JPWO2015147326A1 - Electrode active material - Google Patents

Abstract

Provided is an electrode active material containing a new type of organic compound having good charge / discharge characteristics and excellent cost. An organic compound having a structure in which a cyclohexane ring and / or a benzene ring are condensed to a pyrazine ring, wherein the cyclohexane ring and / or benzene ring is an OX group (X is H, Na, Li, 1 / 2Mg, or none) A secondary battery electrode active material characterized by containing an organic compound that may be substituted by any one), and has good charge / discharge characteristics in aqueous sodium ion secondary batteries and aqueous magnesium ion secondary batteries Demonstrate.

Description

  The present invention belongs to the technical field of secondary batteries, and particularly relates to a novel electrode active material made of an organic material and a secondary battery using the same.

  In recent years, as a secondary battery, a large-sized storage battery that aims at high cost performance is desired. In particular, if the electrolyte solvent can be replaced with a water-based solvent from a conventional non-aqueous solvent, it is possible to use safe water at low cost, which is advantageous in terms of economy and safety.

As an electrode active material used for such an aqueous electrolyte secondary battery, for example, there is NaTi ₂ (PO ₄ ) ₃ used for a negative electrode active material for a sodium ion secondary battery having metallic zinc as a positive electrode (non-contained) Patent Document 1). Further, the composition formula Mg _x M1 _1-y M2 _y O ₂ or Mg _x M1 _1-y M2 _y O ₂ .nH ₂ O used as a positive electrode active material for a magnesium ion secondary battery using a metal magnesium electrode as a negative electrode. (M1 is at least one selected from Mn and Fe; M2 is a transition metal excluding M1 and at least one selected from Al; 0 <x ≦ 0.5; 0 ≦ y <0.4; 4 to 0.6), and the crystal structure has a layered structure (see Patent Document 1). However, these electrode active materials involve resource problems and disposal problems because they use inorganic materials including metals such as rare metals.

  For this reason, the metal free electrode active material which does not contain a metal is desired more. As such an electrode active material, an organic electrode active material containing an organic compound has been proposed. For example, a pyrazine structure bonded to a cycloalkane used as a positive electrode active material for a lithium ion secondary battery is a structural unit. Organic compounds having a non-acene structure contained therein (see Patent Document 2), Radialene compounds having a heteroaromatic group (see Non-Patent Document 2), triquinoxalinylene compounds exhibiting 6-electron transfer (see Non-Patent Document 3) ), And polyatomic redox organic molecules (see Non-Patent Document 4 and Non-Patent Document 5).

  In addition, oxocarbonic acid salts such as disodium rhodizonate, disodium squarate, and disodium croconate used for positive electrodes for sodium ion batteries (see Patent Document 3, Non-Patent Document 6, and Non-Patent Document 7). ), And terephthalic acid (see Non-Patent Document 8) used for negative electrodes for sodium ion batteries have also been proposed.

JP 2002-25555 A JP 2012-79479 A JP 2013-229321 A

Sun Il Park, Irina Gocheva, Shigeto Okada, and Jun-ichi Yamaki, Journal of The Electrochemical Society, 158 (9) 1-4, 2011. Sugimoto Toyonari et al., "Creation of organic secondary batteries using a radialene compound with heteroaromatic groups that undergo multi-electron oxidation-reduction", Proceedings of the 51st Battery Conference, 3G22, p523, 2010 Takayuki Matsunaga, Takayuki Kubota, Toyonari Sugimoto, and Masaharu Satoh, Chem. Lett. 2011, 40, 750 Arisa Masuda et al., "Application of multi-electron redox organic molecules to lithium ion battery cathode materials", Proceedings of the 80th Anniversary of the Electrochemical Society, PBT-24, p490, 2013 Yuki Hanyu, Toyonari Sugimoto, Yoshiyuki Ganbe, Asuna Masuda, and Itaru Honma, Journal of The Electrochemical Society, 161 (1) A6-A9, 2014 Kuniko Chihara et al., "Electrochemical characteristics and charge / discharge mechanism of organic cathode material Na2C6O6 for sodium secondary battery", Proceedings of the 54th Battery Conference, 2F27, p407, 2013 K. Chihara et al., Electrochim. Acta, 110, 240, 2013 Toshifumi Oshima et al., "Characteristics of sodium secondary battery of phthalic acid organic cathode", 50th Chemistry Branch Joint Kyushu Conference, 2_4.083, 2013

  However, these organic electrode active materials are exclusively used for non-aqueous electrolytes, and the organic electrode active materials used for aqueous electrolytes are not yet known. In addition, these organic electrode active materials have sufficient charge / discharge characteristics as a secondary battery except that disodium rhodizonate described in Non-Patent Document 7 is non-aqueous and exhibits a reversible capacity of 300 mAh / g. Not shown.

  The present invention has been proposed in order to solve the above-described problems. An electrode active material containing an organic compound, which can construct a water-based electrolyte secondary battery and can exhibit excellent charge / discharge characteristics and cycle characteristics, is provided. It is to provide.

  As a result of diligent research, the present inventors have developed an electrode active material made of an organic compound capable of constructing a water-based electrolyte secondary battery, and an electrode active material capable of exhibiting charge / discharge characteristics and cycle characteristics superior to those of the prior art. Newly found. Furthermore, it has been found that a water-based electrolyte secondary battery exhibiting high charge / discharge characteristics can be constructed by selecting and combining this electrode active material and a known counter electrode.

  Thus, according to the present invention, an organic compound having a structure in which a cyclohexane ring and / or a benzene ring is condensed to a pyrazine ring, wherein the cyclohexane ring and / or the benzene ring is an OX group (X is H, Na, Li). An electrode active material for a secondary battery is provided, which includes an organic compound that may be substituted with any one of, ½ Mg, or none.

(A) An example of the layer structure of the water-system sodium ion secondary battery containing the electrode active material which concerns on this invention is shown. (B) (c) shows the results ((b) ex situ XRD, (c) ex situ FT-IR) regarding the structural change accompanying charge / discharge of the electrode active material (compound 1-a-1) according to the present invention. (Example 1). (A) (b) Charging / discharging curve (voltage range: (a) -0.5 to 0.5 V, (a) when the electrode active material according to the present invention (compound 1-a-1) is used in an aqueous sodium ion secondary battery, b) -0.8 to 0.5 V) (Example 1). (C) Cycle characteristics when the electrode active material according to the present invention (compound 1-a-1) is used in an aqueous sodium ion secondary battery are shown (Example 1). (A) The charge / discharge curve (voltage range: -0.8-0.5V) at the time of using the electrode active material which concerns on this invention (compound 1-b-1) for a water-system sodium ion secondary battery is shown (Example 2). . (B) Cycle characteristics when the electrode active material according to the present invention (compound 1-b-1) is used in an aqueous sodium ion secondary battery are shown (Example 2). (C) The charging / discharging curve (voltage range: -0.8-0.5V) at the time of using the electrode active material which concerns on this invention (compound 1-c) for an aqueous sodium ion secondary battery is shown (Example 3). (A) (b) Charge / discharge curve (voltage range: (a) -0.5 to 0.5 V, (b) when the electrode active material (compound 2-1) according to the present invention is used in an aqueous sodium ion secondary battery -0.8 to 0.5 V) (Example 4). (C) Cycle characteristics when the electrode active material according to the present invention (Compound 2-1) is used in an aqueous sodium ion secondary battery are shown (Example 4). (A) (b) Charge / discharge curve (voltage range: (a) -0.8 to 0.5 V, (b) when the electrode active material (compound 3-1) according to the present invention is used in an aqueous sodium ion secondary battery -0.9 to 0.5 V) (Example 5). (C) Cycle characteristics when the electrode active material according to the present invention (Compound 3-1) is used in an aqueous sodium ion secondary battery are shown (Example 5). (A) The charging / discharging curve (voltage range: -0.8-0.5V) at the time of using the electrode active material (compound 4-1) which concerns on this invention for an aqueous sodium ion secondary battery is shown (Example 6). (B) Charging / discharging curve when the electrode active material (compound 5) according to the present invention is used in an aqueous sodium ion secondary battery (voltage range: (a) -0.8 to 0.5 V, (b) -0.9 to 0.5 V (Example 7). (C) Cycle characteristics when the electrode active material (compound 5) according to the present invention is used in an aqueous sodium ion secondary battery are shown (Example 7). (D) (e) The results ((d) ex situ XRD, (e) ex situ FT-IR) of the structural change accompanying charge / discharge of the electrode active material (compound 5) according to the present invention are shown (Example 7). ). (A) The charging / discharging curve (voltage range: -0.15-1.7V) at the time of using the electrode active material which concerns on this invention (compound 6-1) for a water-system sodium ion secondary battery is shown (Example 8). (B) Cycle characteristics when the electrode active material according to the present invention (Compound 6-1) is used in an aqueous sodium ion secondary battery are shown (Example 8). (A) The charge / discharge curve (voltage range: -0.8-0.6V) at the time of using the electrode active material which concerns on this invention (compound 1-a-1) for a water-system magnesium ion secondary battery is shown (Example 9). . (B) The charge / discharge curve (voltage range: -0.8-0.7V) at the time of using the electrode active material (compound 1-b-1) which concerns on this invention for an aqueous | water-based magnesium ion secondary battery is shown (Example 10). . (A) The charging / discharging curve (voltage range: -0.8-0.6V) at the time of using the electrode active material (compound 1-c) which concerns on this invention for a water-system magnesium ion secondary battery is shown (Example 11). (B) The charging / discharging curve (voltage range: -0.8-0.6V) at the time of using the electrode active material which concerns on this invention (compound 2-1) for a water-system magnesium ion secondary battery is shown (Example 12). The charging / discharging curve (voltage range: -0.8-0.6V) at the time of using the electrode active material which concerns on this invention (compound 5) for a water-system magnesium ion secondary battery is shown (Example 13).

  The electrode active material according to the present invention is an organic compound having a structure in which a cyclohexane ring and / or a benzene ring are condensed to a pyrazine ring, and the cyclohexane ring and / or the benzene ring is an OX group (X is H, Na, It is characterized by containing an organic compound which may be substituted with Li, 1 / 2Mg, or none).

  Although the number of the pyrazine rings which comprise the said organic compound contained in the electrode active material which concerns on this application is not specifically limited, For example, it can be set to 1-3. Although it does not specifically limit about the number of a cyclohexane ring, For example, it can be set as 0-1. The number of benzene rings is not particularly limited, but may be 1 to 3.

  The OX group is any one of an OH group, an ONa group, an OLi group, an O (1 / 2Mg) group, or an O group (oxo group). Such an OX group is preferably included as a substituent in a part of the organic compound constituting the electrode active material according to the present invention, but it is not always necessary. When the OX group is contained in the organic compound, the number is preferably 2 to 4, and can be 2 or 4, for example.

  Therefore, the organic compound constituting the electrode active material according to the present invention can be selected from the following, for example.

  When the organic compound contains an OX group, it has an OH group having a high affinity with an aqueous solution (aqueous electrolyte) and a C═O bond from the viewpoint of obtaining excellent battery characteristics as a secondary battery. O group (oxo group) is more preferable. Therefore, the organic compound constituting the electrode active material according to the present invention is more preferably one of the following organic compounds.

  Among the above organic compounds, a compound having a structure in which a plurality of rings are condensed in series as a whole (so-called acene compound) is a compound having a structure in which a plurality of rings are bent in a whole in a non-series configuration ( It is more preferable to use the following azaacene compounds because charge / discharge characteristics superior to those of so-called non-acene compounds) can be obtained.

  As used herein, an azaacene compound includes a heterocycle (pyrazine ring) containing a nitrogen atom in a ring constituting an acene compound having a structure in which a plurality of rings described above are condensed in series as a whole. Means the structure. That is, a plurality of rings composed of a benzene ring (essential), a pyrazine ring (essential), and a cyclohexane ring (arbitrary) constituting the organic compound have a structure condensed in series as a whole. It means that

  Any of these azaacene compounds exhibit excellent battery characteristics as electrode active materials for aqueous sodium ion secondary batteries. Among these, from the viewpoint of exhibiting excellent charge / discharge characteristics, compound 1-a-1 (tetraazapentacenedione) and compound 2-1 (1,4-diazaanthraquinone: DAAQ having two oxo groups ) Is more preferred. Since these compounds have two oxo groups, they can be particularly referred to as azaacenedione compounds. Furthermore, among these azaacenedione compounds, compound 1-a-1 is particularly preferable because it can exhibit better charge / discharge characteristics.

Although the mechanism of the excellent charge / discharge characteristics of the azaacenedione compound as the electrode active material according to the present invention has not been elucidated in detail, the adjacent C═N two in the azaacenedione compound is not yet elucidated. When the double bond is interlocked (in some compounds, including the C = O double bond), it is reversibly bound to and dissociated with a divalent ion (for example, magnesium ion), so that good redox activity is divalent. It is assumed that it is expressed by a cation.

The electrode active material according to the present invention can be applied to the negative electrode of an aqueous electrolyte secondary battery (particularly, an aqueous lithium ion secondary battery, an aqueous sodium ion secondary battery, and an aqueous magnesium ion secondary battery). The electrode active material which concerns on this invention has the outstanding characteristic that it can utilize as both a positive electrode active material and a negative electrode active material by selecting the kind of suitable counter electrode (counter electrode). There are not many reports on these water-based electrolyte secondary batteries at present. For example, regarding the negative electrode of the aqueous sodium secondary battery, there are only reports on NaTi ₂ (PO 4) ₃ and activated carbon that is charged and discharged by an adsorption reaction, and it has not been put into practical use.

  Thus, although the mechanism is not elucidated in detail about the high versatility and the outstanding characteristic which the electrode active material which concerns on this invention shows, the following things are guessed. That is, the electrode active material according to the present invention exhibits a multi-electron reaction peculiar to an organic compound, is hydrophobic, and is hardly soluble in an electrolyte solution. Even in the case of a water-based electrolyte secondary battery that is limited to driving in the water, a sufficient operating voltage is obtained, and it is assumed that a sufficient charge / discharge operation can be performed even in a low voltage region. . In addition, there is no report on practical use of water-based magnesium ion secondary batteries at present, but since the valence of magnesium ions is divalent, the charge / discharge is higher than that of monovalent lithium ions and sodium ions. Characteristics are expected.

  As described above, the electrode active material according to the present invention is preferably applied to a secondary battery of an aqueous electrolyte, but may also be applied to a secondary battery of a non-aqueous electrolyte. Is possible.

{Method for producing electrode active material according to the present invention}
The electrode active material according to the present invention can be produced using a known method. For example, in order to obtain the above-mentioned compound 1-a, known literature (Chem. Eur. J. 2009, 15, 3965) and known literature (J. Chem. Soc. 1951, 3211) or known literature (Chem. Comm. 2010, 46, 2977) can be synthesized with reference to known literature (Chem. Eur. J. 2009, 15, 3965) and known literature (J. Chem. Soc. 1951, 3211). Accordingly, compound 1-a can be synthesized by dehydration condensation of o-phenylenediamine and 2,5-dihydroxy-1,4-benzoquinone and subsequent oxidation reaction. In addition, for example, Compound 2 can be synthesized according to known literature (Z. Naturforsch. 1991, 46b, 326). As for Compound 5, a commercially available product may be used as it is.

  Thus, the electrode active material according to the present invention is obtained by a known production method and has an excellent feature that a high energy density is obtained. Although the mechanism that exhibits such an excellent effect has not been elucidated in detail, in the charge / discharge reaction, a C═N bond contained in the electrode active material according to the present invention, a bond between an OX group and carbon (for example, The presence of C═O bond, C—OH bond, etc.) facilitates the movement of electrons, and it is presumed that the oxidation-reduction reaction related to charge / discharge proceeds efficiently.

  In one embodiment, the electrode active material according to the present invention may be used as it is as a positive electrode or a negative electrode of an aqueous sodium ion secondary battery. In order to improve the conductivity (rate characteristic) of the electrode, a known conductive material is used. A complex may be formed. In particular, it is preferable to add and mix a carbon source.

  That is, according to the present invention, from the viewpoint of improving the rate characteristics, the electrode active material obtained above can be carbon coated by pulverizing and mixing together with carbon fine particles in an inert atmosphere. As the inert atmosphere, vacuum, nitrogen gas, argon gas, or the like can be used. For example, argon gas can be used.

  Such addition of the carbon source may be performed in a plurality of times (for example, in two stages). In this case, the primary aim is often pulverization / mixing in the first stage and carbon coating in the second stage. In the first stage, acetylene black, graphite, carbon nanotube, or the like can be used as the carbon source, and among these, acetylene black is particularly preferable from the viewpoint of ease of handling. In the second stage, furnace black, channel black, acetylene black, ketjen black, thermal black, and the like can be used, but acetylene black is preferred because of its high conductivity when used as an electrode. (For example, see the examples below)

  According to the present invention, an aqueous sodium ion secondary battery electrode obtained as described above is provided.

FIG. 1A is a diagram illustrating an example of a layer configuration of an aqueous sodium ion secondary battery as one embodiment of the present invention, and is a diagram schematically illustrating a cross section cut in a stacking direction. The aqueous electrolyte secondary battery according to the present invention is not necessarily limited to this example.
An aqueous electrolyte secondary battery 10 is sandwiched between a positive electrode 6 including a positive electrode active material layer 2 and a positive electrode current collector 4, a negative electrode 7 including a negative electrode active material layer 3 and a negative electrode current collector 5, and a positive electrode 6 and a negative electrode 7. An electrolyte layer 1 is provided.

Thus, in one aspect of the present invention, an aqueous electrolyte secondary battery including a positive electrode and a negative electrode containing an electrode active material and an electrolyte interposed therebetween is provided, and exhibits high energy density. Provided is an aqueous sodium ion secondary battery that has high energy density, can be manufactured at low cost, and is easy to handle.

  The electrode used in the present invention preferably comprises an electrode active material layer containing the above-described electrode active material, and in addition to this, an electrode current collector, and an electrode connected to the electrode current collector Provide leads.

[Current collector]
As the current collector, a conductor such as aluminum, titanium, nickel, stainless steel, or copper is used. Examples of the shape of the current collector include a foil shape, a net shape, and a porous shape. Among these, aluminum foil is preferable because it is stable at the positive electrode operating potential of the secondary battery, easily processed into a thin film, and inexpensive.

[binder]
As the binder, a thermoplastic resin is used. Specifically, polyvinylidene fluoride (hereinafter sometimes referred to as “PVDF”), polytetrafluoroethylene (hereinafter sometimes referred to as “PTFE”). Fluorine resins such as tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer, hexafluoropropylene / vinylidene fluoride copolymer and tetrafluoroethylene / perfluorovinyl ether copolymer; polyethylene And polyolefin resins such as polypropylene. These thermoplastic resins are used alone or in combination of two or more.

[Method for producing electrode for aqueous electrolyte secondary battery]
The electrode for an aqueous electrolyte secondary battery is manufactured by supporting (stacking) an electrode mixture containing an active material, a conductive material, and a binder on a current collector.
As a method for supporting the electrode mixture on the current collector, (1) a method of pressure-molding the electrode mixture, (2) mixing the organic solvent and the electrode mixture to prepare an electrode mixture paste The paste is applied to a current collector, and the paste applied to the current collector is dried and then fixed by pressing or the like.

  Examples of the method of applying the paste to the current collector include a slit die coating method, a screen coating method, a curtain coating method, a knife coating method, a gravure coating method, and an electrostatic spray method. In the present invention, a plurality of these coating methods may be used in combination.

The electrode (positive electrode or negative electrode) facing the electrode of the present invention can be selected in the required characteristics as an aqueous or non-aqueous lithium, sodium, or magnesium secondary battery.

[Aqueous electrolyte]
The aqueous electrolyte in the present invention is an aqueous solution made of a substance containing alkali ions, and mainly contains sodium ions, magnesium ions, and lithium ions as alkali ions.

[Non-aqueous electrolyte]
The non-aqueous electrolyte in the present invention is a liquid or solid made of a substance containing alkali ions, and may contain other alkali ions as the alkali ions.

  The content ratio of sodium ions and magnesium ions contained in the aqueous electrolyte is preferably 50% by mass or more of the total alkali ions. From the battery characteristics, it is desirable to have more.

The aqueous electrolyte in the present invention is usually used as an aqueous electrolytic solution containing an electrolyte and an aqueous solvent.
As the electrolyte, MgSO ₄ or Na ₂ SO ₄ can be used. In addition, as a non-aqueous electrolyte solution, for _{example, LiClO 4, LiPF 6, LiAsF} 6, LiSbF 6, LiBF 4, LiCF 3 SO 3, LiN (SO 2 CF 3) 2, lower aliphatic carboxylic acid lithium salts, LiAlCl ₄ Is mentioned. You may use the mixture which mixed 2 or more types for these.

  In the present invention, in addition to the aqueous electrolyte, when an organic solvent is used for the electrolyte, for example, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, isopropyl methyl carbonate, vinylene carbonate, 4-trifluoromethyl. Carbonates such as -1,3-dioxolan-2-one and 1,2-di (methoxycarbonyloxy) ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropyl methyl ether, 2,2 , 3,3-tetrafluoropropyldifluoromethyl ether, ethers such as tetrahydrofuran, 2-methyltetrahydrofuran; esters such as methyl formate, methyl acetate, γ-butyrolactone; acetonitrile, butyroni Nitriles such as ril; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Carbamates such as 3-methyl-2-oxazolidone; and sulfolane, dimethyl sulfoxide, 1,3-propane sultone and the like Sulfur compounds; or those obtained by further introducing a fluorine substituent into the organic solvent are used.

  The aqueous sodium ion secondary battery obtained in this way has a large discharge capacity maintenance rate when it is repeatedly charged and discharged, compared to the conventional sodium ion secondary battery, due to the excellent battery characteristics obtained in the half cell, Excellent charge / discharge cycle characteristics. Furthermore, the production | generation of sodium dendrite can also be suppressed and it becomes excellent in the stability as a secondary battery.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

(Manufacture of electrode active material for aqueous sodium ion secondary battery)
Hereinafter, in Examples 1-8, the electrode active material for aqueous sodium ion secondary batteries according to the present invention was manufactured, and the battery characteristics as secondary batteries were confirmed.

Example 1
(Production of electrode composed of compound 1-a-1)
As an electrode active material according to the present invention, compound 1-a-1 was prepared according to known literature (Chem. Eur. J. 2009, 15, 3965) and known literature (Chem. Comm. 2010, 46, 2977). It was synthesized by dehydration condensation of o-phenylenediamine (manufactured by Kanto Chemical Co., Inc.) and 2,5-dihydroxy-1,4-benzoquinone (AlfaAeser) followed by oxidation reaction. Using this compound 1-a-1, acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd.) as the conductive material, and polytetrafluoroethylene (manufactured by Daikin Co., Ltd.) as the binder, Each was weighed so that the composition was: conductive material: binder = 50: 45: 5. Thereafter, the compound 1-a-1 and the conductive material were sufficiently mixed in an agate mortar, a binder was further added, and the mixture was continuously mixed to be uniform, and then the mixture was thinly spread to form a sheet. The sheet was sufficiently pressure-bonded to a stainless steel mesh as a current collector by a hand press, and further placed in a dryer and sufficiently dried to obtain a first electrode (negative electrode). The battery was assembled in a glove box with an argon atmosphere.

<Measurement of secondary battery characteristics>
The aqueous sodium ion secondary battery using the electrode active material (compound 1-a-1) according to the present invention was measured using an aqueous Na ₂ SO ₄ solution as the aqueous electrolyte. In this charge / discharge measurement, 20 ml of 2M Na ₂ SO ₄ / H ₂ O was used as the electrolyte, 16 mm diameter zinc metal (manufactured by Sank Metal Co., Ltd.) as the counter electrode, and a silver-silver chloride electrode as the reference electrode (BAS Co., Ltd.) In a beaker cell manufactured by using a company, a constant current mode of a constant charge / discharge current density (current density: 0.1 mA / cm ² ) was set and performed at room temperature (25 ° C.).

  With regard to structural changes associated with charge and discharge, the ex situ XRD results obtained by X-ray diffraction measurement using CuKα rays (using Rigaku TTRIII) are shown in FIG. 1B, and the ex situ FT-IR results are shown in FIG. c). From these results, no significant change was observed.

2A and 2B show the charge / discharge characteristics of compound 1-a-1 with respect to the zinc counter electrode (voltage ranges: (a) -0.5 to 0.5 V, (b) -0.8 to 0.5 V). For the first reversible capacity, 131 mAh / degree of reaction of about 1.5 Na and 2.7 Na respectively in the voltage ranges -0.5 to 0.5 V and -0.8 to 0.5 V with respect to the silver-silver chloride reference electrode. g, 230 mAh / g was observed, and the voltage at the flat portion of the discharge was 2.5 V and 2.3 V in terms of Na ⁺ / Na. Further, as shown in FIG. 2 (c), since the charge / discharge capacity was stably maintained even when the number of cycles exceeded 25, it became clear that the aqueous sodium ion electrolyte exhibited good cycle characteristics.

(Example 2)
(Production of electrode composed of compound 1-b-1)
As an electrode active material according to the present invention, compound 1-b-1 was mixed with o-phenylenediamine (manufactured by Kanto Chemical Co., Ltd.) and rhodizone acid dihydrate (in accordance with known literature (Tetrahedron 1969, 25, 3935) ( AlfaAeser) was synthesized by dehydration condensation followed by oxidation reaction. Using this compound 1-b-1, acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd.) as the conductive material, and polytetrafluoroethylene (manufactured by Daikin) as the binder, these are the mass ratios of compound 1-b-1 Each was weighed so that the composition was: conductive material: binder = 50: 45: 5. Thereafter, the same procedure as in Example 1 was performed.

<Measurement of secondary battery characteristics>
Under the same conditions as in Example 1, charge / discharge measurement of an aqueous sodium ion secondary battery using the electrode active material (Compound 1-b-1) according to the present invention was performed.
FIG. 3A shows the charge / discharge characteristics of compound 1-b-1 with respect to the zinc counter electrode (voltage range: -0.8 to 0.5 V). For the first reversible capacity, 265 mAh / g was observed. In addition, as shown in FIG. 3B, the charge / discharge capacity was stably maintained even after exceeding 15 cycles, and thus it became clear that the aqueous sodium ion electrolyte exhibited good cycle characteristics.

(Example 3)
(Production of electrode composed of compound 1-c)
As an electrode active material according to the present invention, Compound 1-c was subjected to dehydration condensation of o-phenylenediamine (manufactured by Kanto Chemical Co., Inc.) and Compound 1-b-1 according to known literature (Tetrahedron 1969, 25, 3935). Was synthesized. Thereafter, the same procedure as in Example 1 was performed.

<Measurement of secondary battery characteristics>
Under the same conditions as in Example 1 above, charge / discharge measurement of an aqueous sodium ion secondary battery using the electrode active material (Compound 1-c) according to the present invention was performed.
FIG. 3C shows the charge / discharge characteristics of the compound 1-c with respect to the zinc counter electrode (voltage range: −0.8 to 0.5 V). For the first reversible capacity, 240 mAh / g was observed.

Example 4
(Production of electrode composed of compound 2-1)
As an electrode active material according to the present invention, compound 2-1 was prepared according to known literature (Z. Naturforsch. 1991, 46b, 326) according to 2,3-dichloro-1,4-naphthoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.). ) Was converted to an amino group and then synthesized by dehydration condensation with glyoxal trimer dihydrate (Aldrich). Using this compound 2-1 and acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd.) as a conductive material, and polytetrafluoroethylene (manufactured by Daikin Co., Ltd.) as a binder, these are in a mass ratio. Each was weighed to have a composition of binder = 50: 45: 5. Thereafter, the same procedure as in Example 1 was performed.

<Measurement of secondary battery characteristics>
4A and 4B show the charge / discharge characteristics of Compound 2-1 with respect to the zinc counter electrode (voltage range: (a) -0.5 to 0.5 V, (b) -0.8 to 0.5 V). As for the initial reversible capacity, 92 mAh / g and 185 mAh / g were observed in the voltage ranges of −0.5 to 0.5 V and −0.8 to 0.5 V, respectively. In addition, as shown in FIG. 4 (c), in the voltage range of −0.5 to 0.5V, the charge / discharge capacity was stably maintained even after exceeding 40 cycles. It became clear to show the characteristics.

(Example 5)
(Manufacture of electrode composed of compound 3-1)
As an electrode active material according to the present invention, compound 3-1 was prepared according to known literature (Tetrahedron 1969, 25, 3935), o-phenylenediamine (manufactured by Kanto Chemical Co., Inc.) and rosinic acid dihydrate (AlfaAeser). Was synthesized by dehydration condensation. Thereafter, the same procedure as in Example 1 was performed.

<Measurement of secondary battery characteristics>
5A and 5B show the charge / discharge characteristics of Compound 3-1 with respect to the zinc counter electrode (voltage range: (a) -0.8 to 0.5 V, (b) -0.9 to 0.5 V). As for the initial reversible capacity, 290 mAh / g and 480 mAh / g were observed in the voltage ranges of −0.8 to 0.5 V and −0.9 to 0.5 V, respectively. Moreover, as shown in FIG.5 (c), since charging / discharging capacity was stably maintained even if it exceeded 30 cycles, it became clear that a water-system sodium ion electrolyte solution shows a favorable cycle characteristic.

(Example 6)
(Manufacture of electrodes consisting of compound 4-1)
As an electrode active material according to the present invention, compound 4-1 was prepared according to known literature (Tetrahedron 1969, 25, 3935), o-phenylenediamine (manufactured by Kanto Chemical Co., Inc.) and tetrahydroxy-1,4-benzoquinone ( Synthesized by Tokyo Kasei Kogyo Co., Ltd.) and subsequent oxidation reaction. Thereafter, the same procedure as in Example 1 was performed.

<Measurement of secondary battery characteristics>
FIG. 6A shows the charge / discharge characteristics of Compound 4-1 with respect to the zinc counter electrode (voltage range: −0.8 to 0.5 V). With respect to the first reversible capacity, 300 mAh / g was observed, and thus it became clear that the aqueous sodium ion electrolyte exhibited good charge / discharge characteristics.

(Example 7)
(Manufacture of electrode composed of compound 5)
As the electrode active material according to the present invention, Compound 5 (manufactured by Tokyo Chemical Industry Co., Ltd.) was used, and the subsequent procedure was the same as in Example 1.

<Measurement of secondary battery characteristics>
Under the same conditions as in Example 1, charge / discharge measurement of an aqueous sodium ion secondary battery using the electrode active material (Compound 1-b-1) according to the present invention was performed.
FIG. 6B shows the charge / discharge characteristics of the compound 1-b-1 with respect to the zinc counter electrode (voltage range: −0.8 to 0.5 V). For the first reversible capacity, 350 mAh / g was observed. Moreover, as shown in FIG.6 (c), since charging / discharging capacity was stably maintained even if it exceeded 35 cycles, it became clear that a water-system sodium ion electrolyte solution shows a favorable cycle characteristic.

  About the structural change accompanying charging / discharging, the ex situ XRD result obtained by X-ray-diffraction measurement (using Rigaku TTRIII) using a CuK (alpha) ray is shown in FIG.6 (d). When the structural change of the compound 5 accompanying charging / discharging was observed, it was confirmed that the structure was greatly changed at the time of 2Na discharge but returned to the initial structure again at the charging end. This suggests that compound 5 is charged and discharged in a two-phase reaction. Moreover, the ex situ FT-IR result is shown in FIG.6 (e) about the structural change accompanying charging / discharging. From the FT-IR measurement results, remarkable changes were observed during discharge, especially around 1300 and 1500, but it was confirmed that the IR profile was restored to the initial state with good reversibility by charging.

(Example 8)
(Manufacture of electrodes consisting of compound 6-1)
As an electrode active material according to the present invention, compound 6-1 was prepared according to known literature (Tetrahedron 1969, 25, 3935), o-phenylenediamine (manufactured by Kanto Chemical Co., Inc.) and tetrahydroxy-1,4-benzoquinone ( Synthesized by dehydration condensation of Tokyo Chemical Industry Co., Ltd.). Thereafter, the same procedure as in Example 1 was performed.

<Measurement of secondary battery characteristics>
Under the same conditions as in Example 1 above, charge / discharge measurement of an aqueous sodium ion secondary battery using the electrode active material (Compound 6-1) according to the present invention was performed.
FIG. 7A shows the charge / discharge characteristics of Compound 6-1 with respect to the zinc counter electrode (voltage range: −0.15 to 1.7 V). For the first reversible capacity, 220 mAh / g was observed. Further, as shown in FIG. 7 (b), the charge / discharge capacity was stably maintained even after exceeding 25 cycles, and thus it became clear that the aqueous sodium ion electrolyte exhibited good cycle characteristics.

(Measurement as an electrode active material for aqueous magnesium ion secondary batteries)
In the following examples, the aqueous magnesium ion according to the present invention is obtained using the compound 1-a-1, compound 1-b-1, compound c, compound 2-1, compound 5 and compound c obtained above. The charge / discharge characteristics as an electrode active material for a secondary battery were confirmed.

Example 9
(Electrode consisting of compound 1-a-1)
<Measurement of secondary battery characteristics>
Using an aqueous MgSO ₄ solution as the aqueous electrolyte, charge / discharge measurement of an aqueous magnesium ion secondary battery using the electrode active material (compound 1-a-1) according to the present invention was performed. In this charge / discharge measurement, 20 ml of 3M MgSO ₄ / H ₂ O is used for the electrolyte, 16 mm diameter zinc metal (made by Sank Metal) is used for the counter electrode, and a silver-silver chloride electrode (made by BAS Co., Ltd.) is used for the reference electrode. ) Was set to a constant current mode at a constant charge / discharge current density (current density: 0.2 mA / cm ² ) and performed at room temperature (25 ° C.).
FIG. 8A shows the charge / discharge characteristics of Compound 1-a-1 with respect to the zinc counter electrode (voltage range: −0.8 to 0.6 V). For the initial reversible capacity, 280 mAh / g was observed. Moreover, the outstanding charge / discharge characteristic that there exists a 3.6 electronic reaction in charging / discharging was confirmed.

(Example 10)
(Electrode consisting of compound 1-b-1)
<Measurement of secondary battery characteristics>
Under the same conditions as in Example 9 above, charge / discharge measurement of an aqueous magnesium ion secondary battery using the electrode active material (Compound 1-b-1) according to the present invention was performed.
FIG. 8B shows the charge / discharge characteristics of the compound 1-b-1 with respect to the zinc counter electrode (voltage range: −0.8 to 0.7 V). For the first reversible capacity, 195 mAh / g was observed. Moreover, the outstanding charging / discharging characteristic of having 2.6 electronic reaction in charging / discharging was confirmed.

(Example 11)
(Electrode consisting of compound 1-c)
<Measurement of secondary battery characteristics>
Under the same conditions as in Example 9 above, charge / discharge measurement of an aqueous magnesium ion secondary battery using the electrode active material (Compound 1-c) according to the present invention was performed. The charge / discharge characteristics of compound 1-c with respect to the zinc counter electrode are shown in FIG. 9A (voltage range: -0.8 to 0.6 V). For the first reversible capacity, 250 mAh / g was observed.

(Example 12)
(Electrode consisting of Compound 2-1)
<Measurement of secondary battery characteristics>
Under the same conditions as in Example 9 above, charge / discharge measurement of an aqueous magnesium ion secondary battery using the electrode active material (Compound 2-1: DAAQ) according to the present invention was performed.
FIG. 9B shows the charge / discharge characteristics of Compound 2-1 with respect to the zinc counter electrode (voltage range: −0.8 to 0.6 V). For the first reversible capacity, 208 mAh / g was observed.

(Example 13)
(Electrode consisting of Compound 5)
<Measurement of secondary battery characteristics>
Under the same conditions as in Example 9 above, charge / discharge measurement of a water-based magnesium ion secondary battery using the electrode active material (Compound 5) according to the present invention was performed.
FIG. 10 shows the charge / discharge characteristics of Compound 5 with respect to the zinc counter electrode (voltage range: −0.8 to 0.6 V). It was confirmed that the charge / discharge capacity increased each time 10 cycles, 20 cycles and 30 cycles were added, and 93 mAh / g at 40 cycles although not shown in the figure.

In the above examples, sufficient battery characteristics are obtained in the half cell, and therefore, by selecting the opposite electrode, good battery characteristics can be obtained as a full cell secondary battery as described above. is there.

DESCRIPTION OF SYMBOLS 1 Electrolyte layer 2 Positive electrode layer 3 Negative electrode layer 4 Positive electrode collector 5 Negative electrode collector 6 Positive electrode 7 Negative electrode 10 Aqueous electrolyte secondary battery

Claims (6)

  An organic compound having a structure in which a cyclohexane ring and / or a benzene ring are condensed to a pyrazine ring, wherein the cyclohexane ring and / or benzene ring is an OX group (X is H, Na, Li, 1 / 2Mg, or none) An electrode active material for a secondary battery comprising an organic compound which may be substituted with any one). The electrode active material according to claim 1, wherein the organic compound is selected from the following.

The electrode active material according to claim 2, wherein the organic compound is selected from the following.

The electrode active material according to claim 3, wherein the organic compound is selected from the following azaacene compounds.

  An aqueous sodium ion secondary battery comprising the electrode active material according to any one of claims 1 to 4 on a positive electrode or a negative electrode, and a sodium aqueous solution as an electrolyte.   A water-based magnesium ion secondary battery comprising the electrode active material according to any one of claims 1 to 4 on a positive electrode or a negative electrode, and a magnesium aqueous solution as an electrolyte.

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