WO2006098229A1 - Electrode active material containing indrocarbazole derivative - Google Patents

Abstract

Disclosed is an electrode active material which enables to increase the energy density of an electrochemical cell such as a proton migration type secondary battery or capacitor. Specifically disclosed is an electrochemical cell having a structure wherein a positive electrode material layer and a negative electrode material layer are arranged opposite to each other via a separator. An electrode active material is present in the positive electrode material layer or the negative electrode material layer, and an indro[3,2-b]carbazole compound is used as the electrode active material. The indro[3,2-b]carbazole compound is represented, for example, by the following general formula (1). In the formula, R1 represents an electron-withdrawing group or a substituted or unsubstituted aryl group, and R2 represents a hydrogen, a lower alkyl, a halogen, a nitro, a cyano, a substituted carbonyl, a hydroxy, an alkoxy, a phenoxy or a substituted or unsubstituted amino group.

Description

 Specification

 Electrode active materials containing indolopower rubazole derivatives

 Technical field

 [0001] The present invention relates to an electrode active material used in an electrochemical cell such as a secondary battery or a capacitor. More specifically, the present invention relates to an indolo [3, 2-b] force rubazole compound or its acid as an electrode active material. The present invention relates to an electrochemistry cell that uses protons (dehydrogenated products) and protons as charge carriers.

 Background art

 In recent years, demand for power storage devices has increased due to advances in microelectronics. A power storage device is required to be smaller and thinner and to have a larger capacity. Remarkable lithium-ion batteries and high-capacity capacitors typified by electric double layer capacitors are attracting attention as power storage devices. In general, a lithium secondary battery has a large capacity, but a large output can be taken out in a short time and a large amount of power can be charged in a short time. It ’s good.

 On the other hand, an electric double layer capacitor is expected because of its excellent input / output characteristics in a short time, but has a problem of low energy density. Porous graphite is used as the active material of the electric double layer capacitor, and the electric double layer occurs at the interface between the electrolyte and the active material. Therefore, the larger the surface area of the active material graphite, the greater the capacitance of the capacitor. Will grow. In order to increase the surface area of graphite, it is known that if the pore size of graphite is reduced, the capacity of the capacitor increases as the pore surface area is reduced and the surface area of graphite is increased. On the other hand, when the pores are made smaller, the mobility of the electrolytic solution becomes smaller. This increases the internal resistance of the capacitor, making it difficult to input and output at a large rate. In other words, if the capacity is increased, the input / output characteristics originally possessed will be degraded. Therefore, it is very difficult to realize an electric double layer capacitor having excellent input / output characteristics and large capacity.

[0004] Under these circumstances, Patent Documents 1 to 3 describe excellent safety, reliability, current characteristics, long life, and the like for the purpose of improving high-speed current characteristics, which are disadvantages of lithium ion batteries. High volume A quantity of proton transfer type secondary battery has been proposed.

 Patent Document 1: JP-A-10-289617

 Patent Document 2: Japanese Patent Laid-Open No. 2003-123834

 Patent Document 3: Japanese Patent Laid-Open No. 2003-142098

[0005] The electrode active materials used in these high-capacity proton transfer secondary batteries with excellent reliability and current characteristics include polypyridines, polypyrimidines, sulfonic acid side chain systems, hydroquinone polymers, manganese. Acids, indole polymers and the like are disclosed. Since these compounds can easily insert and release protons, the energy density of the battery is inferior to that of conventional batteries.

 [0006] On the other hand, there are a general method for evaluating the usefulness of an electrode active material used in such a battery and a cyclic voltammetry (CV) method. In the evaluation by the CV method, the redox potential (V) and electrode capacity density (Ah / kg) of the active material can be measured. The magnitude of the electrode capacity density of the active material thus measured is one of the important indicators that reflect the energy density that can be output when a battery or capacitor is formed using the active material. That is, if an active material having a large electrode capacity density is used, a battery or capacitor having a high energy density can be obtained.

 Disclosure of the invention

 Problems to be solved by the invention

[0007] Under such circumstances, in order to enable high energy density of electrochemical cells such as secondary batteries or capacitors, development of new electrode active materials having excellent electrode capacity density has been made. Longed for.

 An object of the present invention is to provide an electrode active material having an excellent electrode capacity density for an electrochemical cell, particularly a proton transfer type secondary battery or capacitor.

 Means for solving the problem

[0008] As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an indolo [3, 2-b] force rubazol compound is effective as an electrode active material for a proton transfer secondary battery or a capacitor. As a result, the present invention has been completed. [0009] The present invention relates to an electrode active material involved in an electrode reaction of a secondary battery or a capacitor, and the reaction product in the electrode reaction of the electrode active material or the electrode active material is indolo [3, 2-b] force rubazole. The present invention relates to an electrode active material characterized by being an indolo power rubazole compound containing a skeleton. Moreover, this invention relates to the electrochemical cell containing said electrode active material.

[0010] The indolocarbazole compound includes a compound represented by the following general formula (1).

(However, each R independently represents an electron-withdrawing group or a substituted or unsubstituted aryl group, and each R independently represents hydrogen, lower alkyl, halogen, nitro, or

 2

 It represents either a substituted carbo yl, hydroxy, alkoxy, or a substituted or unsubstituted amino group. )

 [0011] First, the details of the indolo [3, 2-b] strength rubazole compound used as the electrode active material in the present invention will be described. This electrode active material is involved in the electrode reaction of a secondary battery or capacitor, and the reaction product before or after the electrode reaction has an indolo [3, 2-b] force rubazole skeleton. Hereinafter, it may be anything that becomes indolo power rubazol compound. If desired, the skeleton may be contained in a part of the polymer compound.

The electrode active material used in the present invention is an indolo power rubazole compound or a compound that becomes an endocarbazole compound by an electrode reaction. As will be described later, an indolocarbazole compound is composed of a dehydrogenated indolocarbazole compound (hereinafter referred to as indolocarbazole compound (b)) and an indolo structure prior to dehydrogenation. There is a carbazole compound (hereinafter referred to as indolo power rubazole compound (a)). Indropower rubazole compound (a) and Both (b) can be used as an electrode active material in the positive electrode or the negative electrode. When using indolo strength rubazole ( _a ) as the positive electrode active material, indolo strength rubazole ( _a ) becomes indolo strength rubazole (b) by charging and then indolocarbazole (b) becomes indolo strength rubazole by discharge. (a). When indole rubazole (b) is used as the negative electrode active material, indolo rubazole (b) becomes indolo rubazole (a) by charging, and indolo rubazole (a) becomes indolo by discharge. This is rubazole (b).

[0013] In the following, the power mainly explaining the indolocarbazole compound (a) is easily understood because the indolocarbazole compound (b) has the above-mentioned relationship with the indolocarbazole compound (a). The Hereinafter, when an indolo-powered rubazole compound is described as being represented by an indolo-powered rubazole compound (a), it is referred to as an indolocarbazole compound.

 As the indolocarbazole compound, a compound represented by the above general formula (1) is preferably exemplified. In the formula, two Rs each independently represent an electron-withdrawing group or a substituted or unsubstituted aryl group.

[0014] Here, the electron-withdrawing group is a substituent having an effect of attracting π electrons of the central benzene ring in the indolo [3, 2-b] force rubazole skeleton. There are no particular restrictions as long as they are used in the field of organic chemistry. For example, among the substituents described in Advanced Organic Chemi stry (4 ^th edition) Part A, p 208, Table 4.5, a substituent having a positive σ m or σ ρ value is preferable. . More preferred are halogen, nitro group, cyano group, substituted sulfol group, and substituted carboro group. The substituted sulfonyl group here means a linear, branched or cyclic alkylsulfonyl group having 1 to 6 carbon atoms, having or not having a substituent, and having 1 to 3 rings. A carbocyclic aromatic group, or may be a heterocyclic aromatic group having 1 to 3 rings containing 1 to 2 atoms such as nitrogen, sulfur, oxygen, etc. More preferably, a methanesulfol group An ethanesulfol group, a benzenesulfol group, and a toluenesulfol group. In addition, the substituted carbo group here refers to one of the carbonyl groups, hydrogen, hydroxy, linear, branched, or cyclic alkyl having 1 to 6 carbon atoms or alkoxy, phenyl, amino. Carbon groups having 1 to 6 carbon atoms, such as linear, branched, and cyclic alkylamino, dialkylamino, and phenylamine-containing diphenylamino, are preferably carboxy or acetyl groups. [0015] Further, the substituted or unsubstituted aryl group represents a carbocyclic aromatic group having a substituent having or not having a ring power of ^ to 3, preferably a phenol, Naphthyl, anthral, and phenanthryl. Further, furyl, benzofuryl, chael, benzocher, and quinolyl, which may be a heterocyclic aromatic group having 1 to 3 rings containing 1 to 2 atoms such as nitrogen, sulfur, and oxygen, are preferred. Further, the substituent here is preferably an electron-withdrawing group, specifically, the electron-withdrawing group described above.

 [0016] Specific groups represented by R include hydrogen, methyl, ethyl, n propyl, isopropyl, n-butynole, isobutyl, sec butyl, t-butinole, fluoro, black mouth, bromo, and iodine, Nitro, Sheared Carboxy, Phenol, Phenol, 2-Methyl Phenol, 3-Methyl Phenol, 4-Methino-Lefre Nore, 4-Ethino-Lefre-Nore, 4-Bi-N-Neo-Fe-Nole, 4--Eth-Nole-F-Nole, 2 —Methoxyphenol, 3-Methoxyphenyl, 4-Methoxyphenol, 2-Trophele, 3 Nitrophenol, 4 Nitrophenol, 2 Honore, Rofenini, 3 Honore, Rofenino, 4 Lofeninole, 2 Black-mouthed Fuinole, 3 Black-mouthed Fuinole, 4 Black-mouthed Fuinenole, 2 Bromofehl, 3 Bromofehl, 4 Bromofehl, 4-(Methylamino) femoral, 4 — (Yetylami ) Feel, 4— (Dimethylamino) Feel, 4— (Detylamino) Feel, 4 (Formylamino) Four, 4 (Acetylamino) Four, 4 (n—propanoylamino) ), 4 (isopropanoylamino), 4 (n-butylylamino), 4 (sec butyrylamino), 4 (bivaloylamino), 1 naphthyl, 2 Naphthyl, anthryl, phenanthryl, 2 furyl, 3 furyl, benzofuryl, chenil, 2 benzozenyl, 3 benzozoenyl, 2 pyridyl, 3 -pyridyl, 4 pyridinole, 2 quinolinole, 3 quinolinole, acetinol, propionyl, n-butyryl, Isobutyryl, sec butyryl, pivalol, carboxy, methoxycarbonyl, ethoxycarbonyl, n propoxycarbonyl, isopropoxy Kanoreboninore, Benzoi Le, § amino carbonyl, methyl § amino carbonyl, dimethyl § amino carbonyl, Echiruami Roh carbonyl, Jefferies chill § amino carbonyl, phenylalanine § iminocarbonyl, there is Jifuweniruami Bruno carbonyl.

 [0017] There are two R's independently hydrogen, lower alkyl, halogen, nitro, sia substituted substitution

 2

Either carbonyl, hydroxy, alkoxy, or a substituted or unsubstituted amino group Indicates.

 [0018] Lower alkyl is a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 6 carbon atoms. A substituted carbocycle is a substituted carbocyclic group in which any one of alkyl, alkoxy, phenol, amide-containing alkylamino, dialkylamino, and phenyl-aminodiphenylamino is arranged on one side of the carbo group. It is le. Alkoxy is a linear, branched or cyclic aliphatic alkoxy group having 1 to 6 carbon atoms. In addition, a substituted amino group means that 1 or 2 of the two hydrogens of the amino group are each independently a linear, branched or cyclic aliphatic hydrocarbon having 1 to 6 carbon atoms or a ring number of 1 to Or an amino group substituted with a carbocyclic aromatic group having 3 or an acyl group having 1 to 7 carbon atoms.

 [0019] Specific groups represented by R include hydrogen, methyl, ethyl, n-propyl, isopropyl

 2

 , N-butynole, isobutyl, sec butyl, t-butinole, fluoro, black mouth, bromo, iodine, nitro, carboxy-containing acetyl, acetyl, propiol, butyryl, methoxycarboninole, ethoxycanoleboninore, n Propoxycanoleboninore, isopropoxynolevonore, benzil, aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, ethylaminocarbonyl, jetylaminocarbonyl, phenylaminocarbonyl, diphenylamino Canoleboninole, hydroxy, methoxy, ethoxy, n-propoxy, isopropoxy, n butoxy, sec butoxy, t-butoxy, amide-containing methylamino, dimethylamine-containing acetylene-containing ethylamine-containing phenylamine-containing diphenylamine-containing cetylamide-containing propionylamine Roh, isopropionyl Rua Mino, n- Buchiriruamino, Isobuchiriruami input sec Buchiri Ruamino, is Bibaroiruamino.

[0020] Further, preferred examples of the compound represented by the general formula (1) include that each R is independently nitro, sialylated carboxy, substituted carbonyl, or a substituted or unsubstituted aryl group. More preferred is a substituted or unsubstituted aryl group represented by the following formula (2).

(Wherein R to R are independently hydrogen, halogen, alkyl, hydroxy, alcohol,

 3 7

 Xi, substituted or unsubstituted amino-containing carboxy, alkoxy carbo, substituted or unsubstituted amino carbo, nitro or cyan group. )

 [0021] In R to R, alkyl means a linear, branched or cyclic aliphatic carbon having 1 to 6 carbon atoms.

 3 7

 It is a hydrogen fluoride group. Alkoxy is a linear, branched or cyclic aliphatic alkoxy group having 1 to 6 carbon atoms. In addition, the substituted amino group is a group in which 1 or 2 hydrogens of the amino group are each independently a linear, branched, or cyclic aliphatic hydrocarbon group having 1 to 6 carbon atoms, or a ring having 1 to 3 carbon atoms. Or an amino group substituted with an acyl group having 1 to 7 carbon atoms. Further, the alkoxy of the alkoxy carbo group is a linear, branched or cyclic aliphatic alkoxy group having 1 to 6 carbon atoms. In addition, a substituted aminocarbonyl group is a group in which 1 or 2 hydrogens of an amino group are each independently a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 6 carbon atoms, It is an aminocarbo group substituted with a carbocyclic aromatic group having 1 to 3 carbon atoms or an acyl group having 1 to 7 carbon atoms.

[0022] Specific groups represented by R to R include hydrogen, methyl, ethyl, n-propyl, isop

 3 7

Mouth pill, n-butyl, isobutyl, sec-butyl, t-butyl, fluoro, black mouth, bromo, odo, hydroxy, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy, Phenyloxy, amide-containing methylamino, dimethylamino-containing ethylamino, jetylami-containing phenylamine-containing diphenylami-containing acetylamino-containing propionylamino, isopropionylami-containing n-butyrylami-containing isobutyrylamino-containing sec-butyrylamino, bivalloylami-containing methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl , Isopropoxycarbonyl, aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, ethylaminocarbonyl, ethylmethylaminominocarbonyl, There are jetylaminocarbonyl, phenylmethylaminominocarbonyl, diphenylaminocarbonyl.

 [0023] Next, a method for synthesizing the indolo power rubazole derivative used in the present invention will be described. Indolo-powered rubazole derivatives are described in, for example, EP908787, Tetrahedron, vol51, No43, ppl 1801-11808 (1995) or Tetrahedron, vol55, No43, ppl2577-12594 (1999) or an application thereof. Can be synthesized.

 Specifically, it can be synthesized by the method shown in the following formula (3).

 (3)

[0025] That is, indole is dissolved in a suitable solvent, mixed with a suitable acid, and aldehyde (R -C

 1

It is synthesized by a condensation reaction with HO) at an appropriate reaction temperature for a certain period of time.

[0026] In this reaction, a suitable solvent is not particularly limited as long as it has solubility in the indole or aldehyde used, but for example, a chain hydrocarbon such as n-xane, jetyl ether, tetrahydrofuran, Acetonitrile, acetone, water, methanol, ethanol, 1 propanol, 2-propanol, 1-butanol, 2-butanol, tert-butyl alcohol, dioxane, dimethylformamide, dimethyl sulfoxide, benzene, toluene, xylene, pyridine, quinoline Methanol and toluene are more preferable. Moreover, the solvent which mixed these by arbitrary ratios as needed can also be used. The amount of solvent used is suitably 0.1 to L000 parts by weight, more preferably 10 to L00 parts by weight per 1 part by weight of indole. If desired, the reaction can be carried out without a solvent.

[0027] The aldehyde to be used is 0.9.11 mol, more preferably 0.5-10 mol per mol of indole. [0028] The acid to be mixed is preferably Bronsted acid such as hydrochloric acid, sulfuric acid and nitric acid, formic acid, acetic acid, propionic acid, p-toluenesulfonic acid, benzenesulfonic acid, acetic acid and More preferably, they are Lewis acids such as aluminum, boron fluoride and zinc chloride (II). More preferred are p-toluenesulfonic acid and sulfuric acid. Moreover, the acid which mixed these in arbitrary ratios can also be used as needed, and the usage-amount with respect to 1 mol of indole is 0.01 to 50 mol. is there.

 [0029] The reaction temperature is suitably from -80 to 250 ° C, more preferably from 50 to 120 ° C. The reaction time is suitably 0.1 to 48 hours, more preferably 0.5 to 2 hours.

 [0030] The method for isolating and purifying the indolo rubazole compound produced by the reaction represented by the reaction formula (3) is an operation method in a post-treatment after a normal organic reaction, for example, liquid separation operation, filtration operation, column Operation, recrystallization, etc. can be used.

 Depending on the type of aldehyde used, the central benzene ring may become completely aromatic! In some cases, the compound shown in parentheses in formula (3) may stop. In some cases, a dehydrogenation reaction can be added to obtain the target compound. There are no particular restrictions on the dehydrogenating agent used in this case as long as it is a dehydrogenating agent used in ordinary organic reactions, but chlorael, salcomine, palladium on carbon, 2, 3-dichloro-5, 6— Dicyan 1,4-quinone (DDQ), the use of activated carbon is preferred!

 Brief Description of Drawings

[0031] [FIG. 1] A diagram showing a cross-sectional structure of an electrochemical cell.

 Explanation of symbols

 [0032] 1: current collector, 2: positive electrode material layer, 3: separator, 4: negative electrode material layer, 5: gasket, 6: current collector BEST MODE FOR CARRYING OUT THE INVENTION

[0033] When used in an electrochemical cell (preferably a secondary battery or a capacitor) that uses an indolocarbazole compound, two electrons are transferred by the mechanism shown in the following formula (4). It is estimated to be. By smoothly transferring electrons in this mechanism, the proportion of active materials that transfer electrons increases, and as a result, an electrode active material having an excellent energy density is obtained.

 (4) In the formula, IC (a) and IC (b) indicate indolo-powered rubazole compound (a) and indolo-powered rubazole compound (b), and IM (0, IM (ii) and IM (iii) are intermediates. (i), (ii) and (iii) are shown.

[0034] In order to smoothly transfer and receive the electron represented by the formula (4), it is important that the R substituent is an electron-withdrawing group. In other words, the introduction of an electron-withdrawing substituent occurs on the nitrogen atom of the intermediate (i) that is formed after taking out electrons from the lone pair of electrons on the nitrogen atom of the indolodynamic rubazole compound ( _a ). By delocalizing the radical cation to the central benzene ring, there is an effect of stabilizing the molecule, and as a result, the intermediate (i) force also promotes the reaction to the intermediate (ii) and efficiently produces electrons. As a result, an electrode active material having an excellent energy density can be obtained.

 [0035] The electrochemical cell of the present invention preferably has a structure in which a positive electrode material layer and a negative electrode material layer respectively formed on two current collectors are arranged to face each other with a separator interposed therebetween. Then, the electrode active material is present in the positive electrode material layer or the negative electrode material layer.

 Next, the present invention will be described with reference to FIG. 1 which shows a cross-sectional structure of an embodiment of an electrochemical cell for producing a secondary battery or a capacitor.

A positive electrode material layer 2 and a negative electrode material layer 4 formed on the current collectors 1 and 6, respectively, are arranged opposite to each other with a separator 3 interposed therebetween, and the positive electrode material layer 2 and the negative electrode material layer 4 are laminated via the separator 3. A gasket 5 made of insulating rubber or the like is provided on both side surfaces of the laminated body. . The positive electrode material layer 2 (positive electrode) and the negative electrode material layer 4 (negative electrode) are impregnated with an electrolyte containing protons. The compound of the present invention is used as an electrode active material contained in the positive electrode material layer 2 or the negative electrode material layer 4.

In the positive electrode material layer 2 or the negative electrode material layer 4, a conductive auxiliary material can be added as necessary in order to ensure conductivity. Examples of the conductive auxiliary material include conductive materials such as crystalline carbon, carbon black, and graphite. In addition, a binder may be added as necessary in order to maintain the moldability of the electrode or fix these materials on the current collector.

 [0037] The mixing ratio of the constituent materials of the electrode is arbitrary as long as the desired characteristics can be obtained, but considering the efficiency per unit mass or unit capacity, the carbazole compound is 30 to 95% by mass, The range of 5-50% by weight of auxiliary material and 0-20% by weight of binder is desirable.

 The method for producing the electrode is arbitrary as long as the desired characteristics can be obtained, but it can be obtained by kneading the indolo strength rubazole compound, the conductive additive, and the noinder mixed at a desired ratio, and compression-molding the mixture. At this time, an appropriate amount of solvent may be mixed in order to improve moldability. In addition, an appropriate amount of solvent is mixed in the carbazole compound, conductive additive, and binder mixed at a desired ratio and kneaded to form a paste. The paste is applied onto a current collector and dried. Can also be molded. The solvent to be used is not particularly limited, but dimethylformamide, ethylene carbonate, propylene carbonate, dimethyl carbonate and the like are preferable. In order to improve various properties, a salt or a surfactant may be added during kneading.

[0038] As the electrolytic solution, it is preferable to use an aqueous solution or a non-aqueous solution containing protons so that protons can be used as charge carriers of the force rubazole compound. Further, it is preferable that the proton concentration of the electrolytic solution is 10- ³ molZL~18molZL. In addition, a salt or a surfactant may be added to the electrolytic solution in order to improve electrical conductivity or improve various properties.

[0039] As the separator, any film having electrical insulation and ionic conductivity may be used, for example, a porous film such as polyethylene or fluorine resin, which is impregnated with an electrolytic solution. Used. Alternatively, instead of such a separator, An electrolyte such as a copper electrolyte or a solid electrolyte may be interposed between the electrodes.

 Example

 [0040] Next, synthesis examples, reference examples, and examples will be described in more detail. However, the present invention is not limited to the description of the following examples, and may be appropriately modified without changing the gist thereof. It is possible to implement.

 Unless otherwise specified, the analysis data of the synthesized compounds were subjected to 1H-NMR using Nihon Denshi Co., Ltd. SiiNM-LA400 (400 MHz). For mass spectrum, JEOL Ltd. ^ MS-AX505HA was used.

[0041] Synthesis Example 1

 Synthesis of 6,12-difuryl-5,11 -2H-indolo [3,2-b] force rubazole

 In a 500 ml three-necked flask, 11.7 g (0.1 mol) of indoleol, 10.6 g (0.1 mol) of vensanolaldehyde and 200 g of methanol were charged at room temperature and stirred, and 15 Og of sulfuric acid (0.15 mol) was added for 15 minutes. Dripped. The temperature in the tank was raised to 64 ° C in an oil bath and heated to reflux for 3 hours. After cooling to room temperature, the formed precipitate was filtered and dried under reduced pressure at 50 ° C. This precipitate was reslurried with 1 OOg of ethyl acetate and the remaining precipitate was collected by filtration and dried under reduced pressure at 50 ° C. 6,12-diphenyl-5,6,11,12-4H-indolo [3,2- b) 7.4 g of strength rubazole was obtained.

 lH-NMR (DMSO-d6) δ (ppm): 10.69 (2H, brs), 7.33 (4H, d, J = 7Hz), 7.27 (4H, t, J = 7Hz), 7. 23 (2H, d, J = 7Hz), 7.18 (2H, t, J = 7Hz), 7.07 (2H, d, J = 8), 6.94 (2H, dt, J = l, 8Hz ), 6.78 (2H, dt, J = l, 8Hz), 5.69 (2H, s)

 FD-MS (M / z): 410 (M +, base)

[0042] The obtained 6,12-diphenyl-5,6,11,12-4H-indolo [3,2-b] force rubazole 3.3 g (8. Om mol), chloral 2.07 g (8.43 mmol) was suspended in 66 g of xylene and heated to reflux in an oil bath for 5 hours. After cooling to room temperature, the reaction mixture was filtered, and the resulting precipitate was reslurried with 50 g of methanol. This precipitate was dried under reduced pressure at 50 ° C. to obtain 2.73 g of the title compound. lH-NMR (DMSO-d6) δ (ppm): 10.61 (2H, brs), 7.43 (4H, d, J = 7Hz), 7.15-7.34 (8H, m), 7. 05 (2H, d, J = 8Hz), 7.05 (2H, d, J = 8Hz), 6.93 (2H, t, J = 8Hz), 6.80 (2H, t, J = 8Hz) FD-MS (M / z): 408 (M +) ゝ 78 (base)

[0043] Synthesis Example 2

 Synthesis of 6,12-bis- (4-cyanol) -5,11-2H-indolo [3,2-b] force rubazole

 Into a 1L four-necked flask, indole 5.85g (0.05mol), 4-cyanbenzaldehyde 6.5 6g (0.05mol), p-sulfene sulfonic acid 14.8g (0.075mol), 卜 ruen 500g The mixture was sequentially charged at room temperature and stirred, heated in an oil bath to 105 ° C and reacted for 1 hour. After the disappearance of the raw materials, the temperature in the tank was cooled to 70 ° C, and suction filtration was performed when the temperature reached 70 ° C. The filtrate was distilled off under reduced pressure, and the resulting residue was dissolved in 400 g of ethyl acetate, and this solution was washed with 400 g of distilled water. The ethyl acetate layer was dried under reduced pressure, and the resulting residue was washed with methanol lOOg and dried under reduced pressure at 40 ° C. to obtain 1.04 g of the title compound.

 lH-NMR (DMSO-d6) δ (ppm): 10.71 (2H, brs), 8.18 (4H, d, J = 8Hz), 7.91 (4H, d, J = 8Hz), 7. 74 (2H, d, J = 8Hz), 7.52 (2H, d, J = 8Hz), 7. 2 8 (2H, dt, J = l, 8Hz), 6. 87 (2H, dt, J = l, 8Hz),

 FD-MS (M / z): 458 (M +, base)

[0044] Synthesis Example 3

 Synthesis of 6,12-bis- (4-diphenyl) -1,7-2H-indolo [3,2-b] force rubazole

 The same operation was performed except that 4-cianobenzaldehyde in Synthesis Example 2 was changed to 7.56 g (0.05 mol) of 4-nitrobenzaldehyde to obtain 0.70 g of the title compound.

 lH-NMR (DMSO-d6) δ (ppm): 10. 79 (2H, brs), 8. 8. 57 (4H, d, J = 8Hz

), 8.02 (4H, d, J = 8Hz), 7.40 (2H, d, J = 8Hz), 7.30 (2H, t, J = 8Hz), 7

13 (2H, d, J = 8Hz), 6. 88 (2H, t, J = 8Hz)

 FD-MS (M / z): 498 (M +)

[0045] Synthesis Example 4

 Synthesis of 6,12-bis- (4-cyanophyl) -2,8-dimethoxy-5,11-2H-indolo [3,2-b] force rubazole

 The same operation was performed except that the indole of Synthesis Example 2 was changed to 7.36 g (0.05 mol) of 5-methoxyindole to obtain the title compound 1.03 g.

lH-NMR (DMSO-d6) δ (ppm): 10.51 (2H, brs), 8.19 (4H, d, J = 8Hz), 7.91 (4H, d, J = 8Hz), 7.33 (2H, d, J = 8Hz), 6.97 (2H, dd, J = l, 8Hz),

6. 50 (2H, d, J = lHz)

[0046] Synthesis Example 5

 Synthesis of 6,12-bis- (4-cyanophyl) -2,8-methyl-5,11-2H-indolo [3,2-b] force rubazole

 The same operation was performed except that the indole of Synthesis Example 2 was changed to 6.59 g (0. 05 mol) of 5-methylindole to obtain 3.20 g of the title compound.

 lH-NMR (DMSO-d6) δ (ppm): 10. 71 (2H, brs) ゝ 8. 18 (4H, d, J = 8Hz), 7.75 (4H, d, J = 8Hz), 7. 31 (2H, d, J = 8Hz), 6.84 (2H, s), 6.79 (2H, d, J = 8Hz), 2.21 (6H, s)

 FD-MS (M / z): 486 (M +, base)

[0047] Synthesis Example 6

 Synthesis of 6,12-bis- (4-fluorophenol) -5,11-2H-indolo [3,2-b] force rubazole 4-cyanobenzaldehyde from Synthesis Example 2 is converted to 4-fluorobenzaldehyde 6. The same operation was carried out except that the amount was changed to 12 g (0. 05 mol) to obtain 3.23 g of the title compound.

 lH-NMR (DMSO-d6) δ (ppm): 10.57 (2H, brs), 7.73-7.70 (4H, m), 7

60 to 7.54 (4H, m), 7.42 (2H, d, J = 7Hz), 7.26 (2H, d, J = 7Hz), 7.06

(2H, d, J = 7Hz), 6.85 (2H, t, J = 7Hz)

 FD-MS (M / z): 444 (M +, base)

[0048] Synthesis Example 7

 Synthesis of 6,12-bis- (4-carboxyphenol) -5,11-2H-indolo [3,2-b] force rubazole 4-Cyanobenzaldehyde from Synthesis Example 2 is converted to 4-formylbenzoic acid 4. The same operation was performed except that 53 g (0. 05 mol) was changed to obtain 0.88 g of the title compound.

 lH-NMR (DMSO-d6) δ (ppm): 10. 65 (2H, brs), 8. 27 (4H, d, J = 8Hz),

7.93 (2H, bs), 7.84 (4H, d, J = 8Hz), 7.43 (2H, d, J = 8Hz), 7.26 (2H, t, J = 8Hz), 7. 08 (2H, d, J = 8Hz), 6.84 (2H, t, J = 8Hz)

 FD-MS (M / z): 496 (M +, base)

[0049] Synthesis Example 8 Synthesis of dimethyl 5,11-2H-indolo [3,2-b] ruvazole-6,12-dicarboxylate

 In a 500 ml three-necked flask, 23.0 g (0. lOmol) of commercially available dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate, 45.6 g (0.49 mol) of aniline and 250 g of acetic acid were obtained. The mixture was heated and stirred at 105 ° C for 24 hours in an oil bath. After cooling to room temperature, the precipitated solid was filtered off. The obtained solid was rinsed with water and dried under reduced pressure at 60 ° C. to obtain 21. Og of dimethyl 2,5-dianilinoterephthalate.

 1H-NMR (CDC13) δ (ppm): 12. 05 (2H, s), 7.93 (2H, s), 7.26 (4H, t, J = 8Hz), 7. 12 (4H, d, J = 8Hz), 6.95 (2H, t, J = 8Hz), 3.73 (6H, s)

[0050] 7.04 g (0.02 mol) of the obtained dimethyl 2,5-di-linoterephthalate was added to 9.78 g (0.04 mol) of palladium acetate (11) and 350 g of acetic acid in a 300 ml flask. And heated and stirred at 105 ° C for 4 hours in an oil bath. After cooling to room temperature, the precipitated solid was filtered off. The obtained solid was rinsed with dichloromethane and dried under reduced pressure at 120 ° C. to obtain 2.3 g of the title compound.

 lH-NMR (DMSO-d6) δ (ppm): 11.30 (2H, s), 8.46 (2H, d, J = 8Hz), 7.7 (2H, d, J = 8Hz), 7. 49 (2H, t, J = 8Hz), 7.19 (2H, t, J = 8Hz), 4.20 (6 H, s)

 FD-MS (M / z): 372 (M +)

[0051] Synthesis Example 9

 Synthesis of 5,11-2H-indolo [3,2-b] ruvazole-6,12-dicarboxylic acid diamide

Under a nitrogen atmosphere, in a 25 ml flask, 0.511 g of dimethyl 5,11-2H-indolo [3,2-b] ruvazole-6,12-dicarboxylate and 0.43 g of formamide (9. 45 mmol) and 3 g of dehydrated DMF. The mixture was heated to 100 ° C. in an oil bath, and after the internal temperature reached 100 ° C., 0.38 g of 28% sodium methoxide methanol solution was added dropwise. After completion of dropping, the mixture was stirred at 100 ° C for 5 hours. After cooling to room temperature, the precipitated solid was filtered off. The obtained solid was rinsed with isopropyl alcohol and dried under reduced pressure at 120 ° C to obtain 0.1 g of the title compound. LH-NMR (DMSO-d6) δ (p pm): 10. 97 (2H, s) 8.25 (2H, bs), 7.99 (2H, bs), 8.29 (2H, d, J = 8Hz), 7.58 (2H, d, J = 8Hz), 7.38 (2H , t, J = 8Hz) 7.10 (2H, t, J = 8Hz)

 FD MS (M / z): 342 (M +)

[0052] Synthesis Example 10

 Synthesis of 6, 12-di (1 pyrrolidinocarbol) -5, 11-2H-indolo [3,2-b] force rubazole

In a 300 ml three-necked flask, 2.3 g (6.14 mmol) of dimethyl 5,11-2H-indolo [3,2-b] carbazole-6,12-dicarboxylate obtained in Synthesis Example 8 and methanol 24 g, 70 g of toluene and 5.98 g (59.8 mmol) of ION sodium hydroxide aqueous solution were added. The mixture was heated to 105 ° C in an oil bath and stirred for 8.5 hours. After cooling to room temperature, the precipitated solid was filtered off. The mother liquor was separated into oil and water, and 14 g of 35% aqueous sulfuric acid solution was added to the resulting aqueous layer and stirred for 30 minutes, and the resulting solid was filtered off. The obtained solid was washed with water and then dried under reduced pressure at 120 ° C. to obtain 1.84 g of 5,11-2H-indolo [3,2-b] force rubazole-6,12-dicarboxylic acid.

 In a 50 ml round flask, the above-mentioned 5,11-2H-indolo [3,2-b] strength rubazole-6,12-dicarboxylic acid 0.50 g (l. 44 mmol), DMF 12 g, [benzotriazole 1 yloxytris ( Dimethylamino) phospho-hexafluorophosphate] 1. 42g (3.22 mmol), N, N diisopyrutylamine 0.42 g (3.25 mmol), pyrrolidine 0.25 g (3.51 mmol) Trietylamine 0.32 g (3.21 mmol) was added. The mixture was stirred at room temperature for 2 days, and the resulting solution was added to a solution of 200 g of ethyl acetate and 100 g of water. The precipitated solid was filtered off, washed with water, and dried under reduced pressure at 120 ° C. to obtain 0.1 l of the title compound.

 lH-NMR (DMSO-d6) δ (ppm): 11.21 (2H, s), 7.87 (2H, d, J = 8Hz), 7.52 (2H, d, J = 8Hz), 7. 41 (2H, t, J = 8Hz), 7.15 (2H, t, J = 8Hz), 3.20 (8 H, m), 1.70 (8H, m)

[0053] Synthesis Example 11

 Synthesis of 5,11-2H-indolo [3,2-b] force rubazole

In a 200 ml round flask, dissolve 2.91 g (l l.8 mmol) of commercially available 3,3 methylenediindole and 1.75 g (ll.8 mmol) of triethylorthoformate in 54 g of methanol. 200 1 was added. The mixture was heated to reflux for 15 minutes in an oil bath. After cooling to room temperature, the precipitated solid was filtered off. The obtained solid was rinsed with methanol and dried under reduced pressure at 60 ° C. to obtain 1.36 g of the title compound. lH-NMR (DMSO-d6) δ (ppm): 11.00 (2H, s), 8.46 (2H, d, J = 8Hz), 8.10 (2H, s), 7.45 (2H, d, J = 8Hz), 7.36 (2H, t, J = 8Hz), 7.19 (2H, t, J = 8Hz)

[0054] Example 1

 The compounds synthesized in this way were evaluated by the cyclic voltammetry (CV) method. In the following description, the case where it is applied to the electrode material of a secondary battery is described. However, as other electrochemical cells such as an electric double layer capacitor by appropriately setting the capacity and the charge / discharge rate. A suitable configuration can also be adopted.

 HZ-3000 manufactured by Hokuto Denko Co., Ltd. was used for CV measurement. A three-electrode glass cell was used, the working electrode was the sample electrode, Pt was used as the counter electrode, the AgZAgCl electrode was used as the reference electrode, and a 20-40 wt% sulfuric acid aqueous solution was used as the electrolyte. The electrode capacity (effective capacity) per lg of active material was calculated from the CV curve obtained by sweeping in the range of 200 to 1200 mV at a sweep speed of 20 mVZsec.

[0055] A sample electrode manufactured as follows was used. As an electrode active material, after adding 30 wt% of vapor-grown carbon fiber (VGCF) as a conductive additive to the compound ⁷ Owt% obtained in Synthesis Examples 1 to 10, an appropriate amount of solvent is added and mixed. It was made into a paste by glazing. This paste was uniformly applied to a carbon sheet of a certain area and dried under reduced pressure all day and night.

 [0056] The results are shown in Table 1. In Table 1, R1 and R2 represent the two R1 and R2 in the general formula (1).

[table 1]

Synthesis example R 1 R 2 Electrode capacity density (C / g) Theoretical capacity

 (100% purity conversion value) (C / g)

1 Ph H 247 470

2 4-CN-Ph H 343 '420

3 4-N02-Ph H 182 390

4 4-CN-Ph 5-OMe 372 370

5 4-CM-Ph Me 264 395

6 4-F-Ph H 219 455

7 4-COOH-Ph H 130 390

8 COO e H 127 518

9 C0NH2 H 372 564

10 CO- (1 -pyr ro I i d i no) N 256 428

1 1 H H 84 750

[0057] Example 2

 The indolocarbazole compound obtained in Synthesis Example 4 is used as a positive electrode active material, VGCF as a conductive auxiliary agent, PVdF as a binder, active material ZVGCFZPVdF is mixed at a mass ratio of 70Z25Z5, and pressure-molded. An electrode was obtained. Next, a negative electrode was obtained by mixing Polyphenol-Lucinoxaline as an active material, Ketjen black (KB) as a conductive auxiliary agent, and an active material ZKB at a mass ratio of 7030, followed by pressure molding. . The electrolyte used was a 40 wt% sulfuric acid aqueous solution. The separator was a porous nonwoven fabric with a thickness of 50 m. The positive electrode and the negative electrode were opposed to each other through this separator and bonded together, covered with a gasket, and sealed in a coin case to produce a coin-type secondary battery. The cell was charged at 25 ° C for 1 hour and then discharged. The discharge capacity value and average voltage value were converted to energy values. The energy of the coin-type secondary battery was 5.1 mWh.

[0058] From Table 1 (CV evaluation), it has become clear that indolocarbazole compounds having an electron-withdrawing group at R1 have a high electrode capacity density. From Example 2, it is clear that an electrochemical cell containing an indolo power rubazole compound as an electrode active material has a good energy density.

Industrial applicability According to the present invention, an electrode active material having a large electrode capacity density and an electric cell using the same can be provided.

Claims

The scope of the claims  [1] Electrode active material that participates in secondary battery or capacitor electrode reaction, compound power before or after electrode reaction An electrode active material characterized in that  [2] The electrode active material according to claim 1, wherein the indolopower rubazole compound is a compound represented by the following general formula (1).

However,  R each independently represents an electron-withdrawing group or a substituted or unsubstituted aryl group, and each R independently represents hydrogen, lower alkyl, halogen, nitro, or a substituted carbo-substituted group. 2  Or a hydroxy group, a hydroxy group, an alkoxy group, or a substituted or unsubstituted amino group.  [3] The electrode active material according to claim 2, wherein in the general formula (1), each R is independently nitro, carboxy-containing carboxy, substituted carbonyl, or a substituted or unsubstituted aryl group. [4] The electrode active material according to claim 2, wherein in the general formula (1), R is a substituted or unsubstituted aryl group represented by the following formula (2).

However,  R to R are each independently hydrogen, halogen, alkyl, hydroxy, alkoxy, 3 7  A substituted or unsubstituted amino-containing carboxy, alkoxycarbol, substituted or unsubstituted aminocarbol, nitro or cyan group is shown.  [5] An electrochemical cell comprising an indolocarbazole compound having an indolo [3,2-b] force rubazole skeleton as an electrode active material. 6. The electrochemical cell according to claim 5, wherein the indolopower rubazole compound performs electron transfer accompanying an acid-reduction reaction involving proton adsorption / desorption. 7. The electrochemical cell according to claim 5 or 6, wherein the indolo power rubazole compound is a compound represented by the general formula (1).

However, Each R independently represents an electron-withdrawing group or a substituted or unsubstituted aryl group, and each R independently represents hydrogen, lower alkyl, halogen, nitro, or a substituted carbo-substituted group. Or a hydroxy group, a hydroxy group, an alkoxy group, or a substituted or unsubstituted amino group.  8. The electrochemical cell according to claim 7, wherein in the general formula (1), each R is independently nitro, carboxy-containing carboxy, substituted carbonyl, or a substituted or unsubstituted aryl group.  9. The electrochemical cell according to claim 7, wherein in the general formula (1), R is a substituted or unsubstituted aryl group represented by the general formula (2).

However,  R to R are each independently hydrogen, halogen, alkyl, hydroxy, alkoxy, 3 7  A substituted or unsubstituted amino-containing carboxy, alkoxycarbol, substituted or unsubstituted aminocarbol, nitro or cyan group is shown.  [10] The electrochemical cell has a structure in which a positive electrode material layer and a negative electrode material layer are arranged to face each other with a separator interposed therebetween, and an electrode active material is present in the positive electrode material layer or the negative electrode material layer. 5. The electrochemical cell according to 5.  11. The electrochemical cell according to claim 5, wherein the electrochemical cell is a secondary battery or a capacitor.