obtained organic layer with concentrated hydrochloric acid, next, being cleaned with dilute hydrochloric acid, connects down Come, after being cleaned with saturated sodium bicarbonate aqueous solution, dried, and filter, concentrate, thus obtained as red solid with sodium sulphate 16 (58.0mg of compound；Yield 26.5%).In addition, as by-product, 12 (32.2mg of compound is obtained；Yield 14.7%).

The NMR data of compound 16 described below.

¹H NMR(400MHz,CDCl₃) δ 8.73-8.71 (m, 2H), 7.89 (d, J=2.8,2H), 7.79 (d, J=8.0, 2H), 7.71 (td, J=7.6,2.0,2H), 7.65 (d, J=2.8,2H), 7.59-7.57 (m, 2H), 7.48-7.45 (m, 3H), 7.25-7.22 (m, 2H), 6.93 (d, J=4.4,2H), 6.65 (d, J=4.4,2H), 3.48 (s, 6H), 1.31 (s, 18H)；¹³C NMR(100MHz,CDCl₃)δ156.9,153.9,153.3,149.6,147.1,141.5,139.5,138.1,136.2, 134.1,131.1,129.2,129.0,128.7,127.6,127.0,126.8,124.9,122.0,118.8,62.1,34.6, 31.5.

The NMR data of compound 12 described below.

¹H NMR(400MHz,CDCl₃) δ 8.74 (d, J=4.4,1H), 8.17 (d, J=2.8,1H), 7.84 (d, J= 7.6,1H),7.76-7.69(m,3H),7.58-7.55(m,2H),7.49-7.46(m,4H),7.27-7.24(m,1H),7.10 (d, J=4.4,1H), 6.76 (dd, J=7.6,4.4,2H), 6.52 (d, J=5.6,1H), 3.78 (s, 3H), 3.47 (s, 3H), 1.44(s,9H),1.29(s,9H)；¹³C NMR(100MHz,CDCl₃)δ159.7,157.0,154.6,151.9,149.6, 148.7,147.6,145.7,145.1,139.3,138.4,137.9,136.1,134.1,132.2,131.0,130.6, 129.8,128.7,127.7,127.5,127.4,126.8,126.0,125.0,124.8,122.7,122.0,118.1, 114.8,62.1,60.9,34.9,34.6,31.7,31.3.

Make in reaction vessel after argon gas atmosphere, to add in 16 30.0mg of compound (0.428mmol) and dehydration dichloromethane 3mL is stirred using cryostat at -20 DEG C, while the 1.0mol/L dichloromethane solutions of Boron tribromide were added dropwise in 5 minutes used times 0.86mL(0.86mmol).Although interior temperature is unchanged, the color of reaction solution changes from red as blue.It is removed after 30 minutes Cryostat stirs obtained reaction solution 5 and a half hours.After obtained reaction solution is cooled to 0 DEG C, water 1mL is added dropwise, Next it is extracted with chloroform.Obtained organic layer is cleaned with saturated sodium bicarbonate aqueous solution, next washes with water, connects Get off after being cleaned with saturated brine, dried with sodium sulphate, be filtered, concentrate, with developing solvent chloroform：Ethyl acetate=4：1 Silica gel column chromatography is carried out, thus obtains the 13 (17.4mg of compound as violet solid；Yield 60.6%).Gained described below The NMR data of compound 13 arrived.

¹H NMR(400MHz,CDCl₃) δ 8.20 (br, 2H), 8.07 (d, J=8.0,2H), 7.93 (d, J=2.8,2H), 7.85 (d, J=2.8,2H), 7.58-7.44 (m, 7H), 7.03-6.97 (m, 4H), 6.69 (br, 2H)；¹³C NMR(100MHz, CDCl₃)δ157.0,156.0,147.2,141.1,139.4,138.8,136.6,131.8,129.8(br),128.9,127.6, 126.4,126.1,122.3(br),122.1,121.5,119.0,115.9(br),34.4,31.7.

The result that the DART-MS of obtained compound 13 described below is measured.

DART-MS(M/Z)：found；671.4.calcd；671.3(M+H)⁺.

Make in reaction vessel after argon gas atmosphere, to add in the 8.9mg (0.013mmol) of compound 13 being dissolved in chloroform The solution obtained in 3mL, is stirred at room temperature, while adds in cobalt acetate (II) tetrahydrate 9.9mg (0.040mmol) Solution obtained from being dissolved in methanol 3mL.The color of reaction solution is blue by red variation.By obtained reaction solution in room temperature After lower stirring 15 minutes, flow back 2 hours.After obtained reaction solution is cooled down, concentrated, filtered with aqueous suspension, thus Obtain cobalt complex MC6.

[synthesis example 7]

It is added in into reaction vessel and the 330mg (0.47mmol) of compound 15 is dissolved in obtained from dichloromethane 5mL After solution, 10 minutes used times were added dropwise is dissolved in two by 2,3-, bis- chloro- 5,6- dicyano p-benzoquinones (DDQ) 108mg (0.47mmol) Solution obtained from chloromethanes 10mL is stirred at room temperature 1 hour.Hexane 30mL is added in into obtained reaction solution, Utilize developing solvent hexane：Chloroform=1：1 carries out silica gel column chromatography, thus obtains (the receipts amount of compound 17 as red solid 267mg；Yield 81%).The appraising datum of obtained compound 17 described below.

¹H NMR(400MHz,CDCl₃) δ 7.92 (d, J=2.4,2H), 7.57-7.54 (m, 4H), 7.49-7.44 (m, 3H), 6.93 (d, J=4.4,2H), 6.64 (d, J=4.4,2H), 3.76 (s, 6H), 1.37 (s, 18H)；¹³C NMR(100MHz, CDCl₃)δ152.5,152.2,149.1,141.7,139.7,137.7,131.2,131.0,129.4,128.8,127.7, 127.6,125.4,118.6,118.0,61.2,34.8,31.5.

Make in reaction vessel after argon gas atmosphere, to add in 17 30.0mg of compound (0.428mmol) and dehydration dichloromethane 3mL is stirred using cryostat at -20 DEG C, while the 1.0M dichloromethane solutions 0.85mL of Boron tribromide was added dropwise in 5 minutes used times (0.85mmol).Cryostat is removed after 30 minutes, obtained reaction solution is stirred 4 hours.Obtained reaction solution is cold But to after 0 DEG C, water 1mL is added dropwise, is next extracted with chloroform.It is cleaned with saturated sodium bicarbonate aqueous solution obtained organic Layer, next washes with water, after next being cleaned with saturated brine, is dried with sodium sulphate, be filtered, concentrate, molten with being unfolded Agent chloroform carries out silica gel column chromatography, thus obtains red solid (19.3mg).For obtained red solid, mixing includes 3 The 3mL methanol of the cobalt acetate tetrahydrate of equivalent and the mixed solution of 3mL chloroforms, are stirred 2 hours while being heated to 60 DEG C. The concentration of obtained reaction solution is solid, water is added in into obtained residue, carries out suspension filter, thus obtains cobalt complexing Object MC7.The result that the DART-MS of obtained cobalt complex MC7 described below is measured.

DART-MS(M/Z)：found：729.1.calcd：729.0(M+H)⁺.

[embodiment 1]

It is vitreous carbon (diameter 6.0mm) that electrode, which has used pan portion, ring portion is Pt (ring internal diameter 7.3mm, ring outer diameter 9.3mm) Ring-disc electrode.To equipped with cobalt complex MC1 (relative to conductive carbon be 3 mass %) and conductive carbon (Ketjen black EC600JD, Lion Nafion (registered trademark) solution (Aldrich manufacture, 5 mass % are added in the sample bottle of mixture 1mg) Nafion (registered trademark) solution) after 900 μ L of 100 μ L and ethyl alcohol, to sample bottle irradiation ultrasonic wave 15 minutes.By obtained point 7.2 μ L of dispersion liquid are added drop-wise to the pan portion of above-mentioned electrode, and after air-drying 1 hour, obtain measuring electrode.

Using measuring electrode obtained above, the electricity of oxygen reduction reaction is measured with following measurement devices and determination condition Flow valuve.The measure of current value respectively in the state (under nitrogen atmosphere) for making nitrogen saturation, make the state (air atmosphere of the saturation of the air Under) carry out, the electric current obtained by the measure under nitrogen atmosphere is subtracted by the current value obtained by the measure under air atmosphere Value, using obtained value as the current value of oxygen reduction reaction.By the current value divided by the surface area of measuring electrode, thus ask Go out current density.

(measurement device)

The RRDE-1 rotating ring disk electrode (r.r.d.e) devices of day thick measurement company manufacture

The dual electrochemical analyser of ALS 701C types

(determination condition)

Cell solution：1.0mol/L sodium chloride, 0.01mol/L magnesium chloride brines

Solution temperature：25℃

Reference electrode：Silver/silver chloride electrode (saturation potassium chloride)

To electrode：Platinum filament

Sweep speed：10mV/ seconds

Ring current potential：1.125V vs silver/silver chloride electrode (saturation potassium chloride)

Electrode rotating speed：1600rpm

Using the disk current value and loop current value obtained by measure, 4 electron reductions of the oxygen based on electrode catalyst are obtained Rate.4 electron reduction rates are calculated based on following formula.

[mathematical expression 1]

In formula, i_DIndicating panel current density, i_RRepresent circular current density, N_r/dRepresent catching for the disk reaction product in ring electrode Catch rate.Catch rate utilizes [Fe (CN)₆]^3-/4-Redox system be measured, as a result in electrode used in embodiment It is 0.38.

By using above-mentioned catch rate, 4 electron reduction rates of the oxygen based on above-mentioned electrode catalyst are obtained.By the 4 of oxygen Electron reduction rate is shown in table 1 below.

[embodiment 2~8]

It is (real using cobalt complex MC2 (embodiment 2), cobalt complex MC3 respectively instead of cobalt complex MC1 (embodiment 1) Apply example 3), cobalt complex MC4 (embodiment 4), cobalt complex MC5 (embodiment 5), cobalt complex MC6 (embodiment 6), cobalt complexing Object MC7 (embodiment 7) and iron complex MC8 (embodiment 8, iron-phthalocyanine, Aldrich manufacture, product identification 379549, under Formula compound represented), it is evaluated similarly to Example 1.4 electron reduction rates of oxygen are shown in table 1 below.

[comparative example 1]

Carbon is used only without using cobalt complex, is evaluated similarly to Example 1.4 electron reduction rates of oxygen are shown In table 1 below.

[table 1]

Evaluation	4 electron reduction rates (%)
		Embodiment 1	90
Embodiment 2	75
		Embodiment 3	60
Embodiment 4	60
		Embodiment 5	90
Embodiment 6	70
		Embodiment 7	50
Embodiment 8	60
		Comparative example 1	30

It understands：The magnesium air electrode for cell of the present invention can inhibit hydrogen peroxide since 4 electron reduction rates of oxygen are high Generation.

[reference example 1]

By taking cobalt complex MC1 as an example, the calculated example of pair energy variation amount associated with oxygen absorption illustrates.Metal complex Object has acetato- as counter anion, it is assumed that occurs to be hydrated and be detached from as acetate anion on electrode in water, It is respective to single anion state and two anionic states using GAUSSIAN09 programs not have the structure of acetato- Rock-steady structure carries out structure optimization calculating using density functional theory (B3LYP/LANL2DZ), and confirmation form anionic state is three It is most stable of structure, and obtain its energy value under weight state.Later, the metal complex about single anion state is adsorbed with The structure of oxygen molecule also carries out structure optimization calculating, confirms under quintuplet to be most stable of structure, and obtain its energy value. The energy value of metal complex and the individual energy value of oxygen molecule before absorption oxygen molecule are subtracted by obtained energy value, thus Calculate energy variation amount.

About the calculating of the energy variation amount associated with the absorption of hydrone, by the above-mentioned energy associated with the absorption of oxygen molecule The oxygen molecule measured in the calculating of variable quantity is substituted for hydrone, is thus calculated.Confirm the metal complex of Water Molecular Adsorption Object is most stable of structure under triplet.

For other metal complexes, also calculated using method same as described above, but about without halide The metal complex of the neutral state of the counter anions such as ion, acetato-, with single anion state and two anionic states It makes energy calculation respectively, the calculating of each energy variation amount is carried out under most stable of state.It shows the result in table 2 below.

The evaluation of oxygen reduction activity is carried out with electrode using said determination.The current value of oxygen reduction reaction is shown in following tables In 2.It should be noted that current density be relative to silver/silver chloride electrode be -0.1V when value.

[reference example 2]~[reference example 5]

Instead of cobalt complex MC1 (reference example 1) respectively using cobalt complex MC5 (reference example 2), cobalt complex MC6 (ginsengs Examine example 3), iron complex MC8 (reference example 4) and cobalt complex MC9 (reference example 5), be carried out similarly evaluation with reference example 1.Cobalt Complex compound MC9 is synthesized by following synthesis examples 8.

[synthesis example 8]

Compound 11 is synthesized using the method described in J.Am.Chem.Soc.2011,133,10720-10723.Later, Utilize the method synthesis cobalt complex MC9 described in Chem.Eur.J.2012,18,14590-14593.Obtained by described below Cobalt complex MC9 DART-MS measure result.

DART-MS(M/Z)：found：685.4.calcd：685.3(M+H)⁺.

[comparison reference example 1]~[comparison reference example 5]

Instead of cobalt complex MC1 (reference example 1) respectively using cobalt complex RE1 (comparison reference example 1), cobalt complex RE2 (comparison reference example 2) and cobalt complex RE3 (comparison reference example 3), evaluation is carried out similarly with reference example 1.In addition, conduct Without using metal complex, the evaluation of oxygen reduction activity is carried out similarly with reference example 1 for comparison reference example 4.Cobalt complex RE1 The product identification 446645 (following structural formula compound represented) manufactured using Aldrich.Cobalt complex RE2 and cobalt Complex compound RE3 is synthesized respectively by following synthesis examples 9 and synthesis example 10.

[synthesis example 9]

About cobalt complex RE2, according to following reaction equation, ligand and the ethyl alcohol comprising cobalt acetate tetrahydrate are mixed It closes, makes its reaction, thus synthesized.As complexing raw material ligand be based on Tetrahedron., 1999,55,8377 into Row synthesis.

Make in reaction vessel for after nitrogen atmosphere, by the ligand of 0.300g and cobalt acetate tetrahydrate comprising 0.149g 4ml ethyl alcohol is added in the eggplant type flask of 25ml, is stirred 1 hour at 80 DEG C.The obtained tan precipitate of leaching and with ethyl alcohol into Row cleaning, is dried later, thus obtains cobalt complex RE2 (receipts amount is 0.197g).

[synthesis example 10]

Cobalt complex RE3 according to following reaction equation, with reference to Australian Journal of Chemistry, 23, Method described in 2225 (1970) is synthesized.

Make in reaction vessel for after nitrogen atmosphere, add in the 4- methyl of the cobalt chloride hexahydrate comprising 1.9g and 1.31g- The 50ml methanol solutions of 2,6- bis- formyl phenol, are stirred at room temperature later.It is slowly added dropwise into obtained solution Solution obtained from the 1,3- propane diamine of 0.59g is dissolved in the methanol of 20ml.Obtained mixture is flowed back 3 hours, Thus generate dark brown precipitation.The obtained dark brown of leaching is precipitated and is dried, and thus obtains cobalt complex RE3 (receipts amounts 1.75g；Yield 74%).

[table 2]

It understands：Include the energy calculated using density functional theory (B3LYP/LANL2DZ) and absorption oxygen molecule is associated Variable quantity be the electrode of the metal complex of -50kJ/mol~-230kJ/mol since the current density of hydrogen reduction is high, thus oxygen Reducing power it is high, be suitable for the electrode of magnesium air battery.

[reference example 6]~[reference example 7]

Above-mentioned measuring electrode is made using cobalt complex MC7 (reference example 6) and cobalt complex MC10 (reference example 7), And carry out the evaluation of oxygen reduction activity.The current value of oxygen reduction reaction is shown in Table 3 below.It should be noted that current density Be relative to silver/silver chloride electrode be -0.1V when value.Cobalt complex MC10 is synthesized by following synthesis examples 11.

[synthesis example 11]

Using Chem.Commun., the method synthetic ligands (A1) described in 2009,2544-2546.

For ligand (A1) 10mg, the 3mL methanol of cobalt acetate tetrahydrate of the mixing comprising 3 equivalents and mixing for 3mL chloroforms Solution is closed, is stirred while being heated to 60 DEG C 2 hours.By obtained solution concentration it is solid after, into obtained residue Water is added in, suspension filter is carried out, thus obtains cobalt complex MC10.

[comparison reference example 5]~[comparison reference example 6]

(compared using manganese dioxide (comparison reference example 5) and cobalt phthalocyanine respectively instead of cobalt complex MC7 (reference example 6) Reference example 6, Aldrich manufacture, product identification 307696), it is carried out similarly evaluation with reference example 6.It shows the result in down It states in table 3.

[table 3]

Evaluation	A specimen	Current density (mA/cm²)
			Reference example 6	Cobalt complex MC7	0.361
Reference example 7	Cobalt complex MC10	0.274
			Comparison reference example 5	Manganese dioxide	0.006
Comparison reference example 6	Cobalt phthalocyanine	0.026

According to reference example 3 and reference example 5~7 and comparison reference example 4~6 as a result, including the aromatic series shown in formula (1) Compound is current density height of the electrode due to hydrogen reduction of the metal complex of ligand, thus the reducing power of oxygen is high, is suitable Together in the electrode of magnesium air battery.

[embodiment 9]

(making of gas diffusion layers powder)

By carbon black (acetylene black), Triton (Kishida Chemical Inc) and water with 1：1：The ratio of 30 (weight ratios) After mixing, add in PTFE (great Jin, D-210C), make its relative to carbon black be 67 weight %, with Millser crush after five minutes, into Row suction strainer, it is 12 hours dry at 120 DEG C.Obtained dried object with Millser is micronized, 3 are carried out in 280 DEG C, air Hour heat treatment.Obtained heat treatment object with Millser is micronized again, thus obtains gas diffusion layers powder.

(making of catalyst layer powder)

Water 100ml and n-butyl alcohol 1ml is added in into beaker, next, adding in carbon (Ketjen black 600EC) 0.18g and synthesis The cobalt metal complex MC1 0.08g made in example 1.After obtained mixture is stirred 2 hours, add in bit by bit PTFE (great Jin, D-210C) 0.16g, and then stir 1 hour.Suction strainer is carried out to obtained mixture, in 120 DEG C of dryings, is used Millser is crushed, and thus obtains catalyst layer powder.

(making of anode)

Aluminium foil is placed in hot pressing mold, nickel screen (manufacture of ニ U ライ companies) is placed on it, to nickel screen filling gas Diffusion layer electrode powder 60mg, the catalyst filling layer powder 60mg on gas diffusion layers powder.First, with 80kgf/ cm²Pressure be cold-pressed after, using remain 350 DEG C hot press carry out 10 seconds suppress, obtain anode.The reaction surface of anode Product is 1.767cm²。

(magnesium air battery)

Using anode obtained above, as cathode magnesium plate (ELEKIT companies manufacture, magnesium fuel cell vehicle JS- 7900), as the copper foil of the collector of cathode (Aldrich manufacture, product identification 34208), magnesium air battery is assembled.Note Enter the 1M sodium-chloride water solutions as electrolyte, be connected to charge and discharge test machine (manufacture of Toyo System companies, ProductName： TOSCAT-3000U power generation test) is carried out, thus, it is possible to confirm the power generation of magnesium air battery.

Industrial utilizability

Reference sign

1 ... magnesium air battery, 11 ... anode catalytic oxidant layer, 12 ... positive electrode collectors, 120 ... positive terminals, 13 ... cathode Active material layer, 14 ... negative electrode collectors, 140 ... negative terminals, 15 ... electrolyte.

Claims

1. a kind of magnesium air electrode for cell, it includes selected from one or more of group being made of cobalt complex and iron complex Metal complex.

2. magnesium air electrode for cell according to claim 1, wherein, the metal complex is cobalt complex.

3. magnesium air electrode for cell according to claim 2, wherein, the cobalt complex has coordination atom, this is matched At least one of position atom is nitrogen-atoms or oxygen atom.

4. the magnesium air electrode for cell according to Claims 2 or 3, wherein, the cobalt complex has more than two Coordination atom, the coordination atom are nitrogen-atoms and oxygen atom.

5. the magnesium air electrode for cell according to any one of claim 2~4, wherein, the cobalt complex is multinuclear Complex compound.

6. magnesium air electrode for cell according to claim 1, wherein, the metal complex is iron complex.

7. magnesium air electrode for cell according to claim 6, wherein, the iron complex has coordination atom, this is matched The position all nitrogen-atoms of atom.

8. magnesium air electrode for cell according to any one of claims 1 to 7, further includes conductive carbon.

9. magnesium air electrode for cell according to claim 1, wherein, the metal complex meets following conditions,

The energy variation amount associated with the absorption of oxygen molecule being obtained using density functional theory B3LYP/LANL2DZ is -50kJ/ Mol~-230kJ/mol.

10. magnesium air electrode for cell according to claim 9, wherein, the metal complex further meets following Condition,

The energy variation amount associated with the absorption of hydrone being obtained using density functional theory B3LYP/LANL2DZ is 0kJ/ Mol~-80kJ/mol.

11. magnesium air electrode for cell according to claim 9 or 10, wherein, selected from being made of nitrogen-atoms and oxygen atom The atom of one or more of group be coordinated with the element selected from one or more of the group being made of iron and cobalt.

12. the magnesium air electrode for cell according to any one of claim 9~11, wherein, the metal complex is Iron complex, all nitrogen-atoms of coordination atom being coordinated to iron.

13. the magnesium air electrode for cell according to any one of claim 9~11, wherein, the metal complex is Cobalt complex, is two or more to the coordination atom that cobalt is coordinated, which is nitrogen-atoms and oxygen atom.

14. the magnesium air electrode for cell according to any one of claim 9~13, further include conductive carbon and Binding material.

15. magnesium air electrode for cell according to claim 1, wherein, the metal complex has shown in formula (1) Aromatic compound as ligand,

In formula (1), Q¹、R¹、R²And R³It is each independently hydrogen atom or monovalent substituent；Multiple Q¹、R¹、R²And R³It is identical respectively It is or different.

16. magnesium air electrode for cell according to claim 15, wherein, the Q¹It is former for monovalence nitrogen heterocycle or halogen Son.

17. a kind of magnesium air battery, with the magnesium air electrode for cell described in any one of claim 1~16.

18. a kind of aromatic compound is represented by formula (2),

In formula (2), Q²For monovalence nitrogen heterocycle or halogen atom；R⁴、R⁵And R⁶It is each independently hydrogen atom or monovalent substituent； Multiple Q²、R⁴、R⁵And R⁶It is identical or different respectively.

19. a kind of metal complex is the metal complex with ligand and metal,

The ligand is the aromatic compound shown in formula (3),

The metal is the element selected from one or more of the group being made of iron and cobalt,

In formula (3), Q³For monovalence nitrogen heterocycle or halogen atom；R⁷、R⁸And R⁹It is each independently hydrogen atom or monovalent substituent； Multiple Q³、R⁷、R⁸And R⁹It is identical or different respectively.