JP2010239097A - Electrode active material, and electrode using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrode active material affording an electrochemical element high in capacity and energy density and favorable in life characteristics. <P>SOLUTION: The electrode active material is constituted of a precisely polymerized polyfluorene derivative derived from a precisely polymerized polyfluorene in which fluorene rings which constitute polyfluorene are substantially polymerized at 2-position and 7-position and a fluorene ring at a chain terminal has a halogen substitute and is characterized in that the precisely polymerized polyfluorene derivative is a derivative obtained by substituting a phenyl group or a fluorenyl group for the halogen substitute of the fluorene ring at the chain terminal of the precisely polymerized polyfluorene. An electrical double layer capacitor having an electrode containing a conventional conductive polymer is shorter in service life than an electrical double layer capacitor having an electrode containing a carbon material. The electrical double layer capacitor having an electrode containing the electrode active material exhibits the life characteristics equal to that of the capacitor having the electrode containing the carbon material. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an electrode active material that can provide an electrochemical element having a high operating voltage, a high capacity, and a high energy density, and an electrode using the electrode active material.

  Expectations for low-emission vehicles such as electric vehicles and hybrid vehicles to replace gasoline and diesel vehicles from the viewpoint of reducing oil consumption, mitigating air pollution, and reducing emissions of carbon dioxide, which causes global warming. It is growing. As a motor drive power source in such a low pollution vehicle, an electrochemical element such as a secondary battery or an electric double layer capacitor having a high energy density and a high output density is used.

  Secondary batteries include batteries using an aqueous electrolyte and batteries using a non-aqueous electrolyte (organic electrolyte).

  Examples of batteries using acidic or alkaline aqueous electrolyte include lead batteries, nickel / cadmium batteries, nickel metal hydride batteries, and proton batteries. Since these secondary batteries have an electrolysis voltage of water of 1.23 V, a higher operating voltage cannot be obtained. As a power source for an electric vehicle, a high voltage of about 200V is required. To obtain this voltage, many batteries must be connected in series, which is disadvantageous for reducing the size and weight of the power source. is there. However, since the aqueous electrolyte has high ionic conductivity, it has excellent output characteristics that a large current can be obtained during charging and discharging.

On the other hand, lithium ion secondary batteries are well known as batteries using nonaqueous electrolyte solutions. In general, this battery uses a carbon material that occludes and releases lithium ions as a negative electrode, a lithium layered compound such as lithium cobaltate (LiCoO ₂ ) as a positive electrode, and a lithium salt such as lithium hexafluorophosphate (LiPF ₆ ). A solution dissolved in an organic solvent such as ethylene carbonate or propylene carbonate is used as an electrolytic solution. Since such a lithium ion secondary battery has a high electrolysis voltage of the organic solvent, 3.6 V can be obtained as an average operating voltage, and the energy density is also high. However, since the charge / discharge reaction is occlusion and release of lithium ions in the electrode, the output characteristics are inferior, and it is disadvantageous as a power source for an electric vehicle that requires a large instantaneous current.

  The electric double layer capacitor uses a polarizable electrode such as activated carbon as positive and negative electrodes, and uses an electric double layer generated at the interface between the electrode surface and the electrolytic solution as a capacitance. An electric double layer capacitor has a high output density, can be rapidly charged and discharged, and has little capacity deterioration even after repeated charging and discharging. This is because in an electric double layer capacitor, electrolyte ions move only in the electrolytic solution along with charging / discharging and are adsorbed / desorbed to / from the electrode interface, and do not involve an electrochemical reaction as in a battery.

  Also in the electric double layer capacitor, there are a capacitor using an aqueous electrolyte and a capacitor using a non-aqueous electrolyte (organic electrolyte).

  Since the operating voltage of an electric double layer capacitor is mainly determined by the electrolysis voltage of the electrolyte, the capacitor using an aqueous electrolyte has a higher operating voltage than the capacitor using a non-aqueous electrolyte (organic electrolyte). It is disadvantageous in terms. However, it has the advantage of high power density and safety.

  On the other hand, an electric double layer capacitor using a non-aqueous electrolyte solution in which a quaternary onium salt such as boron tetrafluoride or phosphorus hexafluoride is dissolved in an organic solvent such as propylene carbonate has an operating voltage of an aqueous electrolyte solution. It is higher than the capacitor, but lower than the secondary battery. In addition, the energy density due to the electric double layer capacity is lower than that of the secondary battery, and the power source of the electric vehicle is greatly insufficient.

  In order to improve such problems, studies on electrode active materials used in electrochemical devices are underway.

  Patent Document 1 (Japanese Patent Application Laid-Open No. 2003-297362) discloses a positive electrode mainly composed of a p-doped conductive polymer, a negative electrode mainly composed of a carbon material capable of inserting and extracting lithium ions, and a lithium salt. A hybrid secondary power source having an organic electrolyte solution is proposed. A secondary power source using a polythiophene having a weight average molecular weight of 50000, a poly (3-methylthiophene) having a weight average molecular weight of 80000, etc. as a positive electrode, an operating voltage of 4.0 V, and a secondary power source using activated carbon as a positive electrode A secondary power source having a capacity equal to or higher than that of the battery and having high charge / discharge cycle reliability is obtained.

  Patent Document 2 (Japanese Patent Application Laid-Open No. 6-104141) discloses an electrolytic double layer for the purpose of increasing the capacity and reducing the internal resistance of an electric double layer capacitor having an electrode prepared using a conductive polymer powder paste. An electric double layer capacitor using a conductive polymer film obtained by a legal method as a polarizable electrode is proposed. By using the polypyrrole film obtained by the electrolytic polymerization method, an electric double layer capacitor having an operating voltage of 2.6 V and a higher capacity than an electric double layer capacitor having an electrode using a powder paste has been obtained.

  In order to improve the low energy density of the electric double layer capacitor, an electrochemical capacitor using an additional capacitance due to a redox reaction or a charge transfer reaction on the electrode surface in addition to the electric double layer capacitance has been studied. Yes. As an electrode active material for such an electrochemical capacitor, charge transfer by exchange of π-electrons with metal oxides such as ruthenium oxide, manganese oxide, nickel oxide, etc. where an oxidation-reduction reaction easily occurs, and anions and cations of electrolytes Conductive polymers such as polyaniline, polythiophene, polypyrrole and the like in which the above occurs relatively easily have been studied.

  Patent Document 3 (Japanese Unexamined Patent Publication No. 2000-315527) discloses a conductive polymer containing a thin film of triphenylamine as a repeating unit as a positive electrode and a thin film of 2,2′-bipyridine as a repeating unit. A non-aqueous electrochemical capacitor having a negative electrode made of a conductive polymer has been proposed, and a non-aqueous electrochemical capacitor exhibiting an operating voltage of up to 2.7 V and having an energy density more than three times that of an electric double layer capacitor has been obtained. Yes.

  Further, Patent Document 4 (Japanese Patent Laid-Open No. 2006-48974) discloses an electrode material made of polyfluorene or a derivative thereof, and the n-doped redox potential of the polyfluorene derivative is a conventional conductive polymer. The p-doped redox potential of polyfluorene or its derivatives is higher than that of conventional conductive polymers, indicating that this electrode material has high voltage characteristics. When poly (9,9-dimethylfluorene) obtained by polymerization using iron (III) chloride as a catalyst is used as an electrode active material, a secondary battery and an electrochemical capacitor using poly (3-methylthiophene) It shows that a secondary battery and an electrochemical capacitor having a higher operating voltage can be obtained.

  In addition, in the Japanese Patent Application No. 2008-033847 that is unpublished at the time of filing of the present application, the applicant referred to as “precisely polymerized polyfluorene” in which the fluorene ring of polyfluorene is substantially polymerized at the 2-position and the 7-position, Compared to polyfluorene in which the fluorene ring obtained by polymerization using iron (III) chloride as a catalyst is polymerized at irregular positions (hereinafter referred to as “bulk polymerized polyfluorene”), the capacity is greatly increased. Therefore, it was shown that an electrochemical device having a high operating voltage, a high capacity, and a high energy density can be obtained by using an electrode active material made of precision polymerized polyfluorene.

  On the other hand, since an electrode including a conductive polymer has a significantly poor lifetime characteristic compared to an electrode including a carbon material such as activated carbon or carbon nanotube, it has been impeded in practical use (Non-Patent Document 1 (Journal of The 1). (See Electrochemical Society, 150 (6), A747-A752 (2003).) The reason why the life characteristics are poor is that the polymer reacts chemically or electrochemically with the solvent or electrolyte during charge / discharge and deteriorates. Therefore, improvement of lifetime characteristics is being studied by improving the electrolyte (see Non-Patent Document 2 (Electrochimica Acta, 50, 2233-2237 (2005)).

JP 2003-297362 A JP-A-6-104141 JP 2000-315527 A JP 2006-48974 A

Journal of The Electrochemical Society, 150 (6), A747-A752 (2003) Electrochimica Acta, 50, 2233-2237 (2005)

  However, there is a constant demand for miniaturization and weight reduction of motor drive power supplies for electric vehicles, etc. Therefore, there is a strong demand for higher operating voltage, higher capacity, and higher energy density for electrochemical elements used as power supplies. In addition, a long-life electrochemical device is desired.

  Therefore, an object of the present invention is to provide an electrochemical element having a high operating voltage, high capacity, high energy density, and good lifetime characteristics, and higher capacity and higher than conventional conductive polymers. An electrode active material exhibiting voltage characteristics and good life characteristics and an electrode using the same are provided.

  The inventor examined in detail the cause of shortening the life of the electrode containing the conductive polymer, and the point that the polymer reacts chemically or electrochemically with the solvent or electrolyte during the charge and discharge reported so far. In addition, the inventors have come to the idea that impurities contained in the polymer, for example, halogens remaining at the polymer ends, cause the polymer deterioration to progress and deteriorate the life characteristics.

The “precisely polymerized polyfluorene” in which the fluorene ring of polyfluorene is substantially polymerized at the 2-position and the 7-position as shown in the above-mentioned Japanese Patent Application No. 2008-033847 by the applicant is exemplified in the following formula I: Although produced by the Yamamoto coupling method using a nickel catalyst or the Suzuki-Miyaura coupling method using a palladium catalyst exemplified in Formula II, the fluorene ring at the chain end of a precisely polymerized polyfluorene is produced due to the production method. Have a halogen substituent at the 2- or 7-position that is not bonded to the adjacent fluorene ring.

  And the inventor discovered that the said subject was solved by substituting the halogen substituent which remains in the fluorene ring of the chain | strand terminal of precision polymerization polyfluorene by a phenyl group or a fluorenyl group.

  Therefore, the electrode active material of the present invention is a precision polymerized polyfluorene in which the fluorene ring constituting the polyfluorene is polymerized substantially at the 2nd and 7th positions and the fluorene ring at the chain end has a halogen substituent. An electrode active material comprising at least one precision polymerized polyfluorene derivative derived from the above, wherein the precision polymerized polyfluorene derivative is a phenyl group or a fluorenyl group as a halogen substituent of the fluorene ring at the chain end of the precision polymerized polyfluorene. It is a derivative substituted with.

  Hereinafter, among the precisely polymerized polyfluorene derivatives, those in which the halogen substituent of the fluorene ring at the chain end of the precisely polymerized polyfluorene is substituted with a phenyl group are referred to as “precisely polymerized fluorene-terminated phenylene polymer”, which is a fluorenyl group. The one substituted with is represented as “precision polymerized fluorene-terminal fluorene polymer”.

  The term “substantially polymerized at the 2-position and the 7-position” is 90% or more, preferably 95% or more, more preferably 98% or more, particularly preferably the number of fluorene rings contained in polyfluorene. Means that 100% of the fluorene ring is bonded to the adjacent fluorene ring at the 2nd and 7th positions. The term “halogen substituent is substituted with a phenyl group or a fluorenyl group” means that 90% or more, preferably 95% or more, more preferably 98% or more, particularly preferably 100% of the halogen substituent is substituted. Means that

  In the present invention, the precisely polymerized fluorene-terminated phenylene polymer and the precisely polymerized polyfluorene used as the precursor of the precisely polymerized fluorene-terminated fluorene polymer have a fluorene ring polymerized substantially at the 2nd and 7th positions and a chain. As long as the terminal fluorene ring has a halogen substituent, the fluorene ring other than the chain end may be composed only of an unsubstituted fluorene ring and is not bonded to the fluorene ring in the chain end fluorene ring. In addition to the halogen substituent at the 2-position or the 7-position, one or more fluorene rings constituting the precisely polymerized polyfluorene may have a substituent at a position not involved in the polymerization. In the present invention, the fluorene ring of the precisely polymerized polyfluorene may have one or two substituents at the 9-position. The substituent at the 9-position does not decrease the electronic conductivity of the polymer, and the substituent increases the speed of the anion and cation doping and dedoping reactions and improves the output characteristics. The substituent at the 9-position consists of an alkyl group, a carboxyl group, a nitro group, a cyano group, an alkyl cyano group, a phenyl group, a halogen atom, a halogenated methyl group, a halogenated phenyl group, an alkylphenyl group, and an alkylhalogenated phenyl group. Preferably selected from the group.

  The present invention also provides an electrode having an active material layer containing an electrode active material composed of the above-mentioned precision polymerized fluorene-terminated phenylene polymer and / or precision polymerized fluorene-terminated fluorene polymer. Precision polymerized fluorene-terminated phenylene polymer and precision polymerized fluorene-terminated fluorene polymer have high capacity characteristics similar to precision polymerized polyfluorene, and have high voltage characteristics similar to precision polymerized polyfluorene, and also have a long life. Has characteristics. Therefore, the electrode of the present invention can be suitably used to construct an electrochemical device having a high operating voltage, a high capacity, a high energy density, and a long life characteristic. It can be suitably used as one of a pair of electrodes, as one of a pair of electrodes in an electric double layer capacitor, or as at least one of a pair of electrodes in an electrochemical capacitor. In particular, when the electrode of the present invention is used as an electrode for an electric double layer capacitor, the electric double layer capacitor having the same life characteristics as a conventional electric double layer capacitor using an electrode containing a carbon material such as activated carbon or carbon nanotube Is obtained.

  In the electrode of the present invention, the active material layer preferably contains at least one kind of carbon nanotube. Since carbon nanotubes have a high electrical conductivity, a composite with a high electrical conductivity can be obtained by compounding with an active material. Further, since the outer surface area is large, the contact surface with the active material is widened, and it is possible to impart conductivity with high efficiency. Furthermore, the carbon nanotubes themselves have a capacity in contact with the electrolyte solution. Therefore, by using a precision polymerized fluorene-terminated phenylene polymer and / or a precision polymerized fluorene-terminated fluorene polymer in combination with a carbon nanotube, an electrode having high capacity, low impedance characteristics and long life can be obtained. Obtainable.

  The precisely polymerized fluorene-terminated phenylene polymer and / or the precisely polymerized fluorene-terminated fluorene polymer is preferably supported on carbon nanotubes. Since the contact resistance between the carbon nanotube and the precisely polymerized fluorene-terminated phenylene polymer and / or the precisely polymerized fluorene-terminated fluorene polymer becomes small, an electrode having further excellent low impedance characteristics can be obtained.

  Precision polymerized fluorene-terminated phenylene polymer derived from precision polymerized polyfluorene in which the fluorene ring of the present invention is polymerized substantially at the 2-position and 7-position and the fluorene ring at the chain end has a halogen substituent An electrode active material composed of a precisely polymerized fluorene-terminated fluorene polymer has high capacity characteristics and high voltage characteristics, and also has good life characteristics.

  Therefore, an electrode having an active material layer containing the electrode active material of the present invention has a high operating voltage, a high capacity, a high energy density, and a good secondary battery life, electric double layer capacitor, Electrochemical elements such as electrochemical capacitors can be constructed.

It is a figure which shows the result of the lifetime evaluation test regarding the electrode of this invention, and the electrode of a comparative example.

  The electrode active material of the present invention comprises a precisely polymerized fluorene-terminated phenylene polymer and / or a precisely polymerized fluorene-terminated fluorene polymer. The electrode active material of the present invention may be a single material or a mixture of different precisely polymerized fluorene-terminated phenylene polymers and / or precisely polymerized fluorene-terminated fluorene polymers.

The precision polymerized fluorene-terminated phenylene polymer as the electrode active material of the present invention is produced by the method of Formula III using 2,7-dihalogenofluorene and halogenobenzene as starting materials, and is a precision polymerized fluorene-terminal fluorene polymer. Is prepared by the method of formula IV starting from 2,7-dihalogenofluorene and 2-halogenofluorene. In the methods of Formula III and Formula IV, the polymerization of precision polymerized polyfluorene and the reaction of halogenobenzene or 2-halogenofluorene on the terminal fluorene ring occur in parallel.

  Precision polymerized fluorene-terminated phenylene polymer and precision polymerized fluorene-terminated fluorene polymer precursor, which is a polymerized fluorene, are polymerized in the 2nd and 7th positions of the fluorene ring and the fluorene ring at the chain end. As long as it has a halogen substituent, the fluorene ring other than the chain end may be composed only of an unsubstituted fluorene ring, and it is not bonded to the fluorene ring in the fluorene ring at the chain end. In addition to the halogen substituent at the position, one or more fluorene rings constituting the precisely polymerized polyfluorene may have a substituent at a position not involved in the polymerization.

  The fluorene ring in the precision polymerized polyfluorene to be a precursor may have one or two substituents at the 9-position. The substituent at the 9-position does not decrease the electronic conductivity of the polymer, and the substituent increases the speed of the anion and cation doping and dedoping reactions and improves the output characteristics. The substituent at the 9-position consists of an alkyl group, a carboxyl group, a nitro group, a cyano group, an alkyl cyano group, a phenyl group, a halogen atom, a halogenated methyl group, a halogenated phenyl group, an alkylphenyl group, and an alkylhalogenated phenyl group. Preferably selected from the group.

  The substituent at the 9-position of the fluorene ring includes hydroxyl group; nitro group; amino group; alkylamino group such as methylamino, ethylamino, dimethylamino; cyano group; alkylcyano group such as methylcyano, ethylcyano, propylcyano; Halogen atom such as iodine, bromine, chlorine, fluorine; chain or branched alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl It is done. The alkyl group may be substituted by a hydroxyl group, a nitro group, an amino group, a cyano group, a halogen atom, an alkoxy group or an aryl group. Examples include chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl. , Trifluoromethyl, difluoroethyl, methoxyethyl, ethoxyethyl, benzyl, phenethyl, cumyl, hydrocinnamyl.

  Substituents at the 9-position of the fluorene ring further include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl; linear or branched -Like alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy.

  As the substituent at the 9-position of the fluorene ring, an alkenyl group such as ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclopentenyl group, cyclohexenyl group, cyclohexedienyl group; alkynyl group such as Ethynyl, propynyl, butynyl, pentynyl, hexynyl; aromatic groups such as phenyl, naphthyl, anthryl, phenalenyl, phenanthryl, pyrenyl; heterocyclic groups such as pyridyl, pyrazyl, pyrimidyl, pyrrolyl, indenyl, furyl, oxazolyl, thiazolyl, Thienyl is mentioned. These groups may be substituted by hydroxyl group, nitro group, amino group, cyano group, halogen atom, alkyl group, alkoxy group. Examples include styryl, tolyl, xylyl, mesityl, fluorophenyl, fluoromethylphenyl. , Methoxyphenyl, ethoxyphenyl, methylpyridyl, methylpyrazyl.

  As the substituent at the 9-position of the fluorene ring, a carboxyl group; an alkylcarbonyl group such as acetyl, ethylcarbonyl, propylcarbonyl, butylcarbonyl, pentylcarbonyl, hexylcarbonyl; an alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, Propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl; alkylcarbonyloxy groups such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy, butylcarbonyloxy, pentylcarbonyloxy, hexylcarbonyloxy; ester groups such as methyl ester, Ethyl ester, phenyl ester; carbamoyl group such as methylcarbamoyl, ethylcarbamoyl, E carbamoylmethyl and the like.

  Examples of the substituent at the 9-position of the fluorene ring include an alkyl group, a carboxyl group, a nitro group, a cyano group, an alkylcyano group, a phenyl group, a halogen atom, a halogenated methyl group, a halogenated phenyl group, an alkylphenyl group, and an alkylhalogen. Preferred is a phenyl group. Particularly, it is preferable that the substituent at the 9-position is a substituent having an alkyl group or a phenyl group, since the doping reaction and dedoping reaction of the anion and cation to be doped are further accelerated and the output characteristics are improved. Examples of the former include 9,9-dimethylfluorene and 9,9-dioctylfluorene, and examples of the latter include 9-methyl-9-phenylfluorene, 9-methyl-9-benzylfluorene, benzalfluorene, and benzhydrylidinefluorene. be able to. Among these, when doping or dedoping a large molecular cation, an alkyl group having 1 to 8 carbon atoms is preferable.

  The fluorene ring is also involved in binding to the adjacent fluorene ring in addition to the halogen substituent at the 2- or 7-position not bonded to the fluorene ring at the chain-end fluorene ring at positions other than the 9-position. It can have a substituent at a position that does not. Substituents at these positions can also be selected from the range of groups shown above for the 9-position substituent.

  Halogenobenzene subjected to a reaction with a precisely polymerized polyfluorene which is a precursor in the reaction of formula III or formula IV in order to constitute a precisely polymerized fluorene-terminated phenylene polymer and / or a precisely polymerized fluorene-terminated fluorene polymer Alternatively, 2-halogenofluorene may have no substituent other than the halogen substituent that contributes to the reaction with the precisely polymerized polyfluorene, and may be substituted with a halogen at a position other than the position where the halogen substituent is bonded. It may have a substituent other than a group.

  In the case of 2-halogenofluorene, as a substituent other than the halogen substituent involved in the reaction with the precisely polymerized polyfluorene, among the groups shown above for the substituent at the 9-position of the fluorene ring of the precisely polymerized polyfluorene, It can be selected from the range of groups other than.

  In the case of halogenobenzene, as substituents other than halogen substituents involved in the reaction with precision polymerized polyfluorene, hydroxyl group; nitro group; amino group; alkylamino group such as methylamino, ethylamino, dimethylamino; cyano Group; alkyl cyano group such as methyl cyano, ethyl cyano, propyl cyano; chain or branched alkyl group such as methyl, ethyl, propyl, butyl, pentyl and hexyl. The alkyl group may be substituted by a hydroxyl group, a nitro group, an amino group, a cyano group, a halogen atom, an alkoxy group or an aryl group. Examples include chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl. , Trifluoromethyl, difluoroethyl, methoxyethyl, ethoxyethyl, benzyl, phenethyl, cumyl, hydrocinnamyl.

  Substituents for halogenobenzene further include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; linear or branched alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyl. Oxy is mentioned.

  Substituents for halogenobenzene further include alkenyl groups such as ethenyl, propenyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclohexedienyl; alkynyl such as ethynyl, propynyl , Butynyl, pentynyl, hexynyl; aromatic groups such as phenyl, naphthyl, anthryl, phenalenyl, phenanthryl, pyrenyl; aryloxy groups such as phenoxy; heterocyclic groups such as pyridyl, pyrazyl, pyrimidyl, pyrrolyl, indenyl, furyl, Examples include oxazolyl, thiazolyl, and thienyl. These groups may be substituted by hydroxyl group, nitro group, amino group, cyano group, halogen atom, alkyl group, alkoxy group. Examples include styryl, tolyl, xylyl, mesityl, fluorophenyl, fluoromethylphenyl. , Methoxyphenyl, ethoxyphenyl, methylpyridyl, methylpyrazyl.

  Examples of the substituent of halogenobenzene further include formyl group; carboxyl group; alkylcarbonyl group such as acetyl, ethylcarbonyl, propylcarbonyl, butylcarbonyl, pentylcarbonyl, hexylcarbonyl; alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, Propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl; alkylcarbonyloxy groups such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy, butylcarbonyloxy, pentylcarbonyloxy, hexylcarbonyloxy.

  Substituents other than halogen substituents involved in the reaction with precision polymerized polyfluorene in halogenobenzene are preferably selected from the group consisting of alkyl groups, nitro groups, amino groups, cyano groups, carboxyl groups, and formyl groups. .

  The precisely polymerized fluorene-terminated phenylene polymer and / or the precisely polymerized fluorene-terminated fluorene polymer can be subjected to a doping treatment to impart conductivity. As the doping process, either a chemical doping process or an electrochemical doping process may be employed.

Acceptors for chemical doping treatment include halogens such as Br ₂ , I ₂ and Cl ₂ , Lewis acids such as SO ₃ , BF ₃ , PF ₅ , AsF ₅ and SbF ₅ , HNO ₃ and H ₂ SO _4. Protonic acids such as HClO ₄ , CF ₃ SO ₃ H, FSO ₃ H, transition metal halides such as FeCl ₃ , MoCl ₅ , WCl ₅ , SnCl ₄ , MoF ₅ , tetracyanoethylene, tetracyanoquinodimethane, chloranil, etc. Organic materials such as Li, Na, K, and Cs can be used as donors.

As an acceptor for electrochemical doping treatment, Lewis acids such as BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ and SbF ₆ ⁻ , and halogen anions such as I ⁻ , Br ⁻ and Cl ⁻ can be used. As the donor, alkali metal ions such as Li ⁺ , Na ⁺ , K ⁺ , and Cs ⁺ , alkylammonium ions such as tetraethylammonium ions and tetrabutylammonium ions, and the like can be used.

  The doping amount is not particularly limited, but is preferably 5 to 100 mol% per fluorene monomer unit, more preferably 20 to 50 mol% per fluorene monomer unit. Polymerization may be performed after doping in a stage before polymerization, a method of doping after polymerization may be used, or doping may be performed by charging after electrode formation.

  The positive electrode active material subjected to these doping treatments undergoes a discharge reaction and a reduction reaction due to anodization of the anion. Further, the negative electrode active material subjected to these doping treatments causes a discharge reaction and an oxidation reaction due to cation dedoping.

  In addition, in the precision polymerized polyfluorene precursor, an anion that can be covalently bonded to fluorene such as an alkyl sulfonate anion and an alkyl phosphonate anion is reacted with fluorene and polymerized, whereby the polymerized fluorene- A terminal phenylene polymer and / or a precision polymerized fluorene-terminal fluorene polymer can be used as a self-doped positive electrode active material, and in a precursor precision polymerized polyfluorene, a covalent bond with a fluorene such as a tertiary ammonium cation. By reacting a cation that can be reacted with fluorene and polymerizing it, the precisely polymerized fluorene-terminal phenylene polymer and / or the precisely polymerized fluorene-terminal fluorene polymer can be used as a self-doped negative electrode active material.

  The self-doped positive electrode active material causes a discharge reaction and a reduction reaction by doping of cations in the electrolytic solution. In addition, the self-doped negative electrode active material undergoes a discharge reaction and an oxidation reaction by doping anions in the electrolytic solution. When a self-doped positive electrode active material or negative electrode active material is used, the same type and amount of cations or anions are involved in the charge transfer reaction, so that the ion concentration in the electrolyte is kept constant, and therefore the conductivity of the electrolyte is constant. Is kept constant.

  An electrode for an electrochemical device is formed by providing an active material layer containing an electrode active material composed of the precision polymerized fluorene-terminated phenylene polymer and / or precision polymerized fluorene-terminated fluorene polymer of the present invention on a current collector. can do.

  As the current collector, a conductive material such as platinum, gold, nickel, aluminum, titanium, steel, or carbon can be used. As the shape of the current collector, any shape such as a film shape, a foil shape, a plate shape, a net shape, an expanded metal shape, and a cylindrical shape can be adopted.

  The active material layer is prepared by dissolving the above-mentioned precision polymerized fluorene-terminated phenylene polymer and / or precision polymerized fluorene-terminated fluorene polymer in a solvent such as chloroform, tetrahydrofuran, N-methylpyrrolidone, isopropyl alcohol and the like. You may form by apply | coating on a collector and drying. The film-shaped active material layer thus formed has a high capacity, is thin and uniform, and reduces the resistance of the electrode. Therefore, the IR drop during discharge can be reduced and the voltage of the electrode can be kept high. it can. In addition, a current collector is inserted into a solution of a comonomer for forming a precisely polymerized fluorene-terminated phenylene polymer and / or a precisely polymerized fluorene-terminated fluorene polymer, and the active material layer is polymerized on the current collector. It may be formed.

  Further, the active material layer may be formed using a mixed material obtained by mixing a binder and a conductive material with the above-described precision polymerized fluorene-terminal phenylene polymer and / or precision polymerized fluorene-terminal fluorene polymer.

  As the binder, known binders such as polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, polyvinyl fluoride, and carboxymethyl cellulose can be used. The content of the binder is preferably 1 to 20% by mass with respect to the total amount of the active material layer. When it is 1% by mass or less, the strength of the active material layer is not sufficient, and when it is 20% by mass or more, electrochemical characteristics such as capacity are insufficient.

  The conductive material may include known conductive materials such as carbon materials such as carbon black, natural graphite and artificial graphite, metal powders such as nickel and iron, and conductive oxides such as ITO. The content of these conductive materials is preferably 1 to 20% by mass with respect to the total amount of the active material layer. When the content is 1% by mass or less, the conductivity of the active material layer is insufficient, and when the content is 20% by mass or more, electrochemical characteristics such as capacity are insufficient.

  Other active materials may be further mixed in the active material layer as necessary. For example, other electrode active materials, for example, electron conductive polymers such as polythiophene, polypyrrole, and polyacene can be included. The amount of the other additive material is preferably 20% by mass or less based on the total amount of the active material layer. When it is 20% by mass or more, electrochemical characteristics such as capacity become insufficient.

  The electrode using the above-mentioned mixed material is obtained by dispersing the electrode active material of the present invention, a conductive material, and optionally other additive substances in a varnish in which a binder is dissolved, and collecting the obtained dispersion by a doctor blade method or the like. It can also be created by coating on top and drying. Alternatively, the obtained mixed material may be sandwiched between a net-like current collector to form an electrode.

  In a preferred form, the active material layer includes a precisely polymerized fluorene-terminated phenylene polymer and / or a precisely polymerized fluorene-terminated fluorene polymer and a carbon nanotube. As carbon nanotubes, carbon nanotubes obtained by arc discharge method, laser evaporation method, chemical vapor deposition (CVD) method, etc. can be used, and both single-walled carbon nanotubes and multi-walled carbon nanotubes can be used. These may be used in combination. Since carbon nanotubes have a high electrical conductivity, a composite with a high electrical conductivity can be obtained by compounding with an active material. In addition, since the outer surface area is large, the contact surface with the active material is widened, and conductivity can be imparted with high efficiency. Furthermore, the carbon nanotubes themselves have a capacity in contact with the electrolyte solution. Therefore, by using the precision polymerized fluorene-terminated phenylene polymer and / or the precision polymerized fluorene-terminated fluorene polymer in combination with carbon nanotubes, it has high capacity characteristics, high voltage characteristics, long life characteristics and low impedance characteristics. An electrode is obtained.

  An active material layer can be formed by mixing a precisely polymerized fluorene-terminated phenylene polymer and / or a precisely polymerized fluorene-terminated fluorene polymer and a carbon nanotube. At this time, if necessary, the active material layer may be formed by mixing both using a dispersion medium and then drying. However, it is particularly preferable to form an active material layer by supporting a precisely polymerized fluorene-terminated phenylene polymer and / or a precisely polymerized fluorene-terminated fluorene polymer on a carbon nanotube. The carbon nanotubes are immersed in a solution prepared by dissolving a precisely polymerized fluorene-terminated phenylene polymer and / or a precisely polymerized fluorene-terminated fluorene polymer in a solvent such as chloroform, tetrahydrofuran, N-methylpyrrolidone, isopropyl alcohol, and the like for a predetermined time. After the elapse of time, the carbon nanotubes can be collected by filtration and dried. After drying, a film of a precisely polymerized fluorene-terminated phenylene polymer and / or a precisely polymerized fluorene-terminated fluorene polymer is formed on the surface of the carbon nanotube. This film has a high capacity, is thin, uniform and has low resistance, and has good adhesion between the carbon nanotube and the film of the precisely polymerized fluorene-terminated phenylene polymer and / or the precisely polymerized fluorene-terminated fluorene polymer. Since the contact resistance is small, the IR drop during discharge is further reduced, and the voltage of the electrode can be kept higher.

  The mass ratio between the precisely polymerized fluorene-terminated phenylene polymer and / or the precisely polymerized fluorene-terminated fluorene polymer and the carbon nanotube is generally in the range of 9: 1 to 1: 9, preferably 8: 2-2. : 8 range. Beyond this range, the electrochemical properties become insufficient.

  After molding an active material layer containing a precisely polymerized fluorene-terminated phenylene polymer and / or a precisely polymerized fluorene-terminated fluorene polymer and a carbon nanotube into a predetermined shape such as a sheet, the obtained molded product and a current collector, Can be joined to obtain an electrode. For example, an electrode can be obtained by pressure-bonding the obtained molded body on a current collector. Also at this time, a binder or the like may be added as necessary.

  The electrode of the present invention can be suitably used in an electrochemical device having a pair of electrodes, a separator disposed between the electrodes, and an electrolyte solution.

  As a separator used for an electrochemical element, a polyolefin fiber nonwoven fabric, a glass fiber nonwoven fabric, etc. are used suitably, for example. There are a nonaqueous electrolytic solution and an aqueous electrolytic solution as the electrolytic solution, and they are appropriately selected according to the application.

  As the solvent for the non-aqueous electrolyte, electrochemically stable ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, sulfolane, 3-methyl sulfolane, γ-butyrolactone, acetonitrile, and dimethoxyethane, N-methyl-2-pyrrolidone, dimethylformamide or a mixture thereof can be preferably used.

As a solute of the nonaqueous electrolytic solution, a salt that generates lithium ions when dissolved in an organic electrolytic solution can be used without any particular limitation. For _{example, LiPF 6, LiBF 4, LiClO} 4, LiN (CF 3 SO 2) 2, LiCF 3 SO 3, LiC (SO 2 CF 3) 3, LiN (SO 2 C 2 F 5) 2, LiAsF 6, LiSbF 6 Or a mixture thereof can be preferably used. Further, a quaternary ammonium salt or a quaternary phosphonium salt having a quaternary ammonium cation or a quaternary phosphonium cation can be used as a solute of the nonaqueous electrolytic solution. For example, a cation represented by R ¹ R ² R ³ R ⁴ N ⁺ or R ¹ R ² R ³ R ⁴ P ⁺ (where R ¹ , R ² , R ³ and R ⁴ are alkyl having 1 to 6 carbon atoms) Group), PF ₆ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , N (CF ₃ SO ₃ ) ₂ ⁻ , CF ₃ SO ₃ ⁻ , C (SO ₂ CF ₃ ) ₃ ⁻ , N (SO ₂ C ₂ A salt composed of an anion composed of F ₅ ) ₂ ⁻ , AsF ₆ ^— or SbF ₆ ^— , or a mixture thereof can be suitably used. In particular, a salt using PF ₆ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ or N (CF ₃ SO ₃ ) ₂ ⁻ as the anion is preferable as the solute.

  Examples of the solute cations in the acidic, neutral or alkaline aqueous electrolyte include cations of alkali metals such as sodium and potassium, and protons. Solute anions in aqueous electrolytes include anions of inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorosilicic acid, saturated monocarboxylic acids, aliphatic carboxylic acids And anions of organic acids such as oxycarboxylic acid, p-toluenesulfonic acid, polyvinylsulfonic acid and lauric acid.

  The electrode of the present invention can be suitably used as at least one of a pair of electrodes in an electrochemical device. The precisely polymerized fluorene-terminated phenylene polymer and / or the precisely polymerized fluorene-terminated fluorene polymer has high voltage characteristics and high capacity characteristics as well as the precisely polymerized polyfluorene, and also has long life characteristics. Therefore, by using the electrode of the present invention as an electrode of any electrochemical device, an electrochemical device having a high operating voltage, a high capacity, a high energy density and good life characteristics can be obtained. Hereinafter, each case where the electrochemical element is a secondary battery, an electric double layer capacitor, or an electrochemical capacitor will be described.

(Secondary battery)
In the case of a lithium secondary battery, a non-aqueous electrolyte solution having a lithium salt as a solute is used as the electrolyte solution. Then, the electrode of the present invention is used as the positive electrode, and an electrode using an electrode active material that occludes and releases lithium ions such as conventional lithium metal or natural graphite, artificial graphite, and petroleum coke is used as the negative electrode. In the positive electrode of the present invention using a self-doped precision polymerized fluorene-terminated phenylene polymer and / or a precision polymerized fluorene-terminated fluorene polymer as an electrode active material, the same amount of lithium cation is involved in the charge / discharge reaction. As a result, the ion concentration of the electrolytic solution can be kept constant, and the conductivity of the electrolytic solution can be kept constant.

  In the lithium secondary battery having this configuration, the positive electrode of the present invention operates with a high p-doping redox potential, and the electrolysis voltage of the non-aqueous electrolyte is high, so that the operating voltage can be increased. High operating voltage, high capacity, high energy density, and good life characteristics.

  Further, when the electrode active material of the present invention is used for the negative electrode and a conventional layered compound such as lithium cobaltate or a conductive polymer such as polyaniline or polyphenylene is used as the electrode active material for the positive electrode, lithium ion intercalation is caused. Therefore, a lithium secondary battery with improved output characteristics and cycle characteristics, high operating voltage, high capacity, high energy density, and good life characteristics can be obtained.

  In the case of forming a proton battery, an acid aqueous solution having protons is used as an electrolytic solution. And the electrode of this invention is used as a positive electrode, and the negative electrode in well-known proton batteries, such as a quinoxaline type polymer, is used as a negative electrode. The proton battery of this configuration uses an electrolytic solution made of an acid aqueous solution, has good charge / discharge characteristics, high energy density, and the positive electrode of the present invention operates with a high p-doping redox potential, A maximum operating voltage of 1.2 V in a battery using an aqueous electrolyte is shown.

(Electric double layer capacitor)
As the electrolytic solution for the electric double layer capacitor, any of the above-mentioned non-aqueous electrolytic solution and aqueous electrolytic solution can be used. In an electric double layer capacitor using a non-aqueous electrolyte, the electrode of the present invention is used as a positive electrode or a negative electrode, and the other electrode is an electric material such as activated carbon, carbon fiber, phenol resin carbide, vinylidene chloride resin carbide, microcrystalline carbon, etc. An electrode having a double layer capacity is used. Since the positive electrode of the present invention operates in a state where the redox potential of p-doping is high, has a high capacity, and the electrolysis voltage of the non-aqueous electrolyte is high, the operating voltage can be increased. Thus, an electric double layer capacitor having a high capacity, a high energy density and good life characteristics can be obtained.

  In addition, in an electric double layer capacitor using an aqueous electrolyte, the electrode of the present invention is used as a positive electrode, and the other electrode is made of an electric two-layer such as activated carbon, carbon fiber, phenol resin carbide, vinylidene chloride resin carbide, and microcrystalline carbon. An electrode having a multilayer capacity is used. The electric double layer capacitor of this configuration can use acidic, neutral and alkaline electrolytes, has good charge / discharge characteristics, high energy density, and the positive electrode of the present invention has a p-doping redox potential. It operates at a high state and shows a maximum operating voltage of 1.2 V in an electric double layer capacitor using an aqueous electrolyte.

(Electrochemical capacitor)
As an electrolytic solution for the electrochemical capacitor, a nonaqueous electrolytic solution having a quaternary ammonium salt or a quaternary phosphonium salt as a solute is used. Then, the electrode of the present invention can be used as the positive electrode, and an electrode using a conventional conductive polymer such as polyacetylene, polyacene, or polyphenylene having redox reaction characteristics as the negative electrode can be used as the electrode active material. The electrochemical capacitor having this structure operates in a state where the positive electrode of the present invention has a high capacity and a high p-doping oxidation-reduction potential, so that the operating voltage is high, the capacity is high, and the energy density is high. Good long life characteristics.

  In addition, a conventional conductive polymer such as polyaniline, polyacetylene and polyphenylene having redox reaction characteristics or an electrode using a metal oxide such as ruthenium oxide, manganese oxide and nickel oxide as an electrode active material is used as a positive electrode, and this electrode is used as a negative electrode. The electrode of the invention can also be used. The electrochemical capacitor having this configuration operates in a state where the negative electrode of the present invention has a high capacity and a low n-doping oxidation-reduction potential, so that the operating voltage is high, the capacity is high, the energy density is high, and the life characteristics are high. It is good.

  Further, when the electrode of the present invention is used for both of a pair of electrodes in an electrochemical capacitor, the negative electrode has a low n-doping oxidation-reduction potential, the positive electrode has a high p-doping oxidation-reduction potential, and has high capacity characteristics. Therefore, an electrochemical capacitor having an unprecedented high operating voltage, high capacity, high energy density and good life characteristics can be obtained. In addition, when using self-doped precision polymerized fluorene-terminated phenylene polymer and / or precision polymerized fluorene-terminated fluorene polymer, the same type and amount of ions are involved in the reaction. The concentration is kept constant and the conductivity of the electrolyte is kept constant.

  Examples of the present invention are shown below, but the present invention is not limited to the following examples.

Example 1
1-1 Synthesis of precision polymerized fluorene-terminated phenylene polymer 2.2 mL of dimethylformamide with 1 mmol of 2,7-dibromofluorene, 1 mmol of bromobenzene, 0.05 mmol of NiCl ₂ , 3.1 mmol of Zn, 0.1 mmol Of triphenylphosphine and 0.05 mmol of 2,2-bipyridine were added and stirred at 80 ° C. for 20 hours to obtain a product. The product was filtered and washed to obtain a yellow powder precision polymerized fluorene-terminated phenylene polymer represented by the following formula V.

1-2 Preparation of Precision Polymerized Fluorene-Terminated Phenylene Polymer / Carbon Nanotube Composite Electrode 20 mg of precisely polymerized fluorene-terminated phenylene polymer powder and 10 mg of carbon nanotube powder (specific surface area: 200 m ² / g) in 50 mL of isopropyl alcohol And a dispersion was obtained by mechanical stirring. The dispersion was filtered to obtain a sheet of a precisely polymerized fluorene-terminated phenylene polymer / carbon nanotube composite in which a precisely polymerized fluorene-terminated phenylene polymer was supported on carbon nanotubes. The sheet was cut to about 2 cm ² and crimped to an aluminum current collector of the same size to obtain a precision polymerized fluorene-terminated phenylene polymer / carbon nanotube composite electrode.

1-3 Evaluation of capacity density of precision polymerized fluorene-terminated phenylene polymer / carbon nanotube composite electrode Using precision polymerized fluorene-terminated phenylene polymer / carbon nanotube composite electrode as working electrode, activated carbon sheet as counter electrode, and silver as reference electrode -Capacity density was measured by measuring a cyclic voltammogram in a triode cell using a silver ion electrode. As the electrolytic solution, propylene carbonate in which 1M tetraethylammonium tetrafluoroborate was dissolved was used. The potential range was −2 V to +1 V, and the potential scanning speed was 5 mVs ⁻¹ .

Example 2
2-1 Synthesis of precision polymerized fluorene-terminated fluorene polymer 2.2 mL of dimethylformamide with 1 mmol of 2,7-dibromofluorene, 1 mmol of 2-bromofluorene, 0.05 mmol of NiCl ₂ , 3.1 mmol of Zn, 0 0.1 mmol of triphenylphosphine and 0.05 mmol of 2,2-bipyridine were added and stirred at 80 ° C. for 20 hours to obtain a product. The product was filtered and washed to obtain a precision polymerized fluorene-terminated phenylene polymer of yellow powder represented by the following formula VI.

2-2 Preparation of precision polymerized fluorene-terminal fluorene polymer / carbon nanotube composite electrode 20 mg of precision polymerized fluorene-terminal fluorene polymer powder and 10 mg of carbon nanotube powder (specific surface area: 200 m ² / g) in 50 mL of isopropyl alcohol And a dispersion was obtained by mechanical stirring. The dispersion was filtered to obtain a sheet of a precisely polymerized fluorene-terminal fluorene polymer / carbon nanotube composite in which the precisely polymerized fluorene-terminal fluorene polymer was supported on carbon nanotubes. The sheet was cut to about 2 cm ² and crimped to an aluminum current collector of the same size to obtain a precision polymerized fluorene-terminal fluorene polymer / carbon nanotube composite electrode.

2-3 Capacity Density Evaluation of Precision Polymerized Fluorene-Terminal Fluorene Polymer / Carbon Nanotube Composite Electrode Using a precision polymerized fluorene-terminal fluorene polymer / carbon nanotube composite electrode as the working electrode, activated carbon sheet as the counter electrode, and silver as the reference electrode -Capacity density was measured by measuring a cyclic voltammogram in a triode cell using a silver ion electrode. As the electrolytic solution, propylene carbonate in which 1M tetraethylammonium tetrafluoroborate was dissolved was used. The potential range was −2 V to +1 V, and the potential scanning speed was 5 mVs ⁻¹ .

Comparative Example 1
1-1 Synthesis of Bulk Polymerized Polyfluorene 10 mmol of FeCl ₃ was added to acetonitrile in which 10 mmol of fluorene monomer was dissolved, stirred at room temperature for 72 hours, filtered and dried (60 ° C. vacuum drying for 24 hours) to obtain the following formula. A bulk polymerized polyfluorene powder represented by VII was obtained.

1-2 Production of Bulk Polymerized Polyfluorene / Carbon Nanotube Composite Electrode Add 50 mg of bulk polymerized polyfluorene powder and 10 mg of carbon nanotube powder (specific surface area: 200 m ² / g) to 50 mL of isopropyl alcohol, and disperse by mechanical stirring. A liquid was obtained. The dispersion was filtered to obtain a bulk polymerized polyfluorene / carbon nanotube composite sheet in which bulk polymerized polyfluorene was supported on carbon nanotubes. The sheet was cut to about 2 cm ² and pressed onto an aluminum current collector of the same size to obtain a bulk polymerized polyfluorene / carbon nanotube composite electrode.

1-3 Capacity Density Evaluation of Bulk Polymerized Polyfluorene / Carbon Nanotube Composite Electrode Using Bulk Polymerized Polyfluorene / Carbon Nanotube Composite Electrode for Working Electrode, Activated Carbon Sheet for Counter Electrode, and Silver-Silver Ion Electrode for Reference Electrode, Cyclic voltammograms were measured with a triode cell. As the electrolytic solution, propylene carbonate in which 1M tetraethylammonium tetrafluoroborate was dissolved was used. The potential range was −2 V to +1 V, and the potential scanning speed was 5 mVs ⁻¹ .

Comparative Example 2
2-1 Synthesis of precision polymerized polyfluorene 1 mmol 2,7-dibromofluorene, 0.05 mmol NiCl ₂ , 3.1 mmol Zn, 0.1 mmol triphenylphosphine, 0.05 mmol in 1.2 mL dimethylformamide 2,2-Bipyridine was added and stirred at 80 ° C. for 20 hours to obtain the product. The product was filtered and washed to obtain a yellow powder precision polymerized polyfluorene represented by the following formula VIII.

2-2 Production of precision polymerized polyfluorene / carbon nanotube composite electrode Add 50 mg of polymerized polyfluorene powder and 10 mg of carbon nanotube powder (specific surface area: 200 m ² / g) to 50 mL of isopropyl alcohol, and disperse by mechanical stirring. A liquid was obtained. The dispersion was filtered to obtain a sheet of a precisely polymerized polyfluorene / carbon nanotube composite in which precisely polymerized polyfluorene was supported on carbon nanotubes. The sheet was cut to about 2 cm ² and pressed onto an aluminum current collector of the same size to obtain a precisely polymerized polyfluorene / carbon nanotube composite electrode.

2-3 Capacity Density Evaluation of Precision Polymerized Polyfluorene / Carbon Nanotube Composite Electrode Using a precision polymerized polyfluorene / carbon nanotube composite electrode as a working electrode, an activated carbon sheet as a counter electrode, and a silver-silver ion electrode as a reference electrode, Cyclic voltammograms were measured with a triode cell. As the electrolytic solution, propylene carbonate in which 1M tetraethylammonium tetrafluoroborate was dissolved was used. The potential range was −2 V to +1 V, and the potential scanning speed was 5 mVs ⁻¹ .

Table 1 shows the capacity densities of Examples 1 and 2 and Comparative Examples 1 and 2.

  As is clear from Table 1, the precision polymerized fluorene-terminated phenylene polymer / carbon nanotube composite electrode and the precision polymerized fluorene-terminated fluorene polymer / carbon nanotube composite electrode of the examples were the bulk polymerized polyfluorene of Comparative Example 1. / The integration capacity is about 2.3 times that of the carbon nanotube composite electrode. Further, it has a high integration capacity almost equal to that of the precision polymerized polyfluorene / carbon nanotube composite electrode of Comparative Example 2.

Example 3 Production and Life Evaluation of Electric Double Layer Capacitor Cell
The precision polymerized fluorene-terminated phenylene polymer / carbon nanotube composite electrode prepared in Example 1 was used as a positive electrode, the carbon nanotube electrode was used as a negative electrode, and sulfolane in which 1.5M triethylmethylammonium tetrafluoroborate was dissolved was used as an electrolyte. Thus, a laminate cell was produced. Cell energy density evaluation and cell voltage load test were performed. The voltage was 3.2 V and the temperature was 40 ° C.

Comparative Example 3
A test capacitor using a precisely polymerized polyfluorene / carbon nanotube composite electrode prepared in Comparative Example 2 as a positive electrode, a carbon nanotube electrode as a negative electrode, and an electrolyte containing sulfolane in which 1.5M triethylmethylammonium tetrafluoroborate is dissolved A cell was produced. Evaluation similar to Example 3 was performed.

Comparative Example 4
Electrodes were prepared using the carbon nanotubes used in Examples 1 and 2 and Comparative Examples 1 and 2, and the electrodes were used for both positive and negative electrodes, and the electrolyte was sulfolane in which 1.5M triethylmethylammonium tetrafluoroborate was dissolved. A test capacitor cell was fabricated using this. Evaluation similar to Example 3 was performed. The electrodes were produced in the same manner as the methods used in Examples 1 and 2 and Comparative Examples 1 and 2.

Comparative Example 5
An electrode was prepared using an activated carbon electrode as both electrodes, which was used as a positive electrode and a negative electrode, and a test capacitor cell was prepared using sulfolane in which 1.5 M triethylmethylammonium tetrafluoroborate was dissolved as an electrolyte. Similar evaluations were made. The activated carbon used was one having a specific surface area of 1600 m ² / g and coconut shell material, and the activated carbon electrode was obtained by kneading and stretching 10% polytetrafluoroethylene and 5% carbon black.

Table 2 shows the energy density obtained, and FIG. 1 shows the result of the life evaluation test.

  As is clear from FIG. 1, the cell using the precisely polymerized fluorene-terminated phenylene polymer / carbon nanotube composite electrode maintains the capacity against the voltage load than the cell using the precisely polymerized polyfluorene / carbon nanotube composite electrode. It can be seen that the rate is high and the life characteristics are greatly improved. It can be seen that it has life characteristics comparable to those of activated carbon electrodes and carbon nanotube electrodes having extremely good life characteristics. And from Table 2, since it has a high energy density compared with the activated carbon electrode and the carbon nanotube, the precision polymerized fluorene-terminated phenylene polymer / carbon nanotube composite electrode is in view of high energy density and long life. It can be seen that it is very useful as an electrode for an electric double layer capacitor.

Claims (9)

At least one precision derived from precision polymerized polyfluorene in which the fluorene ring constituting the polyfluorene is polymerized substantially at the 2nd and 7th positions and the fluorene ring at the chain end has a halogen substituent. An electrode active material comprising a polymerized polyfluorene derivative,
The electrode active material, wherein the precision polymerized polyfluorene derivative is a derivative obtained by substituting a halogen substituent of a fluorene ring at a chain end of the precision polymerized polyfluorene with a phenyl group or a fluorenyl group.   2. The electrode active material according to claim 1, wherein the precisely polymerized polyfluorene contains at least one fluorene ring having a substituent at the 9-position.   The substituent is a group consisting of an alkyl group, a carboxyl group, a nitro group, a cyano group, an alkylcyano group, a phenyl group, a halogen atom, a halogenated methyl group, a halogenated phenyl group, an alkylphenyl group, and an alkylhalogenated phenyl group. The electrode active material according to claim 2, selected from:   The electrode which has an active material layer containing the electrode active material of any one of Claims 1-3.   The electrode according to claim 4, wherein the active material layer contains at least one carbon nanotube.   The electrode according to claim 5, wherein the precisely polymerized polyfluorene derivative is supported on the carbon nanotube.   The electrode according to any one of claims 4 to 6, which is used as one of a pair of electrodes in a secondary battery.   The electrode according to any one of claims 4 to 6, which is used as one of a pair of electrodes in an electric double layer capacitor.   The electrode according to any one of claims 4 to 6, which is used as at least one of a pair of electrodes in an electrochemical capacitor.

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