JP2008288022A - Electrode active material for energy storage device, and energy storage device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve a problem that, although various studies have been hitherto made for using as an electrode active material, an organic compound, with which weight saving and higher energy density of an energy storage device can be expected, repetition characteristics tend to be deteriorated in accordance with the charge/discharge cycles. <P>SOLUTION: An allene compound (1) capable of forming a conjugate structure by π electrons on an molecular plane is used as an electrode active material. The compound will not change its structure before and after charge/discharge reaction, so that material deterioration due to charge/discharge cycles scarcely occurs if the compound is used for the electrode active material, and an energy storage device with excellent repetition characteristics can be obtained. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electrode active material for an electricity storage device and an electricity storage device.

  Conventionally, chargeable / dischargeable power storage devices are used for power supplies such as hybrid vehicles, mobile communication devices, portable electronic devices, and uninterruptible power supplies that are driven by using two types of energy, gasoline and electricity. It has been. Recently, with the remarkable spread of hybrid vehicles and electronic devices, the demand for higher performance of power storage devices has become very large. Specifically, higher performance is desired for characteristics such as capacity, output, and repetition characteristics. Various studies and proposals have been made for improving the performance of power storage devices. In particular, an increase in energy density of an electrode active material such as a positive electrode active material and a negative electrode active material directly leads to an increase in energy of the electricity storage device itself. For this reason, efforts have been actively made on material development for electrode active materials.

For example, as an electrode active material, a general formula
M ⁺ -S-R-S-M ⁺
[Wherein, R represents a divalent aliphatic organic group or a divalent aromatic organic group. M ⁺ represents a proton or a metal cation. ]
(See, for example, Patent Document 1 and Patent Document 2). This sulfur-containing organic compound forms a disulfide bond by an electrochemical oxidation reaction and bonds to each other.
M ⁺ − ⁻ S−R−S−S−R−S−S−R−S ⁻ −M ⁺
[Wherein, R and M ⁺ are the same as above. ]
It becomes a trimer represented by. In this trimer, the disulfide bond is cleaved by an electrochemical reduction reaction, and the original sulfur-containing organic compound is obtained. As described above, the techniques disclosed in Patent Documents 1 and 2 perform oxidation-reduction reactions using formation and cleavage of disulfide bonds. However, since disulfide bonds are less frequently recombined after cleavage, there is a problem that sulfur-containing organic compounds have low repeatability. Further, the fact that the frequency of recombination after cleavage is low indicates that the reaction site decreases each time the cleavage is repeated. Therefore, although the sulfur-containing organic compound theoretically has a high energy density, the high energy density cannot be maintained for a long time in practical use. It has also been proposed to use sulfur as an electrode active material (see, for example, Patent Document 3). However, this technique also has the problem of low repeatability because it utilizes disulfide bond formation and cleavage.

  Further, as an electrode active material, a tetrathiafulvalene compound (hereinafter referred to as “TTF compound”), which is an organic compound having a π-electron conjugated cloud, has been proposed (see, for example, Patent Document 4 and Patent Document 5). The TTF compounds described in Patent Documents 4 and 5 have two sulfur-containing 5-membered heterocycles that are redox sites in the center of the molecular structure, and an aromatic ring having a π-electron conjugated cloud in the 5-membered heterocycle. It has a substituted chemical structure. In addition, the TTF compound performs a reversible electrochemical reaction at high speed and has a high energy density of 260 mAh / g. However, since the TTF compound is soluble in an organic solvent, there is a problem that when the TTF compound is used as an electrode active material of an electricity storage device, it dissolves in an electrolyte containing the organic solvent. In order to eliminate or alleviate this problem, high molecular weight, derivatization, and the like are performed. Specific examples of the method include introduction of a substituent such as an ethylenedithio group into a TTF compound. In general, introduction of a substituent dramatically changes the physical properties of the organic compound. However, in conventional TTF compounds, the introduction position of the substituent is limited to a five-membered ring that is a redox site. Properties necessary for the reaction may be deteriorated.

US Pat. No. 4,833,048 Japanese Patent No. 2715778 US Pat. No. 5,523,179 JP 2004-111374 A JP 2004-342605 A

  An object of the present invention is to provide an organic compound useful as an electrode active material for an electricity storage device and an electricity storage device containing the organic compound as an electrode active material, exhibiting high capacity, high output, and good long-term repeatability. is there.

In the research process for solving the above-mentioned problems, the present inventors first focused on an organic compound capable of performing a redox reaction. Here, the organic compound capable of performing the oxidation-reduction reaction is an organic compound that can form a chemically stable oxidant and reductant that cause a change in valence along with the oxidation-reduction reaction and hardly undergo decomposition or the like. .
In addition, what kind of oxidation-reduction reaction an organic compound capable of performing oxidation-reduction reaction becomes important. For example, an oxidation-reduction reaction using bond cleavage and recombination has a problem that the frequency of recombination is low and the repetition characteristics are low. In addition, in a redox reaction in which an oxidant and a reductant take a neutral state / radical state, it is necessary to form a chemically stable radical state. Although radical bodies are generally unstable, for example, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl is known as a compound that forms a stable radical state. In this compound, radicals are stabilized by arranging four sterically large methyl groups on both sides of the NO position, which is a site where radicals are generated. However, in this compound, four methyl groups that do not participate in the oxidation-reduction reaction are present in the vicinity of the radical generation site, and further, the radical generation site is limited to only the NO position, so it is difficult to increase the energy density. In order to increase the energy density, it is necessary to have a large number of radical generation sites.

  Therefore, the inventors focused on using electrons on the π-electron conjugated cloud for oxidation and reduction reactions, and further studied. For example, conductive polymer compounds such as polyaniline and polypyrrole are known as organic compounds having a π-electron conjugated cloud and performing a redox reaction. In these molecules, since the π-electron conjugated cloud is greatly spread in the molecule, the number of reaction electrons per unit unit (one aniline ring or one pyrrole ring) is 0.5 electron reaction or less. Therefore, in general, it can be said that a structure in which a π-electron conjugated cloud spreads is not suitable for increasing the energy density.

  Next, the inventors focused on an organic compound that performs an oxidation-reduction reaction in which both an oxidant and a reductant satisfy the Hückel rule, and further conducted intensive studies. As a result, an organic compound having a site containing an aromatic ring such as a benzene ring having a π-electron conjugated cloud at the center of the molecule and a redox site at both ends of the molecule and having a chemical structure different from that of a conventional TTF compound However, it discovered that it was useful as an electrode active material for electrical storage devices. Here, the redox site is a 5-membered heterocyclic group containing two sulfur atoms having a lone electron pair as a heteroatom. This organic compound has a very high energy density even though the aromatic ring having a π-electron conjugated cloud accounts for a large proportion in the molecule. Further, in this organic compound, derivatization is also achieved without reducing various physical properties necessary for the electrode active material by introducing a site containing an aromatic ring between two redox sites. That is, the present inventors have found that, when this organic compound is used as an electrode active material, an electricity storage device having high capacity and output and excellent long-term repeatability can be obtained, and the present invention has been completed.

〔式中、Ａは４価の芳香族基または４価のヘテロ芳香族基を示す。Ａで示される芳香族基およびヘテロ芳香族基は、置換基として、アルキル基、鎖状不飽和脂肪族基、環状不飽和脂肪族基、鎖状飽和脂肪族基、環状飽和脂肪族基、ハロゲン原子、窒素原子、酸素原子、硫黄原子およびシリコン原子よりなる群から選ばれる少なくとも１つの基を有していてもよい。Ｒ₁〜Ｒ₄は、それぞれ独立して、水素原子、フッ素原子、アルキル基またはアルコキシカルボニル基を示す。或いは、Ｒ₁およびＲ₂ならびにＲ₃およびＲ₄は、それぞれ独立して、互いに結合して芳香環を形成してもよい。また、Ｒ₁〜Ｒ₄で示されるアルキル基は、ハロゲン原子、窒素原子、酸素原子、硫黄原子およびシリコン原子よりなる群から選ばれる少なくとも１つの原子を含んでいてもよい。〕
で表されるアレン化合物（１）を電極活物質として含む蓄電デバイス用電極活物質に係る。 That is, the present invention has the general formula

[Wherein, A represents a tetravalent aromatic group or a tetravalent heteroaromatic group. The aromatic group and heteroaromatic group represented by A include, as a substituent, an alkyl group, a chain unsaturated aliphatic group, a cyclic unsaturated aliphatic group, a chain saturated aliphatic group, a cyclic saturated aliphatic group, a halogen You may have at least 1 group chosen from the group which consists of an atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a silicon atom. R _{1 to} R ₄ each independently represent a hydrogen atom, a fluorine atom, an alkyl group or an alkoxycarbonyl group. Alternatively, R ₁ and R ₂ and R ₃ and R ₄ may be independently bonded to each other to form an aromatic ring. Further, the alkyl group represented by R _{1 to} R ₄ may contain at least one atom selected from the group consisting of a halogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a silicon atom. ]
The electrode active material for electrical storage devices which contains the allene compound (1) represented by these as an electrode active material.

〔式中、Ｒ₁〜Ｒ₄は上記に同じ。Ａｒは、ベンゼン環またはベンゼン縮合環を示し、これらの環はそれぞれ置換基として低級アルキル基を有していてもよい。ｎは１以上の整数を示す。〕
で表されるアレン化合物（２）であることが好ましい。 The allene compound (1) has the general formula

[Wherein, R _{1 to} R ₄ are the same as above. Ar represents a benzene ring or a benzene condensed ring, and each of these rings may have a lower alkyl group as a substituent. n represents an integer of 1 or more. ]
It is preferable that it is an allene compound (2) represented by these.

〔式中、Ｒ₁〜Ｒ₄は上記に同じ。Ａ₁はアリーレン基を示す。Ａ₁で示されるアリーレン基は、置換基として、アルキル基、鎖状不飽和脂肪族基、環状不飽和脂肪族基、鎖状飽和脂肪族基、環状飽和脂肪族基、ハロゲン原子、窒素原子、酸素原子、硫黄原子およびシリコン原子よりなる群から選ばれる少なくとも１つの基を有していてもよい。〕
で表されるアレン化合物（３）であることが好ましい。 The allene compound (1) has the general formula

[Wherein, R _{1 to} R ₄ are the same as above. A ₁ represents an arylene group. The arylene group represented by A ₁ includes, as a substituent, an alkyl group, a chain unsaturated aliphatic group, a cyclic unsaturated aliphatic group, a chain saturated aliphatic group, a cyclic saturated aliphatic group, a halogen atom, a nitrogen atom, You may have at least 1 group chosen from the group which consists of an oxygen atom, a sulfur atom, and a silicon atom. ]
It is preferable that it is an allene compound (3) represented by these.

〔式中、Ｒ₁〜Ｒ₄は上記に同じ。は、それぞれ独立して、水素原子、フッ素原子、アルキル基またはアルコキシカルボニル基を示す。或いは、Ｒ₁およびＲ₂ならびにＲ₃およびＲ₄は、それぞれ独立して、互いに結合して芳香環を形成してもよい。Ｒ₅〜Ｒ₈は、それぞれ独立して、水素原子、アルキル基、アルコキシ基または基

（式中Ｒ₁およびＲ₂は上記に同じ。）を示す。〕
で表されるアレン化合物（４）であることが好ましい。 The allene compound (3) has the general formula

[Wherein, R _{1 to} R ₄ are the same as above. Each independently represents a hydrogen atom, a fluorine atom, an alkyl group or an alkoxycarbonyl group. Alternatively, R ₁ and R ₂ and R ₃ and R ₄ may be independently bonded to each other to form an aromatic ring. R _{5 to} R ₈ each independently represents a hydrogen atom, an alkyl group, an alkoxy group or a group

(Wherein R ₁ and R ₂ are the same as above). ]
It is preferable that it is an allene compound (4) represented by these.

〔式中、Ｒ₁〜Ｒ₄は上記に同じ。Ｒ₉〜Ｒ₁₂は、それぞれ独立して、水素原子、アルキル基またはアルコキシ基を示す。〕
で表されるアレン化合物（５）であることが好ましい。 The allene compound (3) has the general formula

[Wherein, R _{1 to} R ₄ are the same as above. R _{9 to} R ₁₂ each independently represent a hydrogen atom, an alkyl group or an alkoxy group. ]
It is preferable that it is an allene compound (5) represented by these.

〔式中、Ｒ₁〜Ｒ₄は上記に同じ。Ａ’は、置換基としてエチニル基、２−プロぺニル基または３−ブテニル基を有する４価の芳香族基または４価のヘテロ芳香族基を示す。Ａ’で示される芳香族基およびヘテロ芳香族基は、置換基として、アルキル基、鎖状不飽和脂肪族基、環状不飽和脂肪族基、鎖状飽和脂肪族基、環状飽和脂肪族基、ハロゲン原子、窒素原子、酸素原子、硫黄原子およびシリコン原子よりなる群から選ばれる少なくとも１つの基を有していてもよい。〕
で表されるアレン化合物（１ａ）の単独重合体、アレン化合物（１ａ）とそれに共重合可能な化合物との共重合体およびポリオレフィンと少なくとも２つのアレン化合物（１ａ）とのグラフト共重合体よりなる群から選ばれる少なくとも１つの重合体を電極活物質として含む蓄電デバイス用電極活物質に係る。 The present invention also provides a general formula

[Wherein, R _{1 to} R ₄ are the same as above. A ′ represents a tetravalent aromatic group or a tetravalent heteroaromatic group having an ethynyl group, a 2-propenyl group or a 3-butenyl group as a substituent. The aromatic group and heteroaromatic group represented by A ′ include, as a substituent, an alkyl group, a chain unsaturated aliphatic group, a cyclic unsaturated aliphatic group, a chain saturated aliphatic group, a cyclic saturated aliphatic group, You may have at least 1 group chosen from the group which consists of a halogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a silicon atom. ]
A homopolymer of the allene compound (1a), a copolymer of the allene compound (1a) and a compound copolymerizable therewith, and a graft copolymer of polyolefin and at least two allene compounds (1a). The present invention relates to an electrode active material for an electricity storage device comprising at least one polymer selected from the group as an electrode active material.

  According to the present invention, in an electricity storage device including a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, and an electrolyte, at least one of the positive electrode active material and the negative electrode active material is selected from the electrode active material for an electricity storage device. It relates to an electricity storage device including at least one.

  The organic solvent preferably contains at least two organic solvents selected from the group consisting of chain carbonates, chain esters, chain ethers, cyclic carbonates and cyclic ethers.

  The allene compound (1) used in the present invention has high capacity, high output, and good repetitive characteristics, and is useful as an electrode active material for an electricity storage device. In addition, an electricity storage device containing the allene compound (1) as an electrode active material has a high capacity, can maintain a high output for a long time, has little decrease in capacity and output even after repeated charge and discharge, and has long-term repeat characteristics. Excellent.

In the present specification, the groups represented by the symbols R _{1 to} R ₈ , A, A ₁ and Ar in each general formula are specifically as follows.
Examples of the tetravalent aromatic group include a tetravalent group including at least one selected from the group consisting of a benzene ring, a condensed ring thereof, and a bonded ring thereof. Examples of the condensed ring of the benzene ring include a naphthalene ring, an anthracene ring, a pyrene ring, a chrysene ring, and a naphthacene ring. Examples of the bond ring of the benzene ring include a biphenylene ring and a bianthracene ring. A bianthracene ring is a ring in which carbon atoms at the same position in two anthracene rings are bonded by a bond chain, such as a bond between two benzene rings in a biphenylene ring. Among these, a benzene ring, a naphthalene ring, an anthracene ring, a naphthacene ring, a biphenylene ring, a bianthracene ring and the like having a symmetrical structure and high crystallinity are particularly preferable. Examples of the tetravalent heteroaromatic group include heteroatoms (sulfur atom, nitrogen, thiophene ring, furan ring, pyrrole ring, indole ring, benzofuran ring, benzothiophene ring, quinoline ring, imidazole ring, benzimidazole ring, etc. And a tetravalent group derived from a monocyclic, bicyclic or tricyclic heteroaromatic ring containing 1 to 2 atoms or oxygen atoms.

  Examples of the chain saturated aliphatic group include an alkyl group, an alkoxy group, a hydroxyalkyl group, and a thioalkyl group. In these groups, the alkyl moiety has 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, n-hexyl, etc. A linear or branched alkyl is preferable, and a linear or branched alkyl having 1 to 4 carbon atoms is preferable. The alkyl group may have an aryl group as a substituent. An alkyl group having an aryl group is called an arylalkyl group. Examples of the arylalkyl group include benzyl, methylbenzyl, nitrobenzyl, methoxybenzyl, chlorobenzyl, phenylethyl, 1-methyl-1-phenylethyl, 1,1-dimethyl-2-phenylethyl, 1,1-dimethyl. Examples thereof include aralkyl groups in which 1 to 3 aryl groups are substituted on a linear or branched alkyl group having 1 to 4 carbon atoms, such as -3-phenylpropyl, α-naphthylmethyl, and β-naphthylmethyl.

Examples of the cyclic saturated aliphatic group include cycloalkyl groups having 3 to 6 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
Examples of the chain unsaturated aliphatic group include an alkenyl group and an alkynyl group. Examples of the alkenyl group include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 2-propenyl and 2-butenyl. C2-C4 linear or branched alkenyl groups such as 1-butenyl and 3-butenyl. Examples of the alkynyl group include linear or branched alkynyl groups having 2 to 4 carbon atoms such as ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl and the like.

  Examples of the cyclic unsaturated aliphatic group include a cycloalkenyl group and an aryl group. Examples of the cycloalkenyl group include C3-C6 cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, methylcyclopentenyl, and the like. Examples of the aryl group include straight chain or branched chain having 1 to 4 carbon atoms on a phenyl ring or naphthalene ring such as phenyl, methylphenyl, nitrophenyl, methoxyphenyl, chlorophenyl, biphenyl, α-naphthyl, β-naphthyl and the like. And an aryl group which may have at least one substituent selected from the group consisting of a chain alkyl group, a linear or branched alkoxy group having 1 to 4 carbon atoms, a nitro group and a halogen atom.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. As the alkoxycarbonyl group, an alkoxycarbonyl group in which the alkyl portion is the same linear or branched alkyl having 1 to 6 carbon atoms as described above, preferably a linear or branched alkyl having 1 to 4 carbon atoms. Is mentioned.
As the arylene group, a linear or branched chain having 1 to 4 carbon atoms on a phenyl ring or a naphthalene ring such as phenylene, methylphenylene, nitrophenylene, methoxyphenylene, chlorophenylene, biphenylene, α-naphthylene, β-naphthylene, etc. And an arylene group optionally having at least one substituent selected from the group consisting of a linear alkyl group, a linear or branched alkoxy group having 1 to 4 carbon atoms, a nitro group and a halogen atom.

Examples of the aromatic ring formed together with the carbon atoms to which R ₁ and R ₂ are bonded to each other include a benzene ring or a condensed ring of two or more benzene rings, and a benzene ring is preferred. In addition, examples of the aromatic ring formed together with the carbon atoms to which R ₃ and R ₄ are bonded to each other include a benzene ring or a condensed ring of two or more benzene rings, and a benzene ring is preferable.

  Further, in this specification, the phrase “may contain at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a silicon atom” may have a group containing at least one of these atoms. Means. Examples of the group having a nitrogen atom include an amino group, an imino group, a cyano group, and a nitro group. Examples of the group having an oxygen atom include an alkoxy group, a hydroxyl group, an alkyl group having a hydroxyl group, and an oxo group. Examples of the group having a sulfur atom include a sulfo group, a sulfonyl group, a sulfonic acid group, a thiocarbonyl group, a sulfamoyl group, and an alkylsulfonyl group. Examples of the group having a silicon atom include a silyl group. In addition, at least one of these atoms may be incorporated in the middle of a saturated or unsaturated carbon chain in an alkyl group, an alkenyl group, or the like.

The electrode active material of the present invention includes at least one selected from the allene compound (1). The allene compound (1) undergoes an oxidation-reduction reaction in which both the oxidant and the reductant satisfy the Hückel rule. In the oxidation-reduction reaction of the allene compound (1), an anion is coordinated on the molecule during oxidation, and the anion coordinated on the molecule during reduction is eliminated. This reaction can be suitably used as an oxidation-reduction reaction in an electricity storage device. Further, the allene compound (1) has a high capacity and output, and is excellent in repeatability.
The capacity is the energy density per active material, and the energy density is defined by the following equation. Therefore, in order to increase the energy density, it is essential that the number of reaction electrons is large and the molecular weight is small. The allene compound (1) has a high energy density because it has the same number of electron reactions and molecular weight as the conventional TTF compound.
Energy density (mAh / g)
= [(Number of reaction electrons × 96500) / (molecular weight)] × (1000/3600)

The output is defined as the reaction rate of the oxidation-reduction reaction. If the oxidation-reduction reaction is fast, it means high output. In order to speed up the oxidation-reduction reaction, it is required that the reaction resistance that inhibits the oxidation-reduction reaction is small. The reaction resistance is specifically a structural change accompanying the oxidation-reduction reaction, and the reaction resistance increases as the degree of change increases. By the way, the oxidation-reduction reaction of the allene compound (1) is not a reaction of bond cleavage and recombination but a reaction in which ions are coordinated on the molecule and desorbed from the molecule, so that a large structural change does not occur. . Therefore, the allene compound (1) exhibits high output.
The repeatability is defined as stability and durability against repeated redox reactions. Repeatability is not good when large structural changes occur with redox reactions. However, since the allene compound (1) is a compound that undergoes a redox reaction without structural change, it is also excellent in repeatability.

  Of the allene compound (1), a compound in which the portion represented by the symbol A is a tetravalent aromatic group is preferable. Moreover, the thing of the molecular weight of 70-300 of the group shown with the code | symbol A is preferable. Thereby, the theoretical capacity as the active material of the allene compound (1) becomes about 100 mAh / g or more, and a larger capacity can be obtained as compared with activated carbon which is an active material conventionally used. In addition, when the code | symbol A is a tetravalent aromatic group and this aromatic group has a substituent, it is good that the molecular weight which combined this aromatic group and a substituent exists in the range of 70-300. . Moreover, the substituent which substitutes for a tetravalent aromatic group has a preferable sterically low bulk substituent.

In the allene compound (1), the substituent represented by R _{1 to} R ₄ is an organic group having a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an electron withdrawing group, or an electron withdrawing group. It is preferable. As a result, the redox potential of the allene compound (1) is shifted to the high potential side, so that the energy density can be increased and the discharge voltage can be further increased. The electron withdrawing group is a substituent whose Hammett's substituent constant σp can take a positive value, specifically, a cyano group, an alkoxycarbonyl group, a carbamoyl group, an imino group, a thiocarbonyl group, A sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, a halogen atom, a sulfo group, a halogen atom and the like can be mentioned. Furthermore, the substituents represented by R _{1 to} R ₄ are particularly preferably the same group.

Therefore, among allene compounds (1), the group represented by the symbol A is a tetravalent aromatic group, and the tetravalent aromatic group may have a substituent, and the molecular weight of this part is 70 to 300. And an allene compound in which the substituent represented by R _{1 to} R ₄ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group, or an alkyl group having 1 to 4 carbon atoms having an electron withdrawing group is preferable. . Further, among these allene compounds, an allene compound in which the substituents represented by R _{1 to} R ₄ are the same group is particularly preferable.

Among the allene compounds (1), examples of the allene compounds in which the symbol A is a tetravalent aromatic group include allene compounds (2) and allene compounds (3). Specific examples of the allene compound (2) include the allene compounds (2a) to (2l) shown below.

  As an allene compound (3), an allene compound (4), an allene compound (5), etc. are mentioned, for example. Specific examples of the allene compound (4) include the allene compounds (4a) to (4e) shown below. Specific examples of the allene compound (5) include allene compounds (5a) to (5b) shown below. Examples of the allene compounds (3) other than the allene compounds (4) and (5) include the allene compounds (6a) to (6b) shown below.

〔式中、Ｒ₁〜Ｒ₄は上記に同じ。Ｒ₁₂およびＲ₁₃はそれぞれ独立して、水素原子、アルキル基またはアルコキシ基を示す。〕
で表されるアレン化合物（７）が挙げられる。 Examples of the allene compound (1) in which the symbol A is a tetravalent heteroaromatic group include, for example, a general formula

[Wherein, R _{1 to} R ₄ are the same as above. R ₁₂ and R ₁₃ each independently represents a hydrogen atom, an alkyl group or an alkoxy group. ]
The allene compound (7) represented by these is mentioned.

〔式中、Ｒ₁〜Ｒ₄、Ｒ₁₂およびＲ₁₃は上記に同じ。〕
で表されるアレン化合物（８）が挙げられる。 Examples of the allene compound (1) in which the symbol A is a tetravalent alicyclic group include, for example, a general formula

[Wherein, R _{1 to} R ₄ , R ₁₂ and R ₁₃ are the same as above. ]
The allene compound (8) represented by these is mentioned.

  In the present invention, as the electrode active material, a polymer compound containing the allene compound (1) in the molecule (hereinafter referred to as “allene compound-containing polymer”) can be used. Examples of the allene compound-containing polymer include a homopolymer of the allene compound (1a), a copolymer of the allene compound (1a) and a compound copolymerizable therewith, and a graft copolymer of the polyolefin and the allene compound (1a). Examples include coalescence. Polymerization of the allene compound (1a) or the allene compound (1a) and a compound copolymerizable therewith can be carried out in the same manner as the polymerization of polyolefin. Here, examples of the polyolefin include polyethylene and polypropylene. Specific examples of the allene compound-containing polymer include the allene compound-containing polymers (9a) to (9c) shown below.

[In each formula, m represents an integer of 10 to 100. ]
The allene compound-containing polymer has a characteristic that it is less soluble in the solvent contained in the electrolyte than the allene compound (1). Therefore, when such a polymer compound is used as an electrode active material, elution of the electrode active material into the electrolyte is suppressed, and stability such as repetition characteristics is further improved. The high molecular compound which contains an allene compound (1) in a molecule | numerator can be used individually by 1 type, or can be used in combination of 2 or more type.

  The allene compound (1) and the allene compound-containing polymer exemplified above are known compounds, such as “Angew. Chem., 1989, 28, 1052.”, “Tetrahedron Lett., 1978, 3703”, “J Chem. Soc., Perkin. Trans., 1990, 2.1777 ”,“ Angew. Chem., 1989, 101, 1090. ”,“ Angew. Chem., 1989, 101, 1090. ”,“ J. Chem. Soc., Perkin.Trans., 1991, 1,157 "," J. Chem. Soc., Chem. Commn., 1990, 470 "," J. Chem. Soc., Chem. Commn., 1990, 471 ". "," J. Chem. Soc., Chem. Comm. , 1990, 472 "," J. Chem. Soc., Perkin. Trans., 1991, 1, 157 "," J. Chem. Soc., Perkin. Trans., 1991, 1, 157 "," J. Chem. Soc., Perkin. Trans., 1991, 1, 157 "," Tetrahedron Lett., 1991, 32, 2897 "," Tetrahedron Lett., 1991, 32, 2897 "," Synth. Metal., 1991, 41 ". -43, 2579 "," Tetrahedron Lett., 1991, 32, 2897 "," Synth. Metal., 1991, 41-43, 2579 "," Tetrahedron Lett., 1991, 32, 2897 "," Synth. ., 1998,94,307 "," Synth.Metal., 1998,94,307 ", are described in the" J.A.C.S.1993,115,3752 "other various literature.

The electrode active material of the present invention contains at least one selected from the group consisting of an allene compound (1) and an allene compound-containing polymer. The electrode active material of the present invention can be used as a positive electrode active material and a negative electrode active material. When producing the electrical storage device containing the electrode active material of this invention, this electrode active material is used for at least one of a positive electrode and a negative electrode. Of course, you may use for both a positive electrode and a negative electrode. When used for one of the positive electrode and the negative electrode, an electrode active material commonly used in an electricity storage device can be used for the other.
The electricity storage device of the present invention includes a positive electrode, a negative electrode, a separator, and an electrolyte. The positive electrode and the negative electrode are arranged to face each other with a separator interposed therebetween.

  The positive electrode includes a positive electrode current collector and a positive electrode active material layer, and is disposed so that the positive electrode active material layer is located on the separator side. As the positive electrode current collector, those commonly used in this field can be used. For example, a porous or non-porous sheet material made of a metal material such as nickel, aluminum, gold, silver, copper, stainless steel, aluminum alloy, or the like A film-like material can be used. Specifically, the sheet or film is a metal foil, a mesh body, or the like. Also, a carbon material such as carbon is applied to the surface of the positive electrode current collector to reduce the resistance value, impart a catalytic effect, and chemically or physically bond the positive electrode active material layer and the positive electrode current collector. The positive electrode active material layer and the positive electrode current collector may be strengthened by bonding.

  The positive electrode active material layer is provided on at least one surface of the positive electrode current collector, includes a positive electrode active material, and includes a conductive auxiliary agent, an ion conductive auxiliary agent, a binder, and the like as necessary. When the electrode active material of the present invention is used as a positive electrode active material, examples of the negative electrode active material include carbon compounds such as graphitized carbon (graphite) and amorphous carbon such as activated carbon, lithium metal, and lithium-containing composite nitriding. Products, lithium-containing titanium oxides, Si, Si oxides, Sn, Sn oxides, carbon, and composites of these with metals other than those described above can be preferably used. The content of at least one selected from the group consisting of the allene compound (1) and the allene compound-containing polymer in the positive electrode active material layer is not particularly limited, but is preferably 20% by weight or more of the total amount of the positive electrode active material layer, more preferably 20 to 95% by weight.

The conductive auxiliary agent and the ion conductive auxiliary agent are used, for example, to reduce the resistance of the electrode. As the conductive auxiliary agent, those commonly used in this field can be used, and examples thereof include carbon materials such as carbon black, graphite and acetylene black, and conductive polymer compounds such as polyaniline, polypyrrole and polythiophene. It is done. Moreover, what is commonly used in this field can also be used as an ion conduction auxiliary agent, for example, solid electrolytes, such as polyethylene oxide, gel electrolytes, such as polymethyl methacrylate and polymethyl methacrylate, etc. are mentioned.
The binder is used, for example, to improve the binding property of the constituent material of the electrode. As the binder, those commonly used in this field can be used. For example, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, polytetrafluoroethylene, styrene -Butadiene copolymer rubber, polypropylene, polyethylene, polyimide and the like.

The negative electrode includes a negative electrode current collector and a negative electrode active material layer, and is disposed so that the negative electrode active material layer is located on the separator side. The negative electrode current collector is a porous or non-porous sheet or film made of the same metal material as the positive electrode current collector. Specifically, for example, a metal foil, a mesh body, and the like. As with the positive electrode current collector, a carbon material such as carbon is applied to the surface of the negative electrode current collector to reduce the resistance value, impart a catalytic effect, and strengthen the bond between the negative electrode active material layer and the negative electrode current collector. You may plan. The negative electrode active material layer is provided on at least one surface of the negative electrode current collector, includes a negative electrode active material, and includes a conductive auxiliary agent, an ion conductive auxiliary agent, a binder, and the like as necessary. When the electrode active material of the present invention is used as a negative electrode active material, lithium-containing metal oxides such as LiCoO ₂ , LiNiO ₂ , and LiMn ₂ O ₄ can be preferably used as the positive electrode active material. The content of at least one selected from the group consisting of the allene compound (1) and the allene compound-containing polymer in the negative electrode active material layer is not particularly limited, but is preferably 20% by weight or more of the total amount of the negative electrode active material layer, more preferably 20 to 95% by weight. As the conductive auxiliary agent, the ionic conduction auxiliary agent, and the binder contained in the negative electrode active material layer, the same conductive auxiliary agent, ionic conduction auxiliary agent, and binder as those contained in the positive electrode active material layer can be used.

  The separator is provided between the positive electrode and the negative electrode. As the separator, a sheet-like material or a film-like material having a predetermined ion permeability, mechanical strength, insulation, and the like are used. Specific examples of the separator include, for example, porous sheet-like materials or film-like materials such as microporous membranes, woven fabrics, and nonwoven fabrics. Various resin materials can be used as the separator material, but polyolefins such as polyethylene and polypropylene are preferable in view of durability, shutdown function, battery safety, and the like. The shutdown function is a function that blocks the through-hole when the battery is abnormally heated, thereby suppressing ion permeation and blocking the battery reaction.

As the electrolyte, for example, a liquid electrolyte, a solid electrolyte, a gel electrolyte, or the like can be used.
The liquid electrolyte contains a supporting salt and, if necessary, an organic solvent. The supporting salt can be appropriately selected depending on the type of the electricity storage device. When the electricity storage device is, for example, a lithium ion battery, a non-aqueous electric double layer capacitor, or the like, a supporting salt composed of the following cation and anion can be used as the supporting salt. As the cation, for example, alkali metal cations such as lithium, sodium and potassium, alkaline earth metal cations such as magnesium, and quaternary ammonium cations such as tetraethylammonium and 1,3-ethylmethylimidazolium can be used. A cation can be used individually by 1 type or in combination of 2 or more types. Examples of the anion include halogen ion, halide anion, perchlorate anion and trifluoromethanesulfonate anion, tetraborofluoride anion, trifluorophosphoric hexafluoride anion, trifluoromethanesulfonate anion, bis (trifluoromethanesulfonyl) imide anion. And bis (perfluoroethylsulfonyl) imide anion. An anion can be used individually by 1 type or in combination of 2 or more types. Specific examples of the supporting salt include, for example, lithium fluoride, lithium chloride, lithium perchlorate, lithium trifluoromethanesulfonate, lithium tetraborofluoride, lithium hexafluorophosphate, lithium bistrifluoromethylsulfonylimide, lithium thiocyanate. , Magnesium perchlorate, magnesium trifluoromethanesulfonate, sodium tetraborofluoride and the like. A supporting salt can be used individually by 1 type, or can be used in combination of 2 or more type.

  When the supporting salt itself is liquid, the supporting salt and the organic solvent may be mixed or not mixed. When the supporting salt is in a solid form, it is preferably used after being dissolved in an organic solvent.

As the organic solvent having a relative dielectric constant of 10 to 30, an organic solvent having a relative dielectric constant in the above range may be used as it is, or an organic solvent having a relative dielectric constant of 10 or less and an organic solvent having a relative dielectric constant of 30 or more. It may be a mixture with a solvent. Examples of the organic solvent having a relative dielectric constant of 10 or less include chain carbonate esters, chain esters, chain ethers, and the like. Examples of the organic solvent having a relative dielectric constant of 30 or more include cyclic carbonates and cyclic ethers.
Examples of chain carbonates include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, dibutyl carbonate, diisopropyl carbonate, and methyl ethyl carbonate. Examples of the chain esters include methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, methyl butyrate, and methyl valerate. Examples of chain ethers include diethyl ether, dimethyl ether, methyl ethyl ether, dipropyl ether, and the like. Examples of the cyclic carbonate include propylene carbonate and ethylene carbonate. Examples of cyclic ethers include 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyl-1,3-dioxolane, 2-methyl-1,3-dioxolane, and the like. . In addition to these, amides such as dimethylformamide and nitriles such as acetonitrile may be used.
As described above, one type of organic solvent may be used alone, or two or more types may be used in combination as necessary. Depending on the type of the electrode active material of the present invention, two or more organic solvents having a relative dielectric constant of 10 or less may be used in combination, or two or more organic solvents having a relative dielectric constant of 30 or more may be combined. May be used.

Examples of the solid electrolyte include Li ₂ S—SiS ₂ —lithium compound (wherein the lithium compound is at least one selected from the group consisting of Li ₃ PO ₄ , LiI and Li ₄ SiO ₄ ), Li ₂ S—P _2. O ₅ , Li ₂ S—B ₂ S ₅ , Li ₂ S—P ₂ S ₅ —GeS ₂ , sodium / alumina (Al ₂ O ₃ ), amorphous polyether having a low phase transition temperature (Tg), amorphous foot And vinylidene chloride copolymers, blends of different polymers, and polyethylene oxide.

Examples of the gel electrolyte include a gel electrolyte containing a resin material, an organic solvent, and a supporting salt. Examples of the resin material include polyacrylonitrile, a copolymer of ethylene and acrylonitrile, and a crosslinked polymer thereof. As the organic solvent, for example, a low molecular weight non-aqueous solvent such as ethylene carbonate and propylene carbonate can be preferably used. As the supporting salt, the same salts as exemplified above can be used.
The electricity storage device of the present invention is an apparatus that can store electrical energy obtained by an electrochemical redox reaction. Specific examples of the electricity storage device include a primary battery, a secondary battery, an electrochemical capacitor, an electrolytic capacitor, a sensor, an electrochromic element, and the like.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In this example, a coin-type secondary battery including the electrode active material of the present invention was produced, and a battery characteristic evaluation test of the obtained secondary battery was performed to evaluate the electrode active material of the present invention.

Example 1
The allene compound (4a) was used as the electrode active material for an electricity storage device of the present invention. The allene compound (4a) was synthesized from Synth. Metal. , 1991, 41-43, 2579.
In an argon gas atmosphere in a dry box equipped with a gas purifier, 30 mg of the allene compound (4a) and 240 mg of acetylene black (conductive auxiliary agent) were uniformly mixed. To the obtained mixture, 60 mg of tetrafluoroethylene resin (binder) was added and mixed uniformly. The obtained black paste was pressure-bonded onto an aluminum mesh foil current collector having a thickness of 280 μm using a rolling roller. This was punched onto a disk having a diameter of 13.5 mm to produce a positive electrode plate. The thickness of the positive electrode plate after drying was about 300 μm.

Next, a coin-type battery 1 having the structure shown in FIG. 1 was produced. FIG. 1 is a longitudinal sectional view schematically showing the structure of a coin-type battery 1 according to an embodiment of the present invention. First, the positive electrode plate (laminated body of the positive electrode active material layer 10 and the positive electrode current collector plate 11) prepared above is disposed in the case 17 so that the positive electrode current collector plate 11 is in contact with the inner surface of the case 17, and a porous material is formed thereon. A separator 14 made of a polyethylene sheet was installed. Next, a liquid electrolyte was poured into the case 17. As the liquid electrolyte, a solution obtained by dissolving lithium borofluoride at a concentration of 1 mol in a mixed solvent of ethylene carbonate and diethyl carbonate in a weight ratio of 1: 5 was used. The relative dielectric constant of this liquid electrolyte was 20.
On the other hand, the negative electrode current collector 13 and the negative electrode active material layer 12 were pressed onto the inner surface of the sealing plate 15 in this order. As the negative electrode, lithium metal having a thickness of 300 μm was used as the negative electrode active material layer 12 and the negative electrode current collector 13.
The case 17 on which the positive electrode is installed and the sealing plate 15 on which the negative electrode is installed are overlapped with a gasket 16 attached to the peripheral edge so that the negative electrode active material layer 12 is pressed against the separator 14, and caulked by a press machine. Then, a coin type secondary battery of the present invention having a thickness of 16 mm and a diameter of 20 mm was produced.

(Example 2)
A coin-type secondary battery of the present invention was produced in the same manner as in Example 1 except that the allene compound (5a) was used instead of the allene compound (4a) as the electrode active material for the electricity storage device.
(Comparative Example 1)
As the positive electrode active material, 2,5-dimercapto-1,3,4-thiadiazole (hereinafter referred to as “DMcT”) (manufactured by Aldrich), which is an organic sulfur-based electrode active material, was used.
In an argon gas atmosphere in a dry box equipped with a gas purifier, 30 mg of DMcT and 240 mg of acetylene black (conductive agent) were mixed thoroughly, and 60 mg of tetrafluoroethylene resin (binder) was added to the resulting mixture. And mixed well. The obtained paste-like mixture was pressure-bonded onto a 280 μm-thick aluminum mesh foil current collector using a rolling roller, and this was punched onto a disk having a diameter of 13.5 mm to produce a positive electrode plate. . The thickness of the positive electrode plate after drying was about 300 μm. Thereafter, a coin-type secondary battery of Comparative Example 1 was produced in the same manner as Example 1.

(Test Example 1)
The coin-type secondary batteries of Examples 1 and 2 and Comparative Example 1 were charged and discharged at a constant current in a voltage range of 3.0 V to 4.0 V at a current of 0.133 mA, and the first cycle, the fifth cycle, and the 10th cycle. The discharge capacity at the cycle was determined, and the characteristics were evaluated. The results are shown in Table 1.

From Table 1, it is clear that in the coin-type secondary batteries of Examples 1 and 2 containing the electrode active material of the present invention, the capacity hardly decreases even after cycling, and the capacity is high and the repetition characteristics are excellent. On the other hand, in the coin-type secondary battery containing DMcT of Comparative Example 1, although a high initial capacity was obtained, the capacity decreased with each cycle, and it was confirmed that the repetitive characteristics were poor as an electrode active material for an electricity storage device. .
From the above results, it is clear that the allene compound (1) has a high capacity and a high output, is excellent in repetitive characteristics, and is a useful compound as an electrode active material for an electricity storage device. By using this electrode active material, it is possible to realize an electricity storage device having excellent repetitive characteristics.

  ADVANTAGE OF THE INVENTION According to this invention, a high output, a lightweight, and high capacity | capacitance electrical storage device can be provided. That is, the electricity storage device of the present invention can be suitably used as a power source for various portable electronic devices, transportation devices, uninterruptible power supplies, and the like.

It is a longitudinal cross-sectional view which shows typically the structure of the coin-type battery which is one Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Coin type battery 10 Positive electrode active material layer 11 Positive electrode current collector plate 12 Negative electrode active material layer 13 Negative electrode current collector 14 Separator 15 Sealing plate 16 Gasket 17 Case

Claims (8)

General formula

[Wherein, A represents a tetravalent aromatic group or a tetravalent heteroaromatic group. The aromatic group and heteroaromatic group represented by A include, as a substituent, an alkyl group, a chain unsaturated aliphatic group, a cyclic unsaturated aliphatic group, a chain saturated aliphatic group, a cyclic saturated aliphatic group, a halogen You may have at least 1 group chosen from the group which consists of an atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a silicon atom. R _{1 to} R ₄ each independently represent a hydrogen atom, a fluorine atom, an alkyl group or an alkoxycarbonyl group. Alternatively, R ₁ and R ₂ and R ₃ and R ₄ may be independently bonded to each other to form an aromatic ring. Further, the alkyl group represented by R _{1 to} R ₄ may contain at least one atom selected from the group consisting of a halogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a silicon atom. ]
The electrode active material for electrical storage devices which contains the allene compound (1) represented by these as an electrode active material. The allene compound (1) has the general formula

[Wherein, R _{1 to} R ₄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group or an alkoxycarbonyl group. Alternatively, R ₁ and R ₂ and R ₃ and R ₄ may be independently bonded to each other to form an aromatic ring. Further, the alkyl group represented by R _{1 to} R ₄ may contain at least one atom selected from the group consisting of a halogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a silicon atom. Ar represents a benzene ring or a benzene condensed ring, and each of these rings may have a lower alkyl group as a substituent. n represents an integer of 1 or more. ]
The electrode active material for an electricity storage device according to claim 1, which is an allene compound (2) represented by: The allene compound (1) has the general formula

[Wherein, A ₁ represents an arylene group. The arylene group represented by A ₁ includes, as a substituent, an alkyl group, a chain unsaturated aliphatic group, a cyclic unsaturated aliphatic group, a chain saturated aliphatic group, a cyclic saturated aliphatic group, a halogen atom, a nitrogen atom, You may have at least 1 group chosen from the group which consists of an oxygen atom, a sulfur atom, and a silicon atom. R _{1 to} R ₄ each independently represent a hydrogen atom, a fluorine atom, an alkyl group or an alkoxycarbonyl group. Alternatively, R ₁ and R ₂ and R ₃ and R ₄ may be independently bonded to each other to form an aromatic ring. Further, the alkyl group represented by R _{1 to} R ₄ may contain at least one atom selected from the group consisting of a halogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a silicon atom. ]
The electrode active material for an electricity storage device according to claim 1, which is an allene compound (3) represented by the formula: The allene compound (3) has the general formula

[Wherein, R _{1 to} R ₄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group or an alkoxycarbonyl group. Alternatively, R ₁ and R ₂ and R ₃ and R ₄ may be independently bonded to each other to form an aromatic ring. Further, the alkyl group represented by R _{1 to} R ₄ may contain at least one atom selected from the group consisting of a halogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a silicon atom. R _{5 to} R ₈ each independently represents a hydrogen atom, an alkyl group, an alkoxy group or a group

(Wherein R ₁ and R ₂ are the same as above). ]
The electrode active material for an electricity storage device according to claim 3, which is an allene compound (4) represented by: The allene compound (3) has the general formula

[Wherein, R _{1 to} R ₄ each independently represents a hydrogen atom, a fluorine atom, an alkyl group or an alkoxycarbonyl group. Alternatively, R ₁ and R ₂ and R ₃ and R ₄ may be independently bonded to each other to form an aromatic ring. Further, the alkyl group represented by R _{1 to} R ₄ may contain at least one atom selected from the group consisting of a halogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a silicon atom. R _{9 to} R ₁₂ each independently represent a hydrogen atom, an alkyl group or an alkoxy group. ]
The electrode active material for an electricity storage device according to claim 3, which is an allene compound (5) represented by: General formula

[Wherein, A ′ represents a tetravalent aromatic group or a tetravalent heteroaromatic group having an ethynyl group, a 2-propenyl group or a 3-butenyl group as a substituent. The aromatic group and heteroaromatic group represented by A ′ include, as a substituent, an alkyl group, a chain unsaturated aliphatic group, a cyclic unsaturated aliphatic group, a chain saturated aliphatic group, a cyclic saturated aliphatic group, You may have at least 1 group chosen from the group which consists of a halogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a silicon atom. R _{1 to} R ₄ each independently represent a hydrogen atom, a fluorine atom, an alkyl group or an alkoxycarbonyl group. Alternatively, R ₁ and R ₂ and R ₃ and R ₄ may be independently bonded to each other to form an aromatic ring. Further, the alkyl group represented by R _{1 to} R ₄ may contain at least one atom selected from the group consisting of a halogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a silicon atom. ]
A homopolymer of the allene compound (1a), a copolymer of the allene compound (1a) and a compound copolymerizable therewith, and a graft copolymer of polyolefin and at least two allene compounds (1a). An electrode active material for an electricity storage device comprising at least one polymer selected from the group as an electrode active material. In an electricity storage device including a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, and an electrolyte,
The electrical storage device in which at least one of a positive electrode active material and a negative electrode active material contains at least 1 chosen from the electrode active material for electrical storage devices in any one of Claims 1-6.   The electricity storage device according to claim 7, wherein the organic solvent contains at least two organic solvents selected from the group consisting of chain carbonates, chain esters, chain ethers, cyclic carbonates and cyclic ethers.

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