JP4752217B2 - Active materials, batteries and polymers - Google Patents

Description

  The present invention provides an electrode active material having a high capacity density and capable of extracting a large current, a battery having a high energy density and a large output, and an electrode active material having the above characteristics. Relates to a polymer.

  In recent years, portable electronic devices such as notebook computers and mobile phones are rapidly spreading with the development of communication systems, and their performance is also improving year by year. However, portable devices tend to increase power consumption as performance improves. Therefore, demands for high energy density, high output, etc. are increasing for the battery as the power source.

  As a high energy density battery, a lithium ion battery has been developed and widely used since the 1990s. This lithium ion battery uses, for example, a lithium-containing transition metal oxide such as lithium manganate or lithium cobaltate as the positive electrode and carbon as the negative electrode, and insertion and desorption reactions of lithium ions into these active materials. Charging and discharging is performed using Such a lithium ion battery has high energy density and excellent cycle characteristics, and is used in various electronic devices such as mobile phones. However, since the reaction rate of the electrode reaction is small, the battery performance is significantly lowered when a large current is taken out. For this reason, it is difficult to produce a large output, and there is a disadvantage that it takes a long time for charging.

  An electric double layer capacitor is known as an electricity storage device capable of producing a large output. Since a large current can be discharged at one time, it is possible to produce a large output, and it has excellent cycle characteristics, and is being developed as a backup power supply. However, since the energy density is very small and it is difficult to reduce the size, it is not suitable as a power source for portable electronic devices.

  In order to obtain an electrode material that is lightweight and has a large energy density, a battery using a sulfur compound or an organic compound as an active material has been developed. For example, Patent Document 1 (US Pat. No. 4,833,048) and Patent Document 2 (Japanese Patent No. 2715778) disclose batteries using an organic compound having a disulfide bond as a positive electrode. This is an electrochemical redox reaction involving generation and dissociation of disulfide bonds, which is used as a battery principle. Since this battery is composed of an electrode material mainly composed of an element having a small specific gravity such as sulfur or carbon, it has a certain effect in terms of a high-capacity battery having a high energy density. However, due to the low efficiency with which the dissociated bonds are recombined and the diffusion of the active material into the electrolyte, there are drawbacks in that the capacity tends to decrease with repeated charge / discharge cycles.

  In addition, as a battery using an organic compound, a battery using a conductive polymer as an electrode material has been proposed. This is a battery based on the principle of doping and dedoping of electrolyte ions with respect to a conductive polymer. The dope reaction is a reaction in which a charged radical generated by oxidation or reduction of a conductive polymer is stabilized by a counter ion. Patent Document 3 (US Pat. No. 4,442,187) discloses a battery using such a conductive polymer as a positive electrode or negative electrode material. This battery was composed only of elements having a small specific gravity such as carbon and nitrogen, and was expected as a high capacity battery. However, conductive polymers have the property that charged radicals generated by redox are delocalized over a wide range of π-electron conjugated systems and interact with each other, resulting in electrostatic repulsion and radical disappearance. . This limits the generated charged radicals, that is, the doping concentration, and limits the capacity of the battery. For example, it has been reported that the doping rate of a battery using polyaniline as a positive electrode is 50% or less, and 7% in the case of polyacetylene. A battery using a conductive polymer as an electrode material has a certain effect in terms of weight reduction, but a battery having a large energy density has not been obtained.

As an electricity storage device using an organic compound, Patent Document 4 (Japanese Patent Laid-Open No. 2000-315527) proposes a nonaqueous electrolyte capacitor using a conductive polymer containing triphenylamine as a repeating unit as an electrode material. Yes. It can produce a large output and has a higher energy density than conventional electric double layer capacitors. However, like the battery using a conductive polymer as an electrode active material, the generated dope concentration is limited, and there is still room for improvement in terms of energy density.
US Pat. No. 4,833,048 Japanese Patent No. 2715778 U.S. Pat. No. 4,442,187 JP 2000-315527 A

  As described above, in a lithium ion battery using a transition metal oxide for the positive electrode, it is difficult to manufacture a battery that can provide a large output. In addition, the electric double layer capacitor can produce a large output, but the energy density is low. In addition, a battery using a sulfur compound or a conductive organic compound as an active material has not yet been obtained.

  The present invention provides an electrode active material having a high capacity density and capable of extracting a large current, a battery having a high energy density and a large output, and an electrode active material having the above characteristics. The object is to provide a polymer which can be obtained.

The present inventors have made intensive studies, as a result, certain organic compounds have not been used as an electrode active material of the electrode to date, i.e. a compound having a structure represented by the following formula (1) in a molecule as (a) The present inventors have found that the above problem can be solved by using a polymer compound having a unit represented by the following formula (2) in the molecule as an electrode active material of an electrode. According to the present invention, by a novel cell using a polymer compound having a unit represented by the following formula (2) in the molecule as an electrode active material, using a redox of this site, high energy It is possible to provide a novel battery capable of producing a high density and high output (specifically, a large current can be discharged).

That is, this invention is an electrode active material containing the high molecular compound which has a unit represented by following formula (2) in a molecule | numerator. Further, as at least one electrode active material of the positive electrode and the negative electrode, a novel cell characterized by using an electrode active material containing a polymer compound having a unit represented by the following formula (2) in the molecule .

In Formula (1) and Formula (2) , R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n -A butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a trifluoromethyl group, or a fluorine atom is represented.

  In the battery of the present invention, the compound (a) undergoes an oxidation-reduction reaction as shown in the following scheme during the charge / discharge process. When the compound (a) is used for the positive electrode, the state changes from (A) to (B) by charging, and electrons are emitted. The state changes from (B) to (A) by discharging, and receives electrons.

  In the battery, the electrode active material is oxidized or reduced by charge / discharge, and therefore the electrode active material takes two states, a starting state and a reduced state. In the present invention, the electrode active material becomes the compound (a) in either a charged or discharged state.

The present invention provides a battery using the electrode reaction of the electrode active material, at least one of the electrode reaction of the positive electrode and the negative electrode, reaction of a polymer having a unit represented by the above formula (2) in a molecule or The present invention relates to a battery characterized by an electrode reaction as a product.

  The present invention also relates to any one of the above batteries, wherein the electrode active material is a positive electrode active material.

  The present invention also relates to any one of the above batteries, wherein the battery is a lithium battery.

This invention was made | formed based on having discovered that the high molecular compound which has a unit represented by Formula (2) in a molecule | numerator among said compound (a) was excellent as an electrode active material. is there. This is because the compound (a) causes a reversible and stable oxidation-reduction reaction at a rate of almost 100% with little side reaction. That is, as the compound (a) , a battery using a polymer compound having a unit represented by the formula (2) in the molecule as an electrode active material can be stably charged and discharged and has excellent cycle characteristics. Battery. In addition, a battery using, as an electrode active material , a high molecular compound having a unit represented by the formula (2) in the molecule as the compound (a) has excellent high output characteristics as compared with a conventional lithium ion battery. This means that a large amount of current can be discharged. Further, the compound (a) can be composed of only elements having a small mass such as carbon, nitrogen, hydrogen and oxygen. For this reason, the mass of the electrode active material can be reduced, and the capacity density per unit mass of an electrode manufactured using the same can be increased. As a result, when a battery is produced using this electrode active material, the energy density per mass is Becomes a big battery.

  Moreover, in this invention, the compound (a) should just contribute directly to the electrode reaction in a positive electrode or a negative electrode, and the electrode used as an electrode active material is not limited to either a positive electrode or a negative electrode. However, from the viewpoint of energy density, it is particularly preferable to use this compound (a) as an electrode active material for the positive electrode. In addition, the battery of the present invention is preferably a lithium battery using carbon capable of inserting and removing metallic lithium or lithium ions in the negative electrode from the viewpoint of obtaining a high capacity.

  The present invention also provides a novel polymer having a unit represented by the following formula (3) in the molecule.

(In Formula (3), R ^{1 ′} represents a hydrogen atom or a methyl group, and R ^{2 ′} and R ^{3 ′} each independently represents a hydrogen atom or a methoxy group.)

The present invention has been proposed an electrode active material containing a polymer compound having a unit represented by the formula (2) in the molecule, a new cell using the electrode active material. This makes it possible to produce a battery composed of light and safe elements that do not contain heavy metals as an electrode active material, and has high capacity (per mass) and excellent charge / discharge cycle stability. In addition, a battery capable of producing a larger output can be realized.

FIG. 1 shows the configuration of one embodiment of the battery of the present invention. In the battery shown in FIG. 1, the positive electrode 6 and the negative electrode 4 arranged on the negative electrode current collector 3 are stacked so as to face each other with a separator 5 containing an electrolyte, and a positive electrode current collector 7 is placed on the positive electrode 6. It has a superposed configuration. These are packaged by an aluminum exterior 1 on the negative electrode side and an aluminum exterior 1 on the positive electrode side, and an insulating packing 2 made of an insulating material such as a plastic resin is disposed between them for the purpose of preventing electrical contact therebetween. . In addition, when using solid electrolyte and gel electrolyte as electrolyte, it can replace with a separator and can also be made into the form which interposes these electrolytes between electrodes.
In the present invention, the present invention is characterized in that the electrode active material used for the negative electrode 4 or the positive electrode 6 or both electrodes is an electrode active material containing a compound (a) described later.

  The battery of the present invention is preferably a lithium battery using the above electrode active material as a positive electrode active material from the viewpoint of battery capacity.

[1] Electrode active material The electrode active material of the electrode in the present invention is a material that directly contributes to electrode reactions such as charge reaction and discharge reaction, and plays a central role in the battery system.

  In this invention, the electrode active material containing the compound (a) which has a structure represented by following formula (1) in a molecule | numerator can be used as an electrode active material.

In the formula (1), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i -A butyl group, a s-butyl group, a t-butyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a trifluoromethyl group, or a fluorine atom is represented. R ² and R ³ are preferably an alkoxy group, that is, a methoxy group, an ethoxy group, an n-propoxy group, or an isopropoxy group in view of charge / discharge stability. In the formula (1), the part where the bond destination group is not described means that it may be bonded to another group. Specifically, a hydrogen atom or a monovalent organic group is bonded. Means that

  In the present invention, the compound (a) contained in the electrode active material may be a low molecular compound or a high molecular compound. In the battery of the present invention, the electrode active material may be fixed to the electrode, or may be dissolved or dispersed in the electrolyte. However, when used in a state of being fixed to the electrode, in order to suppress a decrease in capacity due to dissolution in the electrolytic solution, it is preferably insoluble or low-soluble in the electrolytic solution in the solid state. This is because, when the solubility in the electrolytic solution is high, the electrode active material is eluted from the electrode into the electrolytic solution, so that the capacity decreases with the charge / discharge cycle. Therefore, the compound (a) is preferably a polymer compound having a number average molecular weight of 500 or more, and more preferably a polymer compound having a number average molecular weight of 5000 or more. This is because a polymer compound tends to be in a solid state, and if the number average molecular weight is 500 or more, it is difficult to dissolve in the battery electrolyte, and if the number average molecular weight is 5000 or more, it is almost insoluble. is there. The upper limit of the number average molecular weight is not particularly limited, but a polymer compound having a number average molecular weight of 5000000 or less, more preferably a number average molecular weight of 1000000 or less can be suitably used for the convenience of synthesis. The polymer compound may be in the form of a chain, a branch, or a network. Moreover, the structure which bridge | crosslinked with the crosslinking agent may be sufficient.

  Examples of the compound (a) include a polymer compound having a unit represented by the formula (2) in the molecule and having polyacetylene in the main chain.

In the formula (2), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i -A butyl group, a s-butyl group, a t-butyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a trifluoromethyl group, or a fluorine atom is represented. R ² and R ³ are preferably an alkoxy group, that is, a methoxy group, an ethoxy group, an n-propoxy group, or an isopropoxy group in view of charge / discharge stability.

  As said high molecular compound, the homopolymer which has only the unit represented by Formula (2) can be used, and the copolymer which has another unit can also be used. For the convenience of synthesis, a homopolymer is preferred. In the case of a copolymer, the unit represented by the formula (2) is preferably 70 to 99 unit%, more preferably 80 to 95 unit%, based on all units of the polymer compound.

  Examples of such polymer compounds include polymer compounds having units represented by the following formulas (5) to (18) in the molecule.

The polymer compound having a unit represented by the above formula (5) in the molecule can be synthesized, for example, by the route shown in the following synthesis scheme. Dianisylamine was obtained by a cross-coupling reaction of p-anisidine and p-bromoanisole using a Pd catalyst. The amine was acetylated and then trichlorovinylated using phosphorus pentachloride. Dianisylaminoacetylene was obtained through elimination with n-BuLi. The resulting dianisylaminoacetylene is subjected to coordination polymerization using [Rh (norbornadiene) Cl] ₂ as a catalyst in triethylamine at room temperature to obtain a polymer compound having a unit represented by the formula (6) in the molecule. . Moreover, it is also possible to synthesize | combine by the method as described in the Example mentioned later.

  Other low molecular compounds and polymer compounds that can be used as the compound (a) can also be synthesized by a method similar to the above synthesis method. That is, the target compound can be synthesized by appropriately changing the synthesis scheme, raw materials to be used, reaction conditions and the like, and combining known synthesis techniques.

  In the electrode active material of one electrode of the battery of the present invention, the compound (a) can be used alone, but two or more kinds may be used in combination. Moreover, you may use in combination with another electrode active material. At this time, it is preferable that 10-90 mass% of compounds (a) are contained in an electrode active material, and it is more preferable that 20-80 mass% is contained.

When the compound (a) is used for the positive electrode, metal oxides, disulfide compounds, other stable radical compounds, conductive polymers, and the like can be combined as other electrode active materials. Here, as the metal oxide, for example, lithium manganate such as LiMnO ₂ , Li _x Mn ₂ O ₄ (0 <x <2) or lithium manganate having a spinel structure, MnO ₂ , LiCoO ₂ , LiNiO ₂ , Alternatively, Li _X V ₂ O ₅ (0 <x <2) or the like may be used as disulfide compounds such as dithioglycol, 2,5-dimercapto-1,3,4-thiadiazole, S-triazine-2,4,6-trithiol. Other stable radical compounds include poly (2,2,6,6-tetramethylpiperidinoxyl-4-yl methacrylate) and the like, and conductive polymers include polyacetylene, polyphenylene, polyaniline, and polypyrrole. Etc. In particular, it is preferable to combine with lithium manganate or LiCoO ₂ . In the present invention, these other electrode active materials can be used alone or in combination of two or more.

  When the compound (a) is used for the negative electrode, graphite, amorphous carbon, metallic lithium or lithium alloy, lithium ion storage carbon, metallic sodium, conductive polymer, or the like can be used as the other electrode active material. Moreover, you may use another stable radical compound. Other stable radical compounds include poly (2,2,6,6-tetramethylpiperidinoxyl-4-yl methacrylate). These shapes are not particularly limited. For example, metallic lithium is not limited to a thin film shape, and may be a bulk shape, a powdered shape, a fiber shape, a flake shape, or the like. These other electrode active materials can be used alone or in combination of two or more.

  The battery of the present invention uses the compound (a) as an electrode active material in one electrode reaction of the positive electrode or the negative electrode, or both electrode reactions. Conventionally known electrode active materials such as those exemplified above can be used as the electrode active material. These electrode active materials can be used alone or in combination of two or more thereof, and at least one of these electrode active materials and the compound (a) may be used in combination.

[2] Conductivity imparting agent (auxiliary conductive material) and ion conductivity assisting material In the case of forming an electrode using the compound (a), the conductivity imparting agent is used for the purpose of reducing impedance and improving energy density and output characteristics. (Auxiliary conductive material) or ion conductive auxiliary material can also be mixed. As these materials, as auxiliary conductive materials, carbonaceous fine particles such as graphite, carbon black and acetylene black, carbon fibers such as vapor-grown carbon fibers and carbon nanotubes, conductive materials such as polyaniline, polypyrrole, polythiophene, polyacetylene and polyacene are used. A polymer gel electrolyte, a polymer solid electrolyte, and the like. As a ratio of these materials in an electrode, 10-80 mass% is preferable.

[3] Binder A binder can also be used to strengthen the connection between the constituent materials of the electrode. Examples of such binders include polytetrafluoroethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene / butadiene copolymer rubber, polypropylene, and polyethylene. Resin binders such as polyimide and various polyurethanes. As a ratio of these materials in an electrode, 5-30 mass% is preferable.

[4] Catalyst In order to perform the electrode reaction more smoothly, a catalyst that assists the redox reaction can be used. Examples of such catalysts include conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyacene, basic compounds such as pyridine derivatives, pyrrolidone derivatives, benzimidazole derivatives, benzothiazole derivatives, and acridine derivatives, metal ion complexes, and the like. Can be mentioned. The ratio of these materials in the electrode is preferably 10% by mass or less.

[5] Current collector and separator As the negative electrode current collector and the positive electrode current collector, foils made of nickel, aluminum, copper, gold, silver, aluminum alloy, stainless steel, carbon, etc., metal flat plates, mesh shapes, etc. Things can be used. Further, the current collector may have a catalytic effect, or the electrode active material and the current collector may be chemically bonded. On the other hand, a separator such as a porous film or non-woven fabric made of polyethylene, polypropylene, or the like can be used so that the positive electrode and the negative electrode are not in contact with each other.

[6] Electrolyte In the present invention, the electrolyte performs charge carrier transport between the negative electrode and the positive electrode, and generally has an ionic conductivity of 10 ⁻⁵ to 10 ⁻¹ S / cm at 20 ° C. Preferably it is. As the electrolyte, for example, an electrolytic solution in which an electrolyte salt is dissolved in a solvent can be used. Examples of the electrolyte salt include LiPF ₆ , LiClO ₄ , LiBF ₄ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, Li (C ₂ F ₅ SO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) ₃ C Conventionally known materials such as Li (C ₂ F ₅ SO ₂ ) ₃ C can be used.

  When a solvent is used for the electrolytic solution, examples of the solvent include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, tetrahydrofuran, dioxolane, sulfolane, dimethylformamide, dimethylacetamide, N-methyl- An organic solvent such as 2-pyrrolidone can be used. These solvents can be used alone or in admixture of two or more.

  Furthermore, in the present invention, a solid electrolyte can be used as the electrolyte. Polymer compounds used in these solid electrolytes include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-ethylene copolymer, vinylidene fluoride-monofluoroethylene copolymer, vinylidene fluoride. -Vinylidene fluoride polymers such as trifluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, and acrylonitrile-methyl methacrylate copolymer Polymer, acrylonitrile-methyl acrylate copolymer, acrylonitrile-ethyl methacrylate copolymer, acrylonitrile-ethyl acrylate copolymer, acrylonitrile-methacrylic acid copolymer, acrylonitrile-acrylic Le acid copolymers, acrylonitrile - vinyl acetate copolymer, acrylonitrile-based polymer, further polyethylene oxide, ethylene oxide - propylene oxide copolymers, and polymers of these acrylates body or methacrylate body thereof. These polymer compounds may be used in the form of a gel containing an electrolytic solution, or only a polymer compound containing an electrolyte salt may be used as it is.

[7] Battery shape In the present invention, the shape of the battery is not particularly limited, and a conventionally known battery can be used. Examples of the battery shape include an electrode laminate or a wound body sealed with a metal case, a resin case, or a laminate film made of a metal foil such as an aluminum foil and a synthetic resin film, etc. A mold, a coin mold, and a sheet mold are used, but the present invention is not limited to these.

[8] Battery Manufacturing Method The battery manufacturing method is not particularly limited, and a method appropriately selected according to the material can be used. For example, a solvent is added to an electrode active material, a conductivity-imparting agent, etc. to form a slurry, which is then applied to an electrode current collector, and after heating or volatilizing the solvent at room temperature, it is laminated or wound with a counter electrode and a separator in between. It is a method of wrapping with a body and injecting an electrolyte and sealing. Solvents for slurrying include ether solvents such as tetrahydrofuran and diethyl ether, amine solvents such as N-methylpyrrolidone, aromatic hydrocarbon solvents such as benzene, toluene and xylene, and aliphatic solvents such as hexane and heptane. Examples thereof include hydrocarbon solvents and halogenated hydrocarbon solvents such as chloroform and dichloromethane. In addition, as a method for manufacturing an electrode, there is a method in which an electrode active material, a conductivity-imparting agent, and the like are kneaded in a dry method and then thinned and laminated on an electrode current collector.

When manufacturing a battery, there are a case where a battery is manufactured using the compound (a) itself as an electrode active material and a case where a battery is manufactured using a compound which changes to the compound (a) by an electrode reaction. is there. Such electrodes compound that converts to the compound by the reaction as an example of (a), the compound (a) cationic material to oxidize and PF ₆ ^- or BF ₄ ^-, etc. salt comprising the electrolyte anions such like.

  In the present invention, a conventionally known method can be used as a method for manufacturing a battery for other manufacturing conditions such as taking out leads from electrodes and packaging.

  Hereinafter, although the detail of this invention is concretely demonstrated by a synthesis example and an Example, this invention is not limited to these Examples.

(Synthesis Example 1)
The polymer (6) (a homopolymer having a unit represented by the following formula (6) in the molecule) was synthesized from isopropylsilylacetylene by a four-step reaction.

  [1] Synthesis of 1-bromo-2-isopropylsilylacetylene

To 691 mg (3.79 mmol) of isopropylsilylacetylene, 742 mg (3.81 mmol) of N-bromosuccinimide, 3.4 mg (0.0201 mmol) of AgNO ₃ and 23 ml of acetone were added and stirred at room temperature for 2 hours. After purification by column chromatography (eluent hexane), 971 mg (yield 98.1%) of 1-bromo-2-isopropylsilylacetylene was obtained as a colorless transparent liquid.

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.12 to 1.01 (m, 21H)
¹³ C-NMR (CDCl ₃ ): δ (ppm) 83.5, 61.7, 18.5, 11.3
IR (cm ⁻¹ ): 2132 (ν _C ≡ _C )
Mass (m / z): 261.27 (calculated value), 260, 262 (measured value)
[2] Synthesis of 1-dianisylamino-2-isopropylsilylacetylene

In the ampoule, 120 mg (0.523 mmol) of dianisylamine, 137 mg (0.523 mmol) of 1-bromo-2-isopropylsilylacetylene, 11.9 mg (0.0523 mmol) of Pd (OAc) _2, 44.2 mg (0.0784 mmol) of DPEphos , Cs ₂ CO ₃ 340 mg (1.05 mmol), a stir bar, and 2 ml of distilled toluene were added. After sufficient freezing and degassing, the ampule was burned and sealed. The reaction was carried out at 110 ° C. for 18 hours with sufficient stirring. Purification by preparative high performance liquid chromatography (eluent chloroform) gave 110 mg (yield 47.6%) of 1-dianisylamino-2-isopropylsilylacetylene as colorless plate crystals.

¹ H-NMR (CDCl ₃ ): δ (ppm) 7.20-6.84 (m.8H), 3.79 (s, 6H), 1.12-1.02 (m, 21H)
¹³ C-NMR (CDCl ₃ ): δ (ppm) 156.0, 136.9, 114.4, 103.4, 63.1, 55.6, 18.8, 11.6
IR (cm ⁻¹ ): 2149 (ν _C ≡ _C )
Mass (m / z): 409.24 (calculated value), 409 (measured value)
[3] Synthesis of dianisylaminoacetylene

  1.24 ml of distilled tetrahydrofuran was added to 51 mg (0.124 mmol) of 1-dianisylamino-2-isopropylsilylacetylene. While cooling to −10 ° C., 64.8 mg (0.248 mmol) of TBFA dissolved in 0.248 ml of tetrahydrofuran was added and reacted at −10 ° C. with sufficient stirring for 20 minutes, and then allowed to react for 2 hours while returning to room temperature. After purification by preparative high performance liquid chromatograph (eluent chloroform), 15.1 mg (yield 49.0%) of dianisylaminoacetylene was obtained as colorless plate crystals.

¹ H-NMR (CDCl ₃ ): δ (ppm) 7.18-6.81 (m, 8H), 3.79 (s, 6H), 2.85 (s, 1H)
¹³ C-NMR (CDCl ₃ ): δ (ppm) 156.3, 136.7, 122.1, 119.5, 114.5, 55.6, 53.9
IR (cm ⁻¹ ): 2123 (ν _C ≡ _C )
Mass (m / z): 253.3 (calculated value), 253 (measured value)
[4] Polymerization of dianisylaminoacetylene

NbCl ₅ 2.46 mg (0.00395 mmol) and Ph ₄ Sn 1.69 mg (0.00396 mmol) were added to 10.0 mg (0.0395 mmol) of dianisylaminoacetylene, and the atmosphere was replaced with nitrogen. Under a nitrogen atmosphere, 0.197 ml of toluene was added and allowed to react with stirring for 24 hours. After the reaction, it was diluted with chloroform and purified by reprecipitation into hexane to obtain poly (dianisylaminoacetylene) as a brown powder. The obtained polymer had a number average molecular weight of 2600 (polystyrene conversion) and a dispersity (weight average molecular weight / number average molecular weight) of 1.3 (yield 6.4 mg, yield 64%).

(Synthesis Example 2)
The polymer (12) (a homopolymer having a unit represented by the following formula (12) in the molecule) was synthesized from dianisylaminoacetylene in a two-step reaction.

  [1] Synthesis of 1-dianisylamino-1-propyne

  To 20 mg (0.0790 mmol) of dianisylaminoacetylene, 0.790 ml of tetrahydrofuran was added and cooled to −78 ° C. with dry ice / methanol. 0.750 ml of n-BuLi was gradually added dropwise and reacted for 1 hour using a calcium chloride aqueous solution while raising the reaction temperature to −40 ° C. Thereafter, 44.7 mg of iodomethane was added and stirred for 2 hours while returning to room temperature. After purification by HPLC, 12.1 mg (yield 98.1%) of 1-dianisylamino-1-propyne was obtained as colorless plate crystals.

¹ H-NMR (CDCl ₃ ): δ (ppm) 6.82-6.35 (m.8H), 3.73 (s, 6H), 2.16 (s, 3H)
¹³ C-NMR (CDCl ₃ ): δ (ppm) 155, 137, 129, 113, 82.1, 76.9, 55.5, 30.9
IR (cm ⁻¹ ): 2215 (ν _C ≡ _C )
Mass (m / z): 267.16 (calculated value), 267 (measured value)
[2] Polymerization of 1-dianisylamino-1-propyne

TaCl ₅ 4.01 mg (0.0112 mmol) and Ph ₄ Sn 4.78 mg (0.0112 mmol) were placed in 1-dianisylamino-1-propyne 30.0 mg (0.112 mmol), and the atmosphere was replaced with nitrogen. Under a nitrogen atmosphere, 0.56 ml of toluene was added and reacted with stirring for 24 hours. After the reaction, it was diluted with chloroform and purified by reprecipitation into hexane to obtain a polymer as a brown powder. The polymer obtained had a number average molecular weight of 19000 (polystyrene conversion) and a dispersity (weight average molecular weight / number average molecular weight) of 1.4 (yield 10.8 mg, yield 36%).

Example 1
Polymer (6) synthesized in Synthesis Example 1 (number average molecular weight 2600 (polystyrene conversion), dispersity (weight average molecular weight / number average molecular weight) 1.3) 300 mg, graphite powder 600 mg, polytetrafluoroethylene resin binder 100 mg Weighed and kneaded using an agate mortar. A mixture obtained by dry-mixing for about 10 minutes was subjected to roller stretching under pressure to form a thin film having a thickness of about 120 μm. This was dried overnight at 80 ° C. in a vacuum, and then punched into a circle with a diameter of 12 mm to form a coin battery electrode. The mass of this electrode was 11.83 mg.

Next, the obtained electrode was immersed in an electrolytic solution, and the electrolytic solution was infiltrated into voids in the electrode. As the electrolytic solution, an ethylene carbonate / diethyl carbonate mixed solution (mixing volume ratio 3: 7) containing 1.0 mol / L LiPF ₆ electrolyte salt was used. The electrode impregnated with the electrolytic solution was placed on the positive electrode current collector, and a polypropylene porous film separator impregnated with the electrolytic solution was laminated thereon. Further, a lithium-bonded copper foil serving as a negative electrode was laminated, and aluminum sheaths (made by Hohsen) were superposed from the positive electrode side and the negative electrode side in a state in which an insulating packing was disposed around. This was applied with a caulking machine to form a sealed coin-type battery using the polymer (6) as the positive electrode active material and metallic lithium as the negative electrode active material.

  The coin battery produced as described above was charged with a constant current of 0.1 mA until the voltage reached 4.2 V, and then discharged to 2.8 V with a constant current of 0.1 mA. As a result, the voltage became almost constant for 2 hours and 30 minutes around 3.5 V, and then dropped rapidly. The discharge capacity per electrode active material was 75.1 mAh / g. Similarly, charging / discharging was repeated 50 times in the range of 4.2 to 2.8V. As a result, in all 50 charge / discharge cycles, the voltage became constant at around 3.3 V during discharge, and (50th discharge capacity) / (1st discharge capacity) was 96.1%.

  Next, the coin battery was charged with a constant current of 0.1 mA until the voltage reached 4.2 V, and then discharged with a constant current of 5.0 mA. As a result, the voltage became constant around 3.1 V, and then dropped rapidly. (Discharge capacity at 5.0 mA discharge) / (discharge capacity at 0.1 mA discharge) was 72.5%.

(Example 2)
Polymer (8) (homopolymer having a unit represented by the following formula (8) in the molecule, number average molecular weight is 32000 (polystyrene conversion), dispersity (weight average molecular weight) by the same synthesis scheme as in Synthesis Example 1 / Number average molecular weight) 1.6) was synthesized, and a coin battery was produced in the same manner as in Example 1 using the obtained polymer (8). The positive electrode weight of this coin battery was 10.31 mg.

  The coin battery was charged with a constant current of 0.1 mA until the voltage reached 4.2 V, and then discharged to 2.8 V with a constant current of 0.1 mA. As a result, the voltage became almost constant for 2 hours near 3.5 V, and then dropped rapidly. The discharge capacity per electrode active material was 63.0 mAh / g. Similarly, charging / discharging was repeated 50 times in the range of 4.2 to 2.8V. As a result, in all 50 charge / discharge cycles, the voltage was constant at around 3.3 V during discharge, and (50th discharge capacity) / (1st discharge capacity) was 98.2%.

  Next, the coin battery was charged with a constant current of 0.1 mA until the voltage reached 4.2 V, and then discharged with a constant current of 5.0 mA. As a result, the voltage became constant around 3.15 V and then dropped rapidly. (Discharge capacity at 5.0 mA discharge) / (discharge capacity at 0.1 mA discharge) was 80.0%.

(Example 3)
The polymer (9) (homopolymer having a unit represented by the following formula (9) in the molecule, number average molecular weight 42000 (polystyrene conversion), dispersity (weight average molecular weight / Number average molecular weight) 1.8) was synthesized, and a coin battery was produced in the same manner as in Example 1 using the obtained polymer (9). The positive electrode weight of this coin battery was 12.41 mg.

  The coin battery was charged with a constant current of 0.1 mA until the voltage reached 4.2 V, and then discharged to 2.8 V with a constant current of 0.1 mA. As a result, the voltage became almost constant for 3 hours near 3.3 V, and then dropped rapidly. The discharge capacity per electrode active material was 87.31 mAh / g. Similarly, charging / discharging was repeated 50 times in the range of 4.2 to 2.8V. As a result, in all 50 charge / discharge cycles, the voltage was constant at around 3.3 V during discharge, and (50th discharge capacity) / (1st discharge capacity) was 91.6%.

  Next, the coin battery was charged with a constant current of 0.1 mA until the voltage reached 4.2 V, and then discharged with a constant current of 5.0 mA. As a result, the voltage became constant around 3.10 V and then dropped rapidly. (Discharge capacity at 5.0 mA discharge) / (discharge capacity at 0.1 mA discharge) was 77.0%.

Example 4
Using the polymer (12) synthesized in Synthesis Example 2 (number average molecular weight 19000 (polystyrene conversion), dispersity (weight average molecular weight / number average molecular weight) 1.4), a coin battery was produced in the same manner as in Example 1. Produced. The positive electrode weight of this coin battery was 11.99 mg.

  The coin battery was charged with a constant current of 0.1 mA until the voltage reached 4.2 V, and then discharged to 2.8 V with a constant current of 0.1 mA. As a result, the voltage became substantially constant at around 3.3 V for 2 hours and 30 minutes, and then dropped rapidly. The discharge capacity per electrode active material was 78.91 mAh / g. Similarly, charging / discharging was repeated 50 times in the range of 4.2 to 2.8V. As a result, in all 50 charge / discharge cycles, the voltage became constant at around 3.3 V during discharge, and (50th discharge capacity) / (1st discharge capacity) was 96.2%.

  Next, the coin battery was charged with a constant current of 0.1 mA until the voltage reached 4.2 V, and then discharged with a constant current of 5.0 mA. As a result, the voltage became constant around 3.15 V and then dropped rapidly. (Discharge capacity at 5.0 mA discharge) / (discharge capacity at 0.1 mA discharge) was 82.8%.

(Comparative Example 1)
A coin battery was manufactured in the same manner as in Example 1 except that the polymer (6) was not used and the graphite powder was increased to 700 mg instead. The produced battery was charged and discharged in the same manner as in Example 1. As a result, no flat voltage portion was observed during discharge, the voltage dropped rapidly, and the battery did not operate sufficiently.

(Comparative Example 2)
A coin battery was manufactured in the same manner as in Example 1, except that the polymer (6) was not used and 300 mg of LiCoO ₂ was used instead. The produced battery was charged and discharged in the same manner as in Example 1, and the discharge capacity per electrode active material was calculated to be 96 mAh / g. (Discharge capacity at 5.0 mA discharge) / (discharge capacity at 0.1 mA discharge) was 26.8%.

It is a conceptual diagram which shows an example of a structure of the battery of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Aluminum exterior 2 Insulation packing 3 Negative electrode collector 4 Negative electrode 5 Separator 6 Positive electrode 7 Positive electrode collector

Claims (6)

The electrode active material containing the high molecular compound which has a unit represented by following formula (2) in a molecule | numerator.

(In Formula (2) , R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and trifluoromethyl. Represents either a group or a fluorine atom.)   A battery comprising the electrode active material according to claim 1 as an electrode active material of at least one of a positive electrode and a negative electrode. In a battery using an electrode reaction of an electrode active material, at least one of the positive electrode and the negative electrode reacts with a polymer compound having a unit represented by the following formula (2) in the molecule as a reactant or product. A battery characterized by an electrode reaction.

(In Formula (2) , R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and trifluoromethyl. Represents either a group or a fluorine atom.) The electrode active material, the battery according to claim 2 or 3 as a cathode active material. Cell according to any one of claims 2-4 which is a lithium battery. The polymer which has a unit represented by following formula (3) in a molecule | numerator.

(In Formula (3), R ^{1 ′} represents a hydrogen atom or a methyl group, and R ^{2 ′} and R ^{3 ′} each independently represents a hydrogen atom or a methoxy group.)

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