JP2013116948A - Polyacetylene derivative, positive electrode active material and positive electrode for nonaqueous secondary battery, nonaqueous secondary battery, and vehicle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a polyacetylene derivative for a lightweight and high-capacity nonaqueous secondary battery positive electrode active material; a positive electrode active material; a positive electrode; a nonaqueous secondary battery; and a vehicle equipped with the nonaqueous secondary battery.SOLUTION: The polyacetylene derivative is represented by general formula (I) and can be used in a nonaqueous secondary battery as a positive electrode active material for the nonaqueous secondary battery, and the nonaqueous secondary battery can be incorporated into a vehicle. [In general formula (I): Rdenotes a single bond or a group comprising one or more kinds selected from the group of substituted or unsubstituted aliphatic hydrocarbon groups and substituted or unsubstituted aromatic hydrocarbon groups; R, Rand Reach independently denote a group comprising one or more kinds selected from the group of substituted or unsubstituted aliphatic hydrocarbon groups, substituted or unsubstituted aromatic hydrocarbon groups, substituents and a hydrogen group; Xand Xeach independently denote a substituent or a hydrogen group; n is an integer of ≥2 denoting a polymerization degree; and Rand Ror/and Rand Rmay bond to each other to form a ring].

Description

  The present invention relates to a polyacetylene derivative, a positive electrode active material and a positive electrode for a non-aqueous secondary battery, a non-aqueous secondary battery, and a vehicle.

  Non-aqueous secondary batteries are small and have high energy density, and are widely used as power sources for portable electronic devices. Further, it is considered that secondary batteries are used as driving sources for vehicles. However, since the positive electrode active material of the non-aqueous secondary battery that is currently used mainly uses cobalt or manganese oxide having a large specific gravity, the weight of the entire non-aqueous secondary battery is large. Therefore, in order to reduce the weight of the entire non-aqueous secondary battery, it is conceivable to reduce the proportion of the positive electrode active material in the entire non-aqueous secondary battery.

  In recent years, application of an organic compound or the like made of a light element as an electrode active material has been studied. In particular, a π-electron conjugated conductive polymer is promising as an electrode active material. For example, Non-Patent Document 1 reports a battery using a conductive polymer such as polyaniline as a positive electrode active material. Patent Document 1 describes a secondary battery using, as a positive electrode, a protonated polyaniline derivative compound of a conductive polymer capable of one-step two-electron transfer.

  However, the polyaniline described in Non-Patent Document 1 has a structure in which conjugation is connected in a one-dimensional chain, and when the oxidation or reduction reaction proceeds, a plurality of charges are generated in the polymer chain, and repulsion occurs through the conjugated system. To do. As a result, there is a drawback that the reaction proceeds only to a certain redox level and the battery capacity is limited.

  In addition, in the polyaniline derivative compound described in Patent Document 1, a rare one-step two-electron transfer appears by introducing a phenylenediimine skeleton having a bulky substituent bonded thereto into a polymer chain. There is an advantage that electrons can be extracted more efficiently than the conventional polyaniline using only one electron reaction. However, there is a drawback that the molecular weight per one electron reaction is large and the theoretical battery capacity is low.

  As described above, the polyaniline-based material can reduce the weight of the battery, but it is difficult to achieve a high capacity.

Japanese Patent Laid-Open No. 2005-2278

Organic Electronics (Industry Research Committee) p179

  The present invention has been made in view of the above-described current state of the prior art, and its main purpose is to achieve high capacity in a non-aqueous secondary battery using an organic polymer as an active material. . That is, an object of the present invention is to provide a novel polyacetylene derivative, a positive electrode active material and a positive electrode for a non-aqueous secondary battery, a non-aqueous secondary battery, and a vehicle that can achieve high capacity.

As a result of diligent research, the inventors of the present invention have studied the general formula (I) [in the general formula (I), R ₁ represents a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group. A group consisting of one or more selected from the group or a single bond, wherein R ₂ , R ₃ and R ₄ are each independently a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic carbonization A group consisting of one or more selected from the group consisting of a hydrogen group, a substituent and a hydrogen group; X ₁ and X ₂ each independently represent a substituent or a hydrogen group; and n represents a degree of polymerization 2 A non-aqueous two-component compound using a polyacetylene derivative represented by the following formula: R ₁ and R ₂ or / and R ₃ and R ₄ may combine to form a ring. It has been found that the secondary battery can achieve high capacity.

That is, the polyacetylene derivative of the present invention has the general formula (I) [in the general formula (I), R ₁ is selected from the group consisting of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group. Or a single bond, R ₂ , R ₃ and R ₄ are each independently a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, A group consisting of one or more selected from the group of a substituent and a hydrogen group, X ₁ and X ₂ each independently represent a substituent or a hydrogen group, and n is an integer of 2 or more indicating the degree of polymerization And R ₁ and R ₂ or / and R ₃ and R ₄ may be bonded to form a ring].

The polyacetylene derivative of the present invention is preferably represented by the following general formula (II). In the general formula (II), R ₅ represents a group consisting of one or more selected from the group consisting of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group, or a single bond. X ₁ and X ₂ each independently represent a substituent or a hydrogen group, and n is an integer of 2 or more indicating the degree of polymerization.

  The positive electrode active material for a non-aqueous secondary battery of the present invention is characterized by comprising any one of the above polyacetylene derivatives.

  The positive electrode for a non-aqueous secondary battery of the present invention is characterized by having the above positive electrode active material.

  The non-aqueous secondary battery of the present invention includes the positive electrode, the negative electrode, and an electrolyte.

  The vehicle of the present invention is equipped with the non-aqueous secondary battery.

  The polyacetylene derivative of the present invention can achieve high capacity when used as a positive electrode active material for a battery. Further, since the polyacetylene derivative is used for the non-aqueous secondary battery of the present invention, the positive electrode active material and the positive electrode used therefor, the non-aqueous secondary battery can be a high capacity battery. In addition, since the vehicle of the present invention is equipped with the non-aqueous secondary battery, it can be equipped with a high-capacity battery and can be a high-performance vehicle.

2 is a graph showing a charge / discharge curve of Example 1. FIG. 3 is a graph showing discharge curves of Example 1 and Comparative Example 1. 6 is a graph showing cycle characteristics of discharge capacity up to the 50th cycle of Example 1.

  Below, the polyacetylene derivative of this invention, the positive electrode active material and positive electrode for non-aqueous secondary batteries, a non-aqueous secondary battery, and the form for implementing a vehicle are demonstrated.

(1) Polyacetylene derivative The polyacetylene derivative of the present invention is represented by the general formula (I).

In general formula (I), R ₁ represents a group consisting of one or more selected from the group of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group, or a single bond. R ₂ , R ₃ , and R ₄ are each independently one or more selected from the group consisting of a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a substituent, and a hydrogen group R ₁ and R ₂ or / and R ₃ and R ₄ may be bonded to form a ring.

X ₁ and X ₂ each independently represent a substituent or a hydrogen group, and n is an integer of 2 or more indicating the degree of polymerization.

Here, the substituted aliphatic hydrocarbon group or the substituted aromatic hydrocarbon group means that the aliphatic hydrocarbon group or the aromatic hydrocarbon group is further substituted with a substituent. The arylene group or the substituted cyclic substituent means that the arylene group portion or the cyclic portion of the cyclic substituent has at least one substituent.
R ₁ , R ₂ , R ₃ and R ₄ may be a group consisting of one or more selected from the group consisting of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group. .

The group consisting of one or more selected from the group of unsubstituted aliphatic hydrocarbon groups and unsubstituted aromatic hydrocarbon groups represented by R ₁ , R ₂ , R ₃ , and R ₄ is, for example, each independently a methyl group Chain alkyl groups such as ethyl group, n-propyl group, isopropyl group, sec-butyl group, isobutyl group and tert-butyl group, cyclic alkyl groups such as cyclopentyl group and cyclohexyl group, and alkenyl groups such as vinyl group and allyl group May have an aryl group such as a group, a phenyl group, a tolyl group, and a naphthyl group.

R ₁ , R ₂ , R ₃ , R ₄ substituted by a group consisting of one or more selected from the group of substituted aliphatic hydrocarbon groups and substituted aromatic hydrocarbon groups, ie, aliphatic hydrocarbon groups As the substituent when the aromatic hydrocarbon group is substituted with a substituent, for example, an aryl group such as a phenyl group, a tolyl group, a naphthyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group , Alkoxy groups such as sec-butoxy group and tert-butoxy group. In addition to the hydrocarbon group composed of C (carbon) and H (hydrogen), this substituent may have a group having another element. Examples of groups having other elements include groups having O (oxygen), N (nitrogen), S (sulfur), etc., and specific examples thereof include hydroxyl groups, ether bonds, ketone groups, carbonyl groups, carboxyl groups, nitro groups. Groups, imino groups, amino groups, amide bonds, halogen groups (including, but not limited to, Cl, F, Br, or I).

R ₁ may be a single bond. In this case, the polyacetylene bond portion and the aromatic group portion are directly bonded by a single bond (single bond).

R ₂ , R ₃ and R ₄ may themselves be a substituent. Examples of the substituent include an aryl group and an alkoxy group. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. Can be mentioned. In addition, the substituent may be a group having O (oxygen), N (nitrogen), S (sulfur), etc., and specific examples include a hydroxyl group, a nitro group, an imino group, an amino group, a halogen group (Cl, F, Br). , Or I), and a carbonyl group. R ₂ , R ₃ and R ₄ may be a hydrogen group.

R ₁ , R ₂ , R ₃ and R ₄ may form separate groups. R ₁ and R ₂ may be bonded to each other to form a ring, and R ₃ and R ₄ may be bonded to each other to form a ring. R ₁ and R ₂ or / and R ₃ and R ₄ are combined to form a ring, so that in one unit, a condensed polycyclic aromatic group such as an anthracene skeleton, a naphthacene skeleton, a tetracene skeleton, or a pentacene skeleton May be included. Further, R ₁ and R ₂ may have a part that is bonded to each other to form a ring and a part that forms a separate group, and R ₃ and R ₄ are bonded to each other. Thus, it may have a part forming a ring and a part forming a separate group.

X ₁ and X ₂ each independently represent a substituent or a hydrogen group. Examples of the substituent include an alkyl group, an aryl group, an alkoxy group, a hydroxy group, a nitro group, an imino group, an amino group, a halogen group (including Cl, F, Br, or I), and a carbonyl group. When X ₁ and X ₂ are substituents, X ₁ and X ₂ may be added to any of the ortho, meta and para positions. However, the polyacetylene derivative in which X ₁ or X ₂ is added at the ortho position prevents smooth electron transfer due to its steric factor. Therefore, the polyacetylene derivative having X ₁ or X ₂ added at the ortho position is less likely to exhibit one-step two-electron transfer. In addition, in the polyacetylene derivative in which X ₁ or X ₂ is added to the ortho position, it is difficult to synthesize diimine units due to steric hindrance during the synthesis. Therefore, it is desirable that X ₁ and X ₂ are added to the para position or the meta position.

  N in the general formula (1) indicates the degree of polymerization of the polyacetylene derivative and may be an integer of 2 or more. The degree of polymerization is not particularly limited as long as the degree of polymerization is an integer of 2 or more. However, the higher the degree of polymerization, the more the dissolution in the electrolytic solution is suppressed. The upper limit of the degree of polymerization (n) is about 50,000. Therefore, the weight average molecular weight is 1000 to 10000000.

  The polyacetylene derivative of the present invention is a novel substance synthesized by the inventors' diligent research. The polyacetylene derivative of the present invention has, as a side chain, an oligoaniline structure that is a π-conjugated system with a limited conjugation length on a main chain that is composed of a polyacetylene structure in which a π-conjugated system is connected in a one-dimensional chain.

  In the working voltage range of the present invention (lithium reference 4.5 V to 1.5 V), the side chain oligoaniline site is the redox site instead of the main chain polyacetylene site. When the redox site has a structure in which aromatic groups having a conjugated structure are connected in a one-dimensional chain via an imino group (see Comparative Example 1 described later), multiple charges are generated in the polymer chain, resulting in a conjugated system. Repel through. When repulsion of charges occurs in this way, not all of the redox sites are involved in the reaction, and the redox reaction does not proceed beyond a certain level.

  The polyacetylene derivative of the present invention has an oligoaniline which is a redox site in the side chain, and the conjugation length of the side chain is limited to be short, so that repulsion of charge is suppressed and the redox level is increased. In addition, the polyacetylene main chain does not have a planar structure, but forms a helical structure that is sterically twisted to suppress repulsion of electric charges between side chains.

  The polyacetylene derivative of the present invention has an aromatic group having four imino groups that transfer four electrons in one unit in a side chain. By moving four electrons, the non-aqueous secondary battery using the polyacetylene derivative of the present invention as a positive electrode active material has a capacity density more than twice that of the conventional secondary battery using one-electron reaction or two-electron reaction. I can expect.

  In addition, since the main chain of the polyacetylene derivative of the present invention is polymerized using a double bond, the polymer structure is more stable than a polymer polymerized by a single bond. Therefore, the polyacetylene derivative of the present invention suppresses deterioration of the polymer structure. Therefore, the non-aqueous secondary battery using the polyacetylene derivative of the present invention as the positive electrode active material is excellent in cycle characteristics.

  As the polyacetylene derivative, those represented by the following general formula (II) are preferable.

In general formula (II), R ₅ represents a group consisting of one or more selected from the group consisting of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group, or a single bond. X ₁ and X ₂ each independently represent a substituent or a hydrogen group, and n is an integer of 2 or more indicating the degree of polymerization.

R ₅ is a linking group that links the polyacetylene polymerized moiety and the side chain aromatic ring. Examples of the linking group include a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, substituted or unsubstituted Examples thereof include a substituted thiophenyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted furanyl group, and a substituted or unsubstituted pyrrolyl group. Among these, R ₅ is preferably a substituted or unsubstituted phenyl group, and is preferably an unsubstituted phenyl group. R ₅ may be a single bond. In this case, the polyacetylene polymerization portion and the aromatic group portion are directly bonded by a single bond (single bond).

  The polyacetylene derivative represented by the general formula (II) has an anthracene skeleton in one unit. By having an anthracene skeleton, side reactions such as polymerization between diimine units during synthesis and oxidation-reduction can be suppressed. In addition, smooth electron transfer can be performed by a π-π interaction between anthracene skeletons and / or anthracene skeletons and a carbon material.

(2) Positive electrode active material for non-aqueous secondary battery The positive electrode active material for a non-aqueous secondary battery of the present invention is a polyacetylene derivative, which is a structural unit of a side chain as shown in the general formula (I). It has 4 imino groups in it. Here, the positive electrode active material for a non-aqueous secondary battery refers to a substance that directly contributes to the positive electrode of the non-aqueous secondary battery in the charge reaction and discharge reaction of the non-aqueous secondary battery.

(3) Positive electrode for non-aqueous secondary battery The positive electrode for a non-aqueous secondary battery of the present invention has a positive electrode active material having the polyacetylene derivative. The positive electrode may include the positive electrode active material and a binder that binds the positive electrode active material, and may further include a conductive additive. Note that the positive electrode generally has an active material layer formed by binding at least the positive electrode active material with a binder, and is attached to a current collector. Therefore, the positive electrode is prepared by preparing an electrode mixture layer forming composition containing an active material, a binder and, if necessary, a conductive additive, further adding a suitable solvent to form a paste, and then the surface of the current collector After coating, it can be dried and compressed to increase the electrode density as necessary. Thus, when using a collector, a collector is contained in a positive electrode.

  The binder plays a role of connecting the positive electrode active material and the conductive auxiliary agent. For example, a fluorine-containing resin such as polyvinylidene fluoride, polytetrafluoroethylene, and fluororubber, and a thermoplastic resin such as polypropylene and polyethylene are used. Can be used.

  A conductive additive is added to increase the conductivity of the positive electrode. Examples of the conductive assistant include carbon black, graphite, acetylene black (AB), ketjen black (KB), and carbon fiber, which are carbonaceous particles. These may be added alone or in combination of two or more thereof. The addition amount of the conductive auxiliary is preferably 10 to 2000 parts by mass, more preferably 100 to 1000 parts by mass, and 200 to 800 parts by mass per 100 parts by mass of the positive electrode active material of the present invention. Is more preferable.

  The current collector refers to a chemically inert electronic high conductor that keeps a current flowing through an electrode during discharging or charging of a non-aqueous secondary battery. Examples of the material used for the current collector include a porous or non-porous conductive substrate made of a metal material such as stainless steel, titanium, nickel, aluminum, copper, or a conductive resin. Examples of the porous conductive substrate include a mesh body, a net body, a punching sheet, a lath body, a porous body, a foamed body, a fiber group molded body such as a nonwoven fabric, and the like. Examples of the non-porous conductive substrate include a foil, a sheet, and a film.

  As a method for applying the composition for forming an electrode mixture layer, a conventionally known method such as a roll coating method, a dip coating method, a doctor blade method, a spray coating method, or a curtain coating method may be used.

  As a solvent for adjusting the viscosity, N-methyl-2-pyrrolidone (NMP), methanol, methyl isobutyl ketone (MIBK) and the like can be used.

(4) Non-aqueous secondary battery The non-aqueous secondary battery of the present invention includes at least the positive electrode, the negative electrode, and the electrolyte, and the positive electrode is the positive electrode of the present invention.

  The negative electrode has at least a negative electrode active material. The negative electrode may further include a current collector. As the current collector, nickel, stainless steel, or the like can be used, and the current collector may have any shape such as a foil, a plate, and a mesh.

  As the negative electrode active material, metallic lithium is preferably used. It is possible to use a sheet of metal lithium, or a sheet formed by pressure bonding to a current collector network such as nickel or stainless steel. Instead of metallic lithium, a lithium alloy such as a lithium-aluminum alloy can be used. A battery using metallic lithium or a lithium alloy as the negative electrode active material is called a lithium secondary battery.

  As the negative electrode active material, a negative electrode active material capable of inserting and extracting lithium ions can be used. As the negative electrode active material capable of occluding and desorbing lithium ions, Si-based or / and Sn-based materials, natural graphite, artificial graphite, organic compound heating bodies such as phenol resins, and powdered carbon materials such as coke are used. Can do.

  The negative electrode may include the negative electrode active material and a binder that binds the negative electrode active material, and may further include a conductive additive. Note that the negative electrode may be formed by attaching an active material layer formed by binding at least the negative electrode active material with a binder to the current collector, as in the case of the positive electrode. As the negative electrode binder, a fluorine-containing resin, a thermoplastic resin, or the like can be used as in the positive electrode. As the conductive auxiliary agent for the negative electrode, the same one as described for the positive electrode can be used.

  A battery using a negative electrode active material capable of inserting and extracting lithium ions as a negative electrode active material is called a lithium ion secondary battery.

  Moreover, it can also be set as the sodium secondary battery which used sodium for the negative electrode.

  In the nonaqueous secondary battery of the present invention, a separator may be provided between the positive electrode and the negative electrode. A separator is used as needed. The separator separates the positive electrode and the negative electrode and holds the non-aqueous electrolyte, and a thin microporous film such as polyethylene or polypropylene can be used.

  As the electrolyte, an organic solvent-based electrolytic solution in which an electrolyte is dissolved in an organic solvent called a nonaqueous electrolytic solution, a polymer gel electrolyte composed of a polymer gel containing an electrolytic solution, or the like can be used.

As an electrolyte to be dissolved in an organic solvent, for _{example, LiClO 4, LiPF 6, LiBF} 4, LiAsF 6, LiSbF 6, NaPF 6, NaBF 4, NaAsF 6, LiCF 3 SO 3, LiC 4 F 9 SO 3, LiCF 3 CO ₂ , Li ₂ C ₂ F ₄ (SO ₃ ) ₂ , LiN (CF ₃ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ ) ₃ , LiC _n F _{2n + 1} SO ₃ (n ≧ 2) Or a mixture of two or more. Among these, LiPF ₆ and LiC ₄ F ₉ SO ₃ that can obtain good charge / discharge characteristics are preferably used.

  The organic solvent of the non-aqueous electrolyte is preferably an aprotic organic solvent, and includes, for example, chain carbonates, cyclic carbonates, cyclic esters, nitrile compounds, acid anhydrides, amide compounds, phosphate compounds, amine compounds, and the like. It is. Specific examples include propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethoxyethane, γ-prolactin, N-methylpyrrolidinone, N, One or more selected from N′-dimethylacetamide, a mixture of propylene carbonate and dimethoxyethane, a mixture of ethylene carbonate and diethyl carbonate, and a mixture of sulfolane and tetrahydrofuran can be used.

The concentration of the electrolyte in the electrolytic solution is not particularly limited, but is preferably about 0.3 to 1.7 mol / dm ³ , particularly about 0.4 to 1.5 mol / dm ³ .

  Moreover, in order to improve the safety | security and storage characteristic of a battery, you may make an non-aqueous electrolyte contain an aromatic compound. As the aromatic compound, benzenes having an alkyl group such as cyclohexylbenzene or t-butylbenzene, biphenyl, or fluorobenzenes are preferably used.

  The polymer gel electrolyte is composed of a polymer gel containing an electrolyte solution. As the polymer gel, it is preferable to use a prepolymer TA210 (polyfunctional acrylate polymer having a polyoxyalkylene chain) that is polymerized with a photopolymerization initiator (for example, IRGACURE 184), and acrylonitrile and methyl acrylate or methacrylic acid. Copolymers may be used.

  The polymer gel electrolyte can be obtained by immersing the polymer in the electrolyte solution or polymerizing the polymer structural units (monomer / compound) in the presence of the electrolyte solution.

  A separator is sandwiched between the positive electrode and the negative electrode to form an electrode body. A non-aqueous secondary battery in which a non-aqueous electrolyte is impregnated into the electrode body after connecting between the positive electrode current collector and the negative electrode current collector to the positive electrode terminal and the negative electrode terminal leading to the outside using a current collecting lead or the like It is good to do.

  The shape of the non-aqueous secondary battery is not particularly limited, and various shapes such as a cylindrical shape, a square shape, a coin shape, and a laminate shape can be adopted.

  The non-aqueous secondary battery of the present invention described above is charged with nighttime power in the field of mobile devices such as mobile phones and laptop computers, information-related devices, and supplies power to houses, factories or offices in the daytime. It can also be suitably used in the field of stationary and automobiles such as a battery or a battery that is charged with a solar battery in the daytime and fed at night. For example, if this non-aqueous secondary battery is mounted on a vehicle, the non-aqueous secondary battery can be used as a power source for an electric vehicle.

(5) Vehicle The vehicle of the present invention is equipped with the non-aqueous secondary battery. The vehicle of the present invention can be equipped with a light-weight and long-life non-aqueous secondary battery, and can be a high-performance vehicle. The vehicle may be a vehicle that uses electric energy from a battery as a whole or a part of a power source. For example, an electric vehicle, a hybrid vehicle, a plug-in hybrid vehicle, a hybrid railway vehicle, a forklift, an electric wheelchair, an electric assist. Bicycles and electric motorcycles are examples.

  The embodiments of the polyacetylene derivative of the present invention, the positive electrode active material and positive electrode for a non-aqueous secondary battery, the non-aqueous secondary battery, and the vehicle have been described above, but the present invention is not limited to the above-described embodiment. Absent. The present invention can be implemented in various forms without departing from the gist of the present invention, with modifications and improvements that can be made by those skilled in the art.

  Hereinafter, the present invention will be described in more detail with reference to examples. A method for producing the polyacetylene derivative is shown below.

A polyacetylene derivative was synthesized from commercially available 2-bromoanthraquinone in 4 steps. In the first step, 2- (trimethylsilylethynyl) anthraquinone was obtained by introducing a trimethylsilylethynyl group into 2-bromoanthraquinone by Sonogashira reaction. In the second step, 2- (trimethylsilylethynyl) anthraquinone is converted to imine by dehydration condensation reaction in the presence of 4-aminodiphenylamine and titanium tetrachloride, and in the third step, polymerization is performed by deprotecting the trimethylsilyl group with potassium fluoride. The precursor was obtained in good yield. The polymerization precursor was identified by ¹ H-NMR, FT-IR and high resolution mass spectrum (ESI-MS). The imine substituent can be easily changed by changing the 4-aminodiphenylamine used in the synthesis. The polymerization precursor obtained in the fourth step was polymerized in the presence of an Rh catalyst to obtain a polyacetylene derivative in good yield. The molecular weight of the obtained polymer was determined by GPC.

Example 1
<Synthesis of acetylene derivative>
An acetylene derivative was synthesized by the following method. A synthesis scheme is shown below. The numbers given after products and the like are the numbers in the synthesis scheme.

[(Step 1) Synthesis of 2- (trimethylsilylethynyl) anthraquinone (2)]
Commercially available 2-bromoanthraquinone (1) (0.2897 g, 1.0 mmol), PdCl ₂ (PPh ₃ ) ₂ (0.070 g, 0.1 mmol) and CuI (0.0380 g, 0.2 mmol) were added to tetrahydrofuran. Trimethylsilylacetylene (0.6 ml, 4.3 mmol) was added to a mixed solution dissolved in (THF, 5 ml) and triethylamine (ET ₃ N, 5 ml).

The reaction mixture was stirred at 65 ° C. under Ar atmosphere for 24 hours. The reaction mixture was passed through a short silica gel column and evaporated. The residue was purified by flash silica gel column chromatography (chloroform (CHCl ₃ ): hexane, 1: 4 to 1: 1) to give product (2) (2- (trimethylsilylethynyl) anthraquinone) (0.2914 g, .0. 96 mmol) was obtained with a yield of 96%. The identity and purity of product (2) was confirmed by ¹ H NMR spectrum. ¹ H NMR spectrum (500 MHz, deuterated chloroform (CDCl ₃ )) is as follows: a 8.36 (d, J = 1.8 Hz, 1H), 8.31-8.29 (m, 2H), d 8 .25 (d, J = 8.1 Hz, 1H), 7.83-7.78 (m, 3H), 0.29 (s, 9H).

[(Step 2) Synthesis of Compound (3)]
Products (2) (2- (trimethylsilylethynyl) anthraquinone) (0.1595 g, 0.52 mmol), 4-aminodiphenylamine (0.2661 g, 0.144 mmol) and 1,4-diazabicyclo [2.2.2] To a solution of octane (DABCO) (0.4821 g, 4.30 mmol) in chlorobenzene (10 ml), a solution of titanium tetrachloride (TiCl ₄ ) (0.12 ml, 1.09 mmol) in chlorobenzene (5 ml) was gradually added at room temperature. It was.

The reaction mixture was stirred at 125 ° C. overnight. The precipitate was removed by filtration. The filtrate was evaporated and the residue was purified by flash silica gel column chromatography (CHCl ₃ ) to give compound (3) (0.2509 g, 0.39 mmol) in 75% yield.

^{The 1} H NMR spectrum (500 MHz, deuterated chloroform (CDCl ₃ )) is as follows: δ 8.44-8.26 (m, 2H), 7.83-7.16 (m, 5H), 7.09- 7.05 (m, 9H), 6.97-6.87 (m, 6H), 5.69 (br, 2H), 0.28-0.13 (m, 9H). The IR measurement (ATR, cm ⁻¹ ) results are as follows: 3389, 3022, 2955, 2152, 1589, 1495, 1401, 1304, 1238, 1169, 1107, 1029, 947, 877, 837, 744, 686.

[(Step 3) Synthesis of Compound (4)]
To a solution of compound (3) (0.1500 g, 0.24 mmol) in THF / methanol (6 ml / 6 ml) was added potassium fluoride (KF) (0.050 g, 0.86 mmol). The reaction mixture was stirred for 2 hours at room temperature. Water was added and the mixture was extracted with CHCl ₃ . The organic layer was dried over magnesium sulfate (MgSO ₄ ) and evaporated to give the crude product. The crude product was further purified by flash silica gel column chromatography (CHCl ₃ ) to obtain compound (4) (0.1268 g, 0.23 mmol) in a yield of 95%.

^{The 1} H NMR spectrum (500 MHz, CDCl ₃ ) is as follows: δ 8.47-8.28 (m, 2H), 7.83-7.19 (m, 8H), 7.13-7.04 ( m, 9H), 6.93-6.90 (m, 6H), 5.71 (br, 2H), 3.21-2.99 (m, 1H).

IR measurement (ATR, cm ⁻¹ ) results are as follows: 3389, 3279, 3021, 1589, 1493, 1400, 1302, 1229, 1169, 1107, 988, 944, 906, 831, 742, 685, 617.

The result of high-resolution mass spectrometry spectrum (HRMS) (electrospray ionization method (ESI)) was calculated as C ₄₀ H ₂₉ N ₄ [M + H]: 5655.2392, and the actually measured value was 5655.2399.

<Synthesis of polyacetylene derivative>
[(Step 4) Synthesis of polyacetylene derivative (5)]
Compound (4) (0.05727 g, 0.10 mmol) and triethylamine (Et ₃ N) (30 μl, 0.22 mmol) were dissolved in THF (0.5 ml). [Rh (nbd) Cl] ₂ (0.00187 g, 0.040 mmol) serving as a polymerization catalyst dissolved in THF (0.2 ml) was added to the mixed solution, and the mixture was stirred at 30 ° C. for 24 hours under argon. Thereafter, an excessive amount of methanol was added to the reaction mixture to cause precipitation, and the product was collected by filtration to obtain the desired polyacetylene derivative (5) in a yield of 84% (0.04808 g).

GPC: Number average molecular weight (Mn): 4104. Weight average molecular weight / number average molecular weight (Mw / Mn) = 3.014. IR measurement (ATR, cm ⁻¹ ) results are as follows: 3394, 3053, 1593, 1499, 1400, 1308, 1236, 1173, 1108, 947, 831, 746, 689, 618.

Elemental analysis is _{C 40 H 28 N 4 · 0.2CHCl} 3: C, 82.04; H, 4.83; N, 9.52; was calculated to be. The measured value was C, 81.96; H, 4.74; N, 9.51.

<Production of lithium battery>
The produced polyacetylene derivative (5) (2 mg, 40% by mass), ketjen black (manufactured by Ketjenblack International, 2.5 mg, 50% by mass), polytetrafluoroethylene (PTFE) (manufactured by Daikin Industries) (0. 5 mg, 10% by mass) was mixed to form a sheet, which was pressure-bonded to an aluminum mesh (14φ, manufactured by Niraco) as a current collector. It was dried at 120 ° C. for 6 hours or more under vacuum to produce a positive electrode containing a polyacetylene derivative as a positive electrode active material. After that, it went in the glove box. This positive electrode was placed on a positive electrode can constituting a storage container of a coin battery, and impregnated with an electrolytic solution (1M LiPF ₆ / EC: DEC (1: 1 v / v%)). A separator (Celgard 2400) made of a polypropylene porous film and a glass filter (GA-100 manufactured by Advantech) were stacked on the positive electrode, and a lithium foil (14φ, manufactured by Honjo Metal) serving as a negative electrode was further stacked. Then, the aluminum exterior of a coin battery was piled up in the state where insulating packing was arranged around. This was pressurized by a crimping machine to produce a sealed coin-type lithium secondary battery using a polyacetylene derivative as a positive electrode active material and metallic lithium as a negative electrode active material. This was designated as the lithium secondary battery of Example 1.

(Comparative Example 1)
A lithium secondary battery of Comparative Example 1 was produced in the same manner as in <Preparation of Lithium Secondary Battery> in Example 1 except that the compound represented by the following general formula (III) was used as the positive electrode active material. .

  The polymer represented by the general formula (III) was produced as follows in accordance with Patent Document 1 (Japanese Patent Laid-Open No. 2005-2278).

Anthraquinone (0.520 g, 2.5 mmol), 4,4′-diaminodiphenylamine (0.498 g, 2.5 mmol) and 1,4-diazabicyclo [2.2.2] octane (DABCO) (3.37 g, 30 0.0 mmol) in chlorobenzene (200 ml) was slowly added a solution of titanium tetrachloride (TiCl ₄ ) (0.82 ml, 7.5 mmol) in chlorobenzene (10 ml) at room temperature. The reaction mixture was stirred at 125 ° C. for 12 hours. The precipitate was removed by filtration. The filtrate was evaporated and the residue was separated by GPC through flash silica gel column chromatography (CHCl ₃ ). As a result, 30 mg, 250 mg, 30 mg, 150 mg, 70 mg, and 50 mg of substances with n = 2, 3, 4, 5, 6, and 7 were obtained, respectively. A material with n = 5 was used as Comparative Example 1. The results of IR measurement (ATR, cm ⁻¹ ) of the substance with n = 5 are as follows: 3393, 3026, 1591, 1495, 1401, 1306, 1238, 1169, 1108, 1029, 947, 837, 744, 686.

(Comparative Example 2)
A comparative example was carried out in the same manner as in <Preparation of lithium secondary battery> in Example 1 except that the compound represented by the following general formula (IV), which is a one-stage two-electron transfer polymer, was used as the positive electrode active material. No. 2 lithium secondary battery was produced.

  The polymer represented by the general formula (IV) was produced as follows.

Commercially available 2-bromoanthraquinone (0.2897 g, 1.0 mmol), PdCl ₂ (PPh ₃ ) ₂ (0.070 g, 0.1 mmol) and CuI (0.0380 g, 0.2 mmol) were added to tetrahydrofuran (THF, 5 ml) and triethylamine (ET ₃ N, 5 ml) were added trimethylsilylacetylene (0.6 ml, 4.3 mmol) to a mixed solution.

The reaction mixture was stirred at 65 ° C. under Ar atmosphere for 24 hours. The reaction mixture was passed through a short silica gel column and evaporated. The residue was purified by flash silica gel column chromatography (chloroform (CHCl ₃ ): hexane, 1: 4 to 1: 1) to give 2- (trimethylsilylethynyl) anthraquinone) (0.2914 g, 0.96 mmol) in 96 yield. %.

  2- (Trimethylsilylethynyl) anthraquinone (0.1562 g, 0.51 mmol), aniline (140 μl, 1.54 mmol) and 1,4-diazabicyclo [2.2.2] octane (DABCO) (0.600 g, 5.34 mmol) ) In chlorobenzene (10 ml) was slowly added a solution of titanium tetrachloride (0.11 ml, 1.0 mmol) in chlorobenzene (5 ml) at 50 ° C.

The reaction mixture was stirred at 100 ° C. for 3 hours. The precipitate was removed by filtration. The filtrate was evaporated and the residue was purified by flash silica gel column chromatography (CHCl ₃ : hexane, 1: 1) to give N, N′-diphenyl 2- (trimethylsilylethynyl) anthraquinone diimine (0.1794 g, 0 .40 mmol) was obtained in a yield of 77%.

To a solution of N, N′-diphenyl 2- (trimethylsilylethynyl) anthraquinonediimine (0.0811 g, 0.18 mmol) in THF / methanol (4 ml / 4 ml) was added potassium fluoride (KF) (0.030 g, 0.52 mmol). ) Was added. The reaction mixture was stirred for 30 minutes at room temperature. Water was added and the mixture was extracted with CHCl ₃ . The organic layer was dried over magnesium sulfate (MgSO ₄ ) and evaporated to give the crude product. The crude product was further purified by silica gel chromatography (CHCl ₃ ) to obtain N, N′-diphenyl 2-ethynylanthraquinonediimine (0.0621 g, 0.16 mmol) in a yield of 91%.

N, N′-diphenyl 2-ethynylanthraquinonediimine (0.1143 g, 0.30 mmol) and triethylamine (Et ₃ N) (70 μl, 0.50 mmol) were dissolved in THF (1.3 ml). A polymerization initiator [Rh (nbd) Cl] ₂ (0.00416 g, 0.090 mmol) dissolved in THF (0.3 ml) was added to the mixed solution, and the mixture was stirred at 30 ° C. for 24 hours under argon. Thereafter, the reaction mixture was added with an excess amount of methanol and precipitated, and the product was further purified by GPC to obtain the desired compound (IV) in a yield of 75% (0.8658 g, 0.23 mmol) (the oligomer was Removed by GPC).

GPC: Number average molecular weight (Mn): 53893. Weight average molecular weight / number average molecular weight (Mw / Mn) = 3.209. The results of IR measurement (ATR, cm ⁻¹ ) are as follows: 3057.9, 3026.1, 1666.3, 1621.5, 1584.6, 1479.5, 1446.7, 1291.8, 1227.7 , 1165.4, 1146.2, 1069.7, 1023.5, 985.3, 943.0, 894.3, 830.1, 763.4, 692.0, 674.1, 616.9, 567 0.0, 513.8.

The elemental analysis results were calculated as C ₂₈ H ₂₈ N ₂ .0.15 CHCl ₃ : C, 84.45; H, 4.57; N, 7.00; The measured value was C, 84.77; H, 4.46; N, 6.81.

<Charge / discharge test>
A charge / discharge test was conducted on the lithium secondary batteries of Example 1 and Comparative Examples 1 and 2. In the charge / discharge test, charge / discharge was performed at a current density of 25 mA / g in the range of 4.0V to 2.0V. FIG. 1 shows the charge / discharge curve of Example 1. As can be seen from FIG. 1, Example 1 had plateaus at about 4 V and about 3.3 V, and showed a high capacity of 183.0 mAh / g (discharge capacity at the first cycle). The number of mobile electrons (n) calculated from the theoretical capacity [189.9 mAh / g (the number of mobile electrons (n) was assumed to be 4)] was 3.85.

  The theoretical capacity was calculated by the following formula 1.

Theoretical capacity (Ah / g) = n × e × N A / (3600 × M) ··· ( Equation 1)
n = number of electrons, e = 1.6022 × 10 ⁻¹⁹ C / piece, N _A = 6.022 × 10 ²³ pieces / mol, M = molecular weight of unit g / mol.

  The charge / discharge mechanism of Example 1 is considered that four electrons move between the two-electron oxidant (5 ″) and the two-electron reductant (5 ′) of the polyacetylene derivative (5). The expected reaction formula is shown below.

  That is, the plateau on the high potential side (about 4V) of the discharge curve corresponds to a response from 5 ″ to 5, and the plateau on the low potential side (about 3.3V) corresponds to a response from 5 to 5 ′. It is predicted that That is, it is predicted that the plateau at the first stage: reduction of the —NH—Ph site at the end of the unit, and the plateau at the second stage: reduction of —N = anthracene = N—. Further, it is considered that the substituent (Ph-NH-) has an ability to attract lithium ions and enhances lithium ion conductivity.

  FIG. 2 shows the discharge curves of Example 1 and Comparative Example 1. The discharge capacity of the first cycle of Example 1 was 183.0 mAh / g, whereas the discharge capacity of the first cycle of Comparative Example 1 was 123.0 mAh / g. Although not shown in FIG. 2, the discharge capacity of Comparative Example 2 was 71.0 mAh / g in the first cycle.

  When the discharge capacities of Example 1 and Comparative Example 1 were compared, it was found that the capacity of Example 1 having a shorter conjugate length was significantly large. This value is close to the theoretical capacity calculated above, and it was found that a polymer having this 4-electron transfer structure in the side chain can be charged and discharged very efficiently. Further, comparing the discharge capacities of Example 1 and Comparative Example 2, the discharge capacity of Example 1 is large, and Example 1 can have a higher capacity than a polymer having a one-step two-electron transfer structure in the side chain. I understood.

<Cycle test>
In Example 1, charging and discharging were repeated at a current density of 25 mA / g in the range of 4.0 V to 2.0 V. FIG. 3 shows the cycle characteristics of the discharge capacity up to the 50th cycle of Example 1. As seen from FIG. 3, Example 1 showed good cycle characteristics with almost no decrease in discharge capacity even at the 50th cycle. The number of mobile electrons (n) calculated from the theoretical capacity always showed 3 or more.

<High rate test>
Example 1 was charged and discharged at a current density of 500 mA / g (equivalent to about 3C). As a result, even at a high rate, it had a two-stage plateau and showed a high capacity of 141.3 mAh / g at the 20th cycle. Good cycle characteristics were exhibited even at high rates.

  As described above, the lithium secondary battery of Example 1 has the redox site not in the main chain but in the side chain, and by shortening the conjugation length of the side chain, the redox reaction can proceed efficiently, and the high capacity And high cycle characteristics. Moreover, it turned out that the lithium ion secondary battery of Example 1 has a high capacity and a high cycle characteristic even at a high rate.

Claims (6)

General Formula (I) [In General Formula (I), R ₁ is a group consisting of one or more selected from the group consisting of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group; Or R ₂ , R ₃ and R ₄ each independently represents a group of a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a substituent and a hydrogen group And X ₁ and X ₂ each independently represents a substituent or a hydrogen group, n is an integer of 2 or more indicating the degree of polymerization, and R ₁ and R ₂ Or / and R ₃ and R ₄ may combine to form a ring].

The polyacetylene derivative according to claim 1, which is represented by the following general formula (II).

(In the general formula (II), R ₅ represents a group consisting of one or more selected from the group consisting of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group, or a single bond. X ₁ and X ₂ each independently represent a substituent or a hydrogen group, and n is an integer of 2 or more indicating the degree of polymerization.   A positive electrode active material for a non-aqueous secondary battery, comprising the polyacetylene derivative according to claim 1.   A positive electrode for a non-aqueous secondary battery, comprising the positive electrode active material according to claim 3.   A non-aqueous secondary battery comprising the positive electrode according to claim 4, a negative electrode, and an electrolyte.   A vehicle equipped with the nonaqueous secondary battery according to claim 5.

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