JP5617828B2 - Cross-linked polyaniline derivative, positive electrode active material and positive electrode for non-aqueous secondary battery, non-aqueous secondary battery, and vehicle - Google Patents

Description

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

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

  In recent years, it has been studied to apply a light organic compound as an electrode active material. Patent Document 1 describes that a radical organic compound having a Feldacyl skeleton capable of one-step multi-electron transfer is used as an electrode active material.

  Among organic electrode active materials, in particular, a π-electron conjugated conductive polymer is promising as an electrode active material. For example, Non-Patent Document 1 reports a battery using a conductive polymer such as polyaniline as a positive electrode active material.

  Patent Document 2 describes a novel polyaniline derivative capable of one-step two-electron transfer and a secondary battery using a protonated version of the compound as a positive electrode. According to Patent Document 2, since the electrode material using the compound of the novel polyaniline derivative has a high energy density, it is stated that using the electrode material as a positive electrode is useful in a secondary battery.

  In Patent Document 3, when a conductive polymer using a copolymer such as polyanthracene, polyaniline, or polyacetylene is formed in an electrode, an electrode having excellent cycle life characteristics and high rate discharge characteristics can be obtained. Have been described.

  Patent Document 4 describes that by using an quinazone polymer obtained by reacting anthraquinone with an aromatic diisocyanate compound or a triisocyanate compound as an electrode, cycle characteristics are improved.

  Patent Document 5 describes a positive electrode active material layer composed of a conjugated conductive polymer compound and an ionic conductive polymer compound, and aminoanthracene or polyaniline compound is used as the conjugated conductive polymer compound. In addition, it is described that a crosslinked body such as a polyether polymer compound is used as the ion conductive polymer compound.

  In Patent Document 6, by providing an electrode active material layer containing a conductive polymer having a polyaniline as a main chain, the main chain forming a cross-linked structure and a cross-linked chain or side chain having a polyether structure. It is described that the dope / dedope (oxidation / reduction) cycle becomes stable.

  Patent Document 7 describes that a copolymer of aminoanthracene and aniline has electrical conductivity.

JP 2007-305481 A (paragraph 13) Japanese Patent Laying-Open No. 2005-2278 (paragraphs 8 and 54) JP 2000-173598 A (paragraphs 33 and 34) JP 59-196666 (columns 6 to 8) JP-A-5-166511 (paragraphs 7 to 10) JP-A-6-140041 (paragraph 5) JP 2006-265565 A (paragraphs 80 and 82)

Organic Electronics Industry Research Committee p179

  However, there is a problem that the organic material deteriorates or elutes into the electrolytic solution every time the charge / discharge cycle is repeated, and satisfactory cycle characteristics cannot be obtained.

  The present invention has been made in view of such circumstances, and a crosslinked polyaniline derivative capable of improving the cycle characteristics of the battery when used as a positive electrode active material, and a non-aqueous secondary battery using the crosslinked polyaniline derivative. It is an object to provide a positive electrode active material, a positive electrode, a non-aqueous secondary battery, and a vehicle.

  (1) The crosslinked polyaniline derivative of the present invention is characterized by having a structure represented by the following general formula (1).

(In the general formula (1), R1 represents a group containing one or more selected from the group of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group, or a single bond; R2, R3, and R4 each independently represent a group containing one or more selected from the group consisting of a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a substituent, and a hydrogen group. R5 represents a group containing one or more selected from the group of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group, or a single bond, X1 and X2 are Each independently represents a substituent or a hydrogen group, l represents an integer of 1 or more, and n represents an integer of 2 or more, and R1 and R2 or / and R3 and R4 combine to form a ring. May be.)

  (2) The positive electrode active material for a non-aqueous secondary battery of the present invention is characterized by comprising the above-mentioned crosslinked polyaniline derivative.

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

  (4) A non-aqueous secondary battery of the present invention includes the positive electrode described above, a negative electrode, and an electrolyte.

  (5) The vehicle of the present invention includes the non-aqueous secondary battery described above.

  Since the crosslinked polyaniline derivative of the present invention has the structure represented by the general formula (1), the cycle characteristics of the battery can be improved when used as a positive electrode active material. Moreover, since the positive electrode active material of this invention consists of the said bridge | crosslinking polyaniline derivative, the cycling characteristics of a battery can be improved. Moreover, since the non-aqueous secondary battery of the present invention uses the positive electrode active material, it has excellent cycle characteristics. In addition, since the vehicle of the present invention is equipped with the non-aqueous secondary battery, it can exhibit high output.

It is a diagram which shows the FT-IR spectrum of compound 2,3,5,6,8,9. It is a diagram showing a GPC chart of compounds 5, 6, 8, and 9. It is a figure which shows the charging / discharging curve of compound 3,6,9. It is a figure which shows the discharge capacity in the different current density of the compound 9.

  The cross-linked polyaniline derivative, which is an embodiment of the present invention, and a positive electrode active material and positive electrode for a non-aqueous secondary battery using the cross-linked polyaniline derivative, a non-aqueous secondary battery, and a vehicle will be described in detail.

(1) Crosslinked polyaniline derivative The crosslinked polyaniline derivative has a structure represented by the general formula (1). Since this crosslinked polyaniline derivative is a crosslinked product obtained by crosslinking the polyaniline derivative, elution into the electrolytic solution can be suppressed. In the crosslinked polyaniline derivative according to the present invention, the polyaniline derivative is polymerized by a double bond with an ethynyl group, so that the polyaniline derivatives are crosslinked with each other. For this reason, the polymer structure is more stable than a polymer polymerized by a single bond. Therefore, the deterioration of the polymer structure is suppressed, and the charge / discharge cycle characteristics are improved in the case of a battery.

  Polyaniline derivatives that are cross-linked with each other have an aromatic ring in the main chain, and the aromatic ring is bonded via an imino group to form a polymer. In the battery reaction, Li ions are coordinated to the nitrogen atom of the imino group, and electrons are transferred between the nitrogen atom and the aromatic rings on both sides thereof, so that a large number of electrons move in one step. . Since it has such a one-stage multi-electron transfer aromatic ring, it produces many electrons in the battery reaction and has a high energy density. In the crosslinked polyaniline derivative, the π-conjugated system is widened, and smooth multi-electron transfer is possible. Therefore, a battery using the crosslinked polyaniline derivative of the present invention as a positive electrode active material is expected to have a high charge / discharge capacity.

  Furthermore, the following can be said when the crosslinked polyaniline derivative of the present invention is compared with a polymer having a radical molecule (for example, Patent Document 1). The behavior of electrons in radical molecules is multistage multielectron transfer. In radical molecules, the redox sites are basically largely separated in the first and second stages. Further, the redox potential at the second stage remains at a low potential of, for example, less than 3V. Therefore, when a polymer having radical molecules in the side chain is used as the positive electrode active material, the average voltage is lower than the average voltage desired for the battery, and the energy density is lowered. In the unit of the crosslinked polyaniline derivative of the present invention, the second electron moves in concert with the potential of the first electron which is lower than the potential energy of the first step. For this reason, in the unit of the crosslinked polyaniline derivative of the present invention, multiple electrons can be easily transferred in one step, and the average voltage and energy density can be increased by using the unit as a positive electrode active material of a battery.

  In the crosslinked polyaniline derivative of the present invention, the polyaniline derivatives are crosslinked through an ethynyl group. The ethynyl group has a double bond, and the polyaniline derivative is cross-linked through the double bond. Therefore, electrons can be exchanged between and within the polyaniline derivative, and the conductivity is high.

In the general formula (1), R1 represents a group containing one or more selected from the group consisting of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group, or a single bond; , R3 and R4 each independently represents a group containing at least one selected from the group consisting of a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a substituent, and a hydrogen group. R5 represents a group containing one or more selected from the group of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group, or a single bond, and X1 and X2 are Each independently represents a substituent or a hydrogen group, l represents an integer of 1 or more, and n is an integer of 2 or more. R1 and R2 or / and R3 and R4 may be bonded to form a ring. Since the ortho position prevents smooth electron transfer due to its steric factor, ortho substitution does not exhibit one-step two-electron transfer. In addition, diimine units are difficult to synthesize due to steric hindrance at the ortho position. Therefore, it is desirable that X ₁ and X ₂ are added to the para position or the meta position.

  Here, the substituted aliphatic hydrocarbon group or the substituted aromatic hydrocarbon group means that the aliphatic hydrocarbon group or the aromatic hydrocarbon group is further substituted with a substituent. The arylene group or the substituted cyclic substituent means that the arylene group portion or the cyclic portion of the cyclic substituent has at least one substituent.

  R 1, R 2, R 3, R 4 and R 5 may be a group consisting of one or more selected from the group of a substituted aliphatic hydrocarbon group and a substituted aromatic hydrocarbon group. The substituent of the aliphatic hydrocarbon group and the aromatic hydrocarbon group, that is, the substituent when the aliphatic hydrocarbon group and the aromatic hydrocarbon group are substituted with the substituent is not particularly limited. However, for example, the substituent is an aryl group such as a phenyl group, a tolyl group or a naphthyl group, an alkoxyl group such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a sec-butoxy group or a tert-butoxy group. Is mentioned. In addition to the hydrocarbon group composed of C (carbon) and H (hydrogen), this substituent may have a group having another element. Examples of groups having other elements include groups having O (oxygen), N (nitrogen), S (sulfur), etc., and specific examples thereof include hydroxyl groups, ether bonds, ketone groups, carbonyl groups, carboxyl groups, nitro groups. Groups, imino groups, amino groups, amide bonds, halogen groups (including Cl, F, Br, or I) and the like.

  R1, R2, R3, R4, and R5 may be a group consisting of one or more selected from the group of an unsubstituted aliphatic hydrocarbon group and an unsubstituted aromatic hydrocarbon group.

  The group consisting of one or more selected from the group of unsubstituted aliphatic hydrocarbon groups and unsubstituted aromatic hydrocarbon groups represented by R1, R2, R3, R4, and R5 is, for example, each independently a methyl group, ethyl Group, chain alkyl group such as n-propyl group, isopropyl group, sec-butyl group, isobutyl group and tert-butyl group, cyclic alkyl group such as cyclopentyl group and cyclohexyl group, alkenyl group such as vinyl group and allyl group, You may have aryl groups, such as a phenyl group, a tolyl group, and a naphthyl group.

  R1 may be a single bond. In this case, the ethynyl group bridging moiety in the general formula (1) and the aromatic group moiety are directly bonded by a single bond (single bond). R1 is a group consisting of one or more selected from the group consisting of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group, that is, an aromatic hydrocarbon group in the general formula (1) And a linking group that links the ethynyl group. When R1 is a linking group, R1 is preferably a phenyl group.

  R5 may be a single bond. In this case, the phenyl group in the unit in the general formula (1) and the phenyl group in the other unit are directly bonded by a single bond (single bond). R5 represents a group consisting of one or more selected from the group consisting of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group, that is, a phenyl group in the unit of the general formula (1). And a linking group that links the phenyl group in another unit. A linking group that links an aromatic hydrocarbon group and an ethynyl group may also be used. When R5 is a linking group, R5 is preferably an aliphatic hydrocarbon group such as an ethylene group.

  R2, R3, and R4 may themselves be a substituent. The substituent is not particularly limited. For example, the substituent may be an aryl group such as a phenyl group, a tolyl group, or a naphthyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, sec. An alkoxyl group such as a -butoxy group and a tert-butoxy group can be mentioned. In addition, the substituent may be a group having O (oxygen), N (nitrogen), S (sulfur), etc., and specific examples include a hydroxyl group, a nitro group, an imino group, an amino group, a halogen group (Cl, F, Br). , Or I). R2, R3, and R4 may be a hydrogen group.

  R1, R2, R3 and R4 may form a group different from each other. R1 and R2 may be bonded to each other to form a ring, and R3 and R4 may be bonded to each other to form a ring. R1 and R2 or / and R3 and R4 combine to form a ring, thereby forming a condensed polycyclic aromatic group such as a benzene skeleton, a naphthacene skeleton, an anthracene skeleton, or a pentacene skeleton in one unit. . Furthermore, R1 and R2 may have a portion that is bonded to each other to form a ring and a portion that forms a separate group. R3 and R4 may have a portion that is bonded to each other to form a ring, and a portion that forms a separate group.

  X1 and X2 in the general formula (1) each independently represent a substituent or a hydrogen group. Examples of the substituent include aryl groups such as phenyl group, tolyl group, and naphthyl group, and alkoxyl groups such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, sec-butoxy group, and tert-butoxy group. In addition to the hydrocarbon group composed of C (carbon) and H (hydrogen), this substituent may have a group having another element. Examples of groups having other elements include groups having O (oxygen), N (nitrogen), S (sulfur), etc., and specific examples thereof include hydroxyl groups, ether bonds, ketone groups, carbonyl groups, carboxyl groups, nitro groups. Groups, imino groups, amino groups, amide bonds, halogen groups (including Cl, F, Br, or I) and the like.

  In the general formula (1), l represents a degree of cross-linking in which the polyaniline derivatives in the cross-linked polyaniline derivative are cross-linked via an ethynyl group, and may be an integer of 1 or more.

  In the general formula (1), l indicating the degree of crosslinking of the ethynyl group is expressed when the molecular chains of the polyaniline derivative are bonded to each other (intermolecular: in the case of crosslinking) and when bonded within one molecular chain (intramolecular )

  N in the general formula (1) indicates the degree of polymerization of the unit of the polyaniline derivative in the crosslinked polyaniline derivative, and may be an integer of 2 or more. Preferably, n is 2 or more and 2000 or less, and more preferably 50 or more and 500 or less. When n is less than 50, the crosslinked polyaniline derivative may be dissolved in the electrolytic solution. When n exceeds 500, there is a possibility that polymerization within the molecule will occur preferentially.

  The crosslinked polyaniline derivative may have a structure represented by the following general formula (2).

  In general formula (2), R1, R2, R3, R4, R5, X1, X2, l, and n are R1, R2, R3, R4, R5, X1, X2, and l in general formula (1). , N. In general formula (2), m is an integer of 1 or more.

  In the crosslinked polyaniline derivative of the general formula (2), the ethynyl group in the polyaniline derivative is crosslinked with the ethynyl group of another polyaniline derivative. It is not necessary for all ethynyl groups contained in the crosslinked polyaniline derivative to be crosslinked, and as shown in the general formula (2), uncrosslinked ethynyl groups may remain. In this case, the degree of freedom of the uncrosslinked unit is high, and it becomes easy for many electrons to move in one stage within each unit, and the battery capacity is increased.

  In one polyaniline derivative among the crosslinked polyaniline derivatives, the unit having a cross-linked ethynyl group and the unit having an uncross-linked ethynyl group may be arranged regularly or irregularly. . All units of ethynyl groups of one polyaniline derivative may be cross-linked with other polyaniline derivatives, or one or more units of ethynyl groups in one polyaniline derivative are cross-linked with other polyaniline derivatives. May be.

  Specific examples of the crosslinked polyaniline derivative include a compound represented by the following general formula (3). Among these, the compound represented by the general formula (3) is preferable because the battery capacity can be increased when used as a positive electrode active material.

  In general formula (3), R5 represents a group containing one or more selected from the group of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group, or a single bond. R6 represents a group containing one or more selected from the group of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group, or a single bond, and R7, R8, and R9 are substituted Or a group containing at least one selected from the group of an unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, a substituent, and a hydrogen group, and X1 and X2 are each independently, Represents a substituent or a hydrogen group, l represents an integer of 1 or more, and n represents an integer of 2 or more.

  The general formula (3) is a crosslinked product in which a polyaniline derivative having an anthracene ring as a main chain is crosslinked via an ethynyl group. The compound represented by the general formula (3) has an anthracene skeleton, and when used as a positive electrode active material, a smooth electron transfer can be performed by an anthracene skeleton or / and a π-π interaction between the anthracene skeleton and the carbon material. This is preferable because the battery capacity can be increased. In the general formula (3), an ethynyl group is connected to the 2-position of the anthracene ring via R6. R6 between the ethynyl group and the anthracene ring is a linking group or a single bond.

  When R6 is a linking group, the linking group comprises at least one selected from the group consisting of a substituted or unsubstituted aliphatic hydrocarbon group or a substituted or unsubstituted aromatic hydrocarbon group. For example, the linking group may be, for example, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, substituted or unsubstituted Examples thereof include an unsubstituted thiophenyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted furanyl group, and a substituted or unsubstituted pyrrolyl group. Among these, R6 is preferably a substituted or unsubstituted phenyl group, and is preferably an unsubstituted phenyl group.

  R7, R8 and R9 in the general formula (3) may each independently constitute a substituted or unsubstituted aliphatic hydrocarbon group or a substituted or unsubstituted aromatic hydrocarbon group. R7, R8, and R9 may themselves constitute a substituent of the anthracene ring or may be a hydrogen group. R5, l and n in the general formula (3) are the same as R5, l and n in the general formula (1).

  The crosslinked polyaniline derivative may have a structure represented by the general formula (4).

  In general formula (4), R5, R6, R7, R8, R9, X1, X2, l, and n are R5, R6, R7, R8, R9, X1, X2, and l in general formula (3). , N. In general formula (4), m is an integer of 1 or more.

  It is not necessary that all ethynyl groups contained in the crosslinked polyaniline derivative represented by the general formula (3) are crosslinked, and an uncrosslinked ethynyl group may remain as represented by the general formula (4). In this case, the degree of freedom of the uncrosslinked unit is high, and it becomes easy for many electrons to move in one stage within each unit, and the battery capacity is increased.

  In one polyaniline derivative among the crosslinked polyaniline derivatives, the unit having a cross-linked ethynyl group and the unit having an uncross-linked ethynyl group may be arranged regularly or irregularly. . All units of ethynyl groups of one polyaniline derivative may be cross-linked with other polyaniline derivatives, or one or more units of ethynyl groups in one polyaniline derivative are cross-linked with other polyaniline derivatives. May be.

  The crosslinked polyaniline derivative of the present invention is produced by crosslinking an ethynyl group of a polyaniline derivative with an ethynyl group of another polyaniline derivative.

A catalyst may be added when the polyaniline derivative is crosslinked. As the catalyst, known transition metal compounds such as Rh, Ru, W, and Mo may be used. Examples thereof include Rh catalyst (norbornadiene rhodium chloride dimer), WCl ₆ , MoCl _{6 and the} like.

  Cross-linking of the polyaniline derivative proceeds even at room temperature, but it may be performed at 0 to 180 ° C, preferably 10 to 100 ° C. The polymerization time is 1 to 48 hours, preferably 6 to 30 hours, although it depends on the amount of monomer, the type of polymerization catalyst and other polymerization conditions.

  The crosslinking reaction for crosslinking the polyaniline derivative can be performed even in the presence of a carbon material such as carbon black. As carbon black, ketjen black, acetylene black, etc. can be used. The crosslinked polyaniline derivative formed by crosslinking in the presence of the carbon material is adsorbed on the carbon material having conductivity. For this reason, electron conductivity becomes high and high-speed electron movement becomes possible.

  In synthesizing the polyaniline derivative before crosslinking, for example, an aromatic compound in which two oxo groups are bonded to the imino group introduction site is prepared as a starting material. An ethynyl group is introduced into this aromatic compound. The ethynyl group is preferably protected with a protecting group. Dianilines are bonded to the aromatic compound by dehydration condensation reaction to the aromatic compound into which the ethynyl group has been introduced. At this time, the oxo group of the aromatic compound is replaced with the nitrogen atom of the dianiline, and the dianiline is bonded to the aromatic compound via the imino group. Thereby, the polyaniline derivative which a dianiline and an aromatic compound connect alternately and continues is obtained.

  Specifically, for example, when the crosslinked polyaniline derivative has a structure in which a phenyl group is bonded to an anthracene ring via an imino group as shown in chemical formula (3), the polyaniline derivative before the crosslinking is For example, in step 1, 2- (trimethylsilylethynyl) anthraquinone is converted to an imine by performing a dehydration condensation reaction in the presence of dianilines, titanium tetrachloride and a base. At this time, the anthracene ring and the dianiline are linked via the imino group to produce a polyaniline derivative. The 2- (trimethylsilylethynyl) anthraquinone used here is obtained by introducing a trimethylsilylethynyl group into 2-bromoanthraquinone by Sonogashira reaction. The dianilines are compounds in which two aromatic hydrocarbon groups having an amino group are linked by a single bond or a linking group, and the aromatic hydrocarbon group may have a substituent in addition to the amino group. It does not have to have a substituent. The base is not particularly limited as long as it is a basic catalyst, and examples thereof include 1,4-diazabicyclo [2,2,2] octane (DABCO).

In step 2, the polyaniline derivative before crosslinking of the crosslinked polyaniline derivative represented by the chemical formula (3) can be synthesized by deprotecting the trimethylsilyl group with a desilylating agent. As the desilylating agent, tetraalkylammonium fluoride, alkali metal fluoride such as potassium fluoride, acid or alkali can be used, but as a preferable desilylating agent, tetrabutylammonium fluoride (nBu ₄ NF) is used. ) Tetraalkylammonium fluoride.

(2) Positive electrode active material for non-aqueous secondary battery The positive electrode active material for non-aqueous secondary battery of the present invention is the above-mentioned crosslinked polyaniline derivative, and has at least two imino groups in one unit of the polyaniline derivative. . Here, the positive electrode active material for a non-aqueous secondary battery refers to a substance that directly contributes to the positive electrode of the non-aqueous secondary battery in the charge reaction and discharge reaction of the non-aqueous secondary battery.

(3) Positive electrode for non-aqueous secondary battery The positive electrode for a non-aqueous secondary battery of the present invention has a positive electrode active material having the crosslinked polyaniline derivative. The positive electrode is preferably provided with the positive electrode active material described above on at least the surface of the current collector. The current collector refers to a chemically inert electronic high conductor that keeps a current flowing through an electrode during discharging or charging of a non-aqueous secondary battery. The current collector has a shape such as a foil, a plate, or a mesh formed of the electronic high conductor. Examples of the material used for the current collector include copper and aluminum. Among these, copper is preferable.

  One method for providing the positive electrode active material on at least the surface of the current collector includes, for example, applying the positive electrode active material to the surface of the current collector. Although it does not specifically limit as a coating method, For example, a roll coat method, a dip coat method, a doctor blade method, a spray coat method, a curtain coat method etc. are mentioned.

  The positive electrode for a non-aqueous secondary battery of the present invention is preferably provided with a conductive additive on the current collector surface together with the positive electrode active material of the present invention. A conductive additive is added to increase the conductivity of the positive electrode. Examples of the conductive aid include carbon black, graphite, acetylene black, ketjen black, and carbon fiber, which are carbonaceous particles. These may be added alone or in combination of two or more thereof. The addition amount of the conductive auxiliary is preferably 10 to 2000 parts by mass, more preferably 100 to 1000 parts by mass, and 200 to 800 parts by mass per 100 parts by mass of the positive electrode active material of the present invention. Is more preferable.

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

  The negative electrode has a negative electrode active material. The negative electrode is preferably composed of a negative electrode active material and a current collector provided with at least the surface of the negative electrode active material. As the negative electrode active material, metallic lithium or a lithium alloy is preferably used. As the current collector, nickel, stainless steel, or the like can be used, and the current collector may have any shape such as a foil, a plate, and a mesh. A battery using metallic lithium or a lithium alloy as the negative electrode active material is referred to as a lithium secondary battery. As the negative electrode active material, a Si-based material and / or a Sn-based material can be used instead of metallic lithium or a lithium alloy. A secondary battery using a lithium metal or lithium alloy capable of occluding and releasing Li ions as a negative electrode active material is called a lithium secondary battery, and other materials that can occlude and release Li ions are used. Is called a lithium ion secondary battery.

  Moreover, the negative electrode may be comprised from the negative electrode active material and binder which can occlude / desorb lithium ion like a positive electrode. As the negative electrode active material, for example, a natural graphite, artificial graphite, an organic compound heating body such as a phenol resin, or a carbonaceous powder such as coke can be used. As the binder, as in the positive electrode, a fluorine-containing resin, a thermoplastic resin, or the like can be used. Moreover, it can also be set as the sodium secondary battery which used sodium for the negative electrode.

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

The electrolyte may be contained in the nonaqueous electrolytic solution. The nonaqueous electrolytic solution is obtained by dissolving a fluoride salt as an electrolyte in an organic solvent. The electrolyte fluoride salt is preferably an alkali metal fluoride salt soluble in an organic solvent. Examples of the alkali metal fluoride include LiPF ₆ , LiBF ₄ , LiAsF ₆ , NaPF ₆ , NaBF ₄ , NaAsF _6, CF ₃ SO ₃ Li, C ₄ F ₉ SO ₃ Li, (CF ₃ SO ₂ ) ₂ NLi , (CF ₃ SO ₂ ) ₃ CLi, and LiClO ₄ may be used. The organic solvent of the non-aqueous electrolyte is preferably an aprotic organic solvent, and includes, for example, chain carbonates, cyclic carbonates, cyclic esters, nitrile compounds, acid anhydrides, amide compounds, phosphate compounds, amine compounds, and the like. It is. Specific examples include propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethoxyethane, γ-prolactin, N-methylpyrrolidinone, N, One or more selected from N′-dimethylacetamide, a mixture of propylene carbonate and dimethoxyethane, a mixture of ethylene carbonate and diethyl carbonate, and a mixture of sulfolane and tetrahydrofuran can be used.

  The electrolyte may be a polymer gel electrolyte composed of a polymer gel containing an electrolyte solution. Examples of the electrolyte contained in the polymer gel electrolyte include lithium salts such as.

  As the polymer gel, it is preferable to use a prepolymer TA210 (polyfunctional acrylate polymer having a polyoxyalkylene chain) that is polymerized with a photopolymerization initiator (for example, IRGACURE 184), and acrylonitrile and methyl acrylate or methacrylic acid. Copolymers may be used. The polymer gel electrolyte can be obtained by immersing the polymer in the electrolyte solution or polymerizing the polymer structural units (monomer / compound) in the presence of the electrolyte solution.

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

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

(5) Vehicle, etc. The nonaqueous secondary battery may be mounted on the vehicle. By driving the traveling motor with a non-aqueous secondary battery using negative electrode active material particles having the above particle size characteristics, it can be used for a long time with a large capacity and a large output. The vehicle may be a vehicle that uses electric energy from a non-aqueous secondary battery for all or a part of its power source, for example, an electric vehicle or a hybrid vehicle. When mounting the non-aqueous secondary battery of the present invention on a vehicle, a plurality of non-aqueous secondary batteries may be connected in series to form an assembled battery.

  The non-aqueous secondary battery can be used for various home appliances, office devices, and industrial devices driven by batteries such as personal computers and portable communication devices, in addition to vehicles.

  As shown below, three kinds of crosslinked polyaniline derivatives of the present invention were synthesized in Examples 1 to 3, and battery characteristics were evaluated together with the polyaniline of Comparative Example 1 and the polyaniline derivative of Comparative Example 2.

Example 1
The synthesis scheme of the crosslinked polyaniline derivative of Example 1 was synthesized as shown in “Chemical Formula 5”.

In step 1, 2- (trimethylsilylethynyl) anthraquinone (0.1533 g, 0.50 mmol), 4,4'- ethylenedianiline (0.10736 g, 0.50 mmol), and 1,4-diazabicyclo [2.2.2] octane (DABCO) To a mixed solution of (0.51720 g, 4.6 mmol) of chlorobenzene (5 ml), a solution of titanium tetrachloride TiCl4 (0.1 ml, 0.91 mmol) in chlorobenzene (1 ml) was gradually added at 90 ° C. The reaction mixture was stirred at 125 ° C. overnight. The precipitate was removed by filtration. The filtrate was evaporated and reprecipitated in a large amount of methanol to obtain a polymer compound 1 (0.17567 g, 0.40 mmol) in a yield of 73%. Gel permeation gas chromatograph (GPC): number average molecular weight (Mn) = 8412, mass average molecular weight / number average molecular weight (Mw / Mn) = 1.416. Infrared absorption spectrum (IR) (ATR, cm-1) 1622, 1589, 1559, .1498, 1473, 1456, 1293, 1247, 1093, 880, 834, 758, 729, 677, 649, 637, 571, 518. 1H-NMR spectrum (500 MHz, CDCl3) d 8.42-8.24 (m, 2H), 7.62-7.00 (m, 9H), 6.82-6.72 (m, 4H), 2.91 (brs, 4H), 0.27-0.09 (m , 9H).

In Step 2, tetrabutylammonium fluoride (n-Bu ₄ NF) (0.9 ml, 1M in THF) was added to a solution of Compound 1 (0.11389 g, 0.24 mmol) in tetrahydrofuran (THF) (4 ml). The reaction mixture was stirred at room temperature for 3 hours. The reaction mixture was reprecipitated in a large amount of methanol to obtain Compound 2 (0.07233 g, 0.18 mmol) in 94% yield. GPC: M _n = 6895, M _w / M _n = 1.517. IR spectrum (ATR, cm ⁻¹ ) 1624, 1591, 1499, 1296, 1270, 1234, 946, 911, 835, 771, 680, 650, 639, 621, 582, 559, 539, 490, 442, 407. ¹ H-NMR spectrum (500 MHz, CDCl ₃ ) d 8.43-8.27 (m, 2H), 7.64-7.06 (m, 9H), 6.81-6.72 (m, 4H), 3.26-3.10 (m, 9H), 2.91 (brs, 4H).

In Step 3, a mixed solution of Compound 2 (0.04026 g, 0.099 mmol) and triethylamine (Et ₃ N) (100 μl) in THF (4.5 ml) was mixed with norbornadiene rhodium chloride dimer [Rh (nbd) Cl] ₂ ( 0.00275 g, 0.0060 mmol) in THF (0.5 ml) was added and the reaction mixture was allowed to stir at 30 ° C. for 24 hours in the presence of argon. The reaction mixture was reprecipitated in a large amount of methanol to quantitatively obtain Compound 3 (0.0402 g, 0.099 mmol). IR spectrum (ATR, cm ⁻¹ ) 1620, 1587, 1497, 1454, 1439, 1291, 1230, 1174, 1142, 1095, 1015, 943, 910, 828, 769, 677, 577, 535, 519.

The obtained Compound 3 is a crosslinked polyaniline derivative represented by “Chemical Formula 6”. This compound 3 contains an electrolyte (1M LiPF ₆ / ethylene carbonate (EC): diethylene carbonate (DEC) (1: 1 volume / volume%)) and a common organic solvent (trichloromethane (CHCl ₃ ), THF, dimethyl sulfoxide). In other words, each of these solvents was added to Compound 3 and allowed to stand, and then the visible ultraviolet spectrum of each supernatant was measured in the range of 250 nm to 800 nm. When measured in the range of 250 nm to 800 nm, the absorbance in that range was 0 (zero).

  Further, Fourier transform infrared spectroscopy (FT-IR) spectra were measured for compound 2 before the crosslinking reaction shown in step 3 and compound 3 after the crosslinking reaction. As a result, as shown in the upper part of FIG. 1, there was no change in the spectrum between compounds 2 and 3. From this, it is considered that in step 3, the crosslinking reaction proceeded while maintaining the structure of the one-step two-electron transfer unit.

(Example 2)
The synthesis scheme of the crosslinked polyaniline derivative of Example 2 was synthesized as shown in “Chemical Formula 7”. In Example 2, in Step 1, 2- (trimethylsilylethynyl) anthraquinone, anthraquinone having no trimethylsilylethynyl group, and 4,4′-ethylenedianiline were used as starting materials in a 1: 4: 5 (molar ratio). ) Is different from Example 1 in that the dehydration condensation reaction is carried out at a ratio of

In this Example 2, in step 1, 2- (trimethylsilylethynyl) anthraquinone (0.03045 g, 0.10 mmol), anthraquinone (0.08337 g, 0.40 mmol), 4,4′-ethylenedianiline (0.10619 g, 0.50 mmol), And 1,4-diazabicyclo [2.2.2] octane (DABCO) (1.02402 g, 9.1 mmol) in chlorobenzene (5 ml) were mixed with TiCl ₄ (0.1 ml, 0.91 mmol) in chlorobenzene (2 ml) at 90 ° C. Added at. The reaction mixture was stirred at 125 ° C. overnight. The precipitate was removed by filtration. The filtrate was evaporated and reprecipitated in a large amount of methanol to obtain a polymer compound 4 (0.15131 g, 0.38 mmol) in a yield of 75%. GPC: M _n = 6868, M _w / M _n = 1.581; IR spectrum (ATR, cm ^-1 ) 1670, 1623, 1590, 1499, 1302, 1272, 1233, 1158, 1145, 1095, 960, 946, 881, 833, 783, 759, 670, 638, 581, 519.
In Step 2, n-Bu ₄ NF (0.5 ml, 1M in THF) was added to a solution of compound 4 (0.08044 g, 0.20 mmol) in THF (5 ml). The reaction mixture was stirred at room temperature for 5 hours. The reaction mixture was reprecipitated with a large amount of methanol to obtain Compound 5 (0.05606 g, 0.14 mmol) in a yield of 72%. GPC: M _n = 6988, M _w / M _n = 1.521; IR spectrum (ATR, cm ^-1 ) 1622, 1590, 1499, 1301, 1271, 1231, 960, 945, 828, 782, 757, 669, 633, 581, 519, 482, 463, 442, 419, 404.
In Step 3, compound 5 (0.04026 g, 0.099 mmol) and triethylamine (Et ₃ N) (100 μl) in THF (4.5 ml) were mixed with [Rh (nbd) Cl] ₂ (0.00273 g, 0.0059 mmol) in THF. (0.5 ml) solution was added and the reaction mixture was stirred at 30 ° C. for 24 hours in the presence of argon. The reaction mixture was reprecipitated with a large amount of methanol to obtain Compound 6 (0.03918 g, 0.099 mmol) in a yield of 97%. GPC: M _n = 12940, M _w / M _n = 2.982; IR (ATR, cm ^-1 ) 1622, 1590, 1499, 1301, 1271, 1231, 1158, 1144, 1094, 960, 945, 828, 782, 669 , 632, 579, 552, 516, 470, 411.

  The obtained compound 6 is a crosslinked polyaniline derivative represented by “Chemical Formula 8”. FT-IR spectra of compounds 5 and 6 were measured. As shown in the middle part of FIG. 1, there was no change in the IR spectrum between compounds 5 and 6. From this, it is considered that in step 3, the crosslinking reaction proceeded while maintaining the structure of the one-step two-electron transfer unit.

The GPC (gel permeation gas chromatograph) chart of compounds 5 and 6 is shown in the upper part of FIG. As shown in the upper part of FIG. 2, the number average molecular weight M _n of the compound 5 before the step 3 which is a crosslinking reaction was 6988, whereas the M _n of the compound 6 after the step 3 was about 12940. It was found that the number increased twice. From this, it is presumed that the compound 6 has undergone a crosslinking reaction and the polyaniline derivatives (the molecules of the compound 5) are crosslinked.

  Further, the same amount of ethylene carbonate was added to Compound 5 and Compound 6, and after standing, the visible ultraviolet spectrum of the supernatant was measured in the range of 250 nm to 800 nm. As a result, the absorbance of Compound 6 in the visible ultraviolet spectrum was higher than that of Compound 5. Diminished. From this, it can be seen that the solubility in the electrolytic solution is lower than that of the compound 5.

Example 3
The synthesis scheme of the crosslinked polyaniline derivative of Example 3 was synthesized as shown in “Chemical Formula 9”. In Example 3, in Step 1, as starting materials, 2- (4-triisopropylsilylethynylphenyl) anthraquinone, anthraquinone having no 4-triisopropylsilylethynylphenyl group, and 4,4′-ethylenedianiline Is different from Example 1 in that the dehydration condensation reaction is carried out at a ratio of 1: 4: 5 (molar ratio).

In Example 3, in step 1, 2- (4-triisopropylsilylethynylphenyl) anthraquinone (0.04656 g, 0.10 mmol), anthraquinone (0.08334 g, 0.40 mmol), and 4,4′-ethylenedianiline (0.10623 g, 0.50 mmol), and 1,4-diazabicyclo [2.2.2] octane (DABCO) (1.0423 g, 9.29 mmol) in chlorobenzene (5 ml) mixed with TiCl ₄ (0.1 ml, 0.91 mmol) in chlorobenzene. (2 ml) was added slowly at 90 ° C. The reaction mixture was stirred at 125 ° C. overnight. The precipitate was removed by filtration. The filtrate was evaporated and reprecipitated with a large amount of methanol to give compound 7 (0.16589 g, 0.38 mmol) in 76% yield. GPC: M _n = 6969, M _w / M _n = 1.609; IR spectrum (ATR, cm ^-1 ) 1622, 1590, 1499, 1460, 1302, 1271, 1231, 1158, 1145, 1094, 1015, 960, 944, 828, 782, 756, 669, 574, 518.
In Step 2, n-Bu ₄ NF (0.5 ml, 1M in THF) was added to a solution of compound 7 (0.10032 g, 0.23 mmol) in THF (5 ml). The reaction mixture was stirred at room temperature for 4.5 hours. The reaction mixture was reprecipitated with a large amount of methanol to obtain Compound 8 (0.09056 g, 0.22 mmol) in a yield of 97%. GPC: M _n = 6988, M _w / M _n = 1.521; IR spectrum (ATR, cm ^-1 ) 1669, 1622, 1590, 1499, 1302, 1271, 1231, 1158, 1145, 1094, 960, 945, 828, 783, 757, 670, 633, 579, 543, 518.
In step 3, compound 8 (0.04051 g, 0.10 mmol) and Et ₃ N (100 μl) in THF (4.5 ml) were mixed with [Rh (nbd) Cl] ₂ (0.00249 g, 0.0054 mmol) in THF (0.5 ml). The solution was added. The reaction mixture was stirred for 24 hours at 30 ° C. in the presence of argon. The reaction mixture was reprecipitated with a large amount of methanol to obtain Compound 9 (0.03842 g, 0.095 mmol) in a yield of 95%. GPC: M _n = 12940, M _w / M _n = 2.982; IR spectrum (ATR, cm ^-1 ) 1622, 1589, 1498, 1301, 1271, 1230, 1158, 1145, 1094, 1015, 960, 944, 827, 782, 669, 639, 580, 551, 517, 409.

  The resulting compound 9 is a crosslinked polyaniline derivative represented by “Chemical Formula 10”. FT-IR spectra of compounds 8 and 9 were measured. As shown in the lower part of FIG. 1, there was no change in the IR spectrum between compounds 8 and 9. From this, it is considered that in step 3, the crosslinking reaction proceeded while maintaining the structure of the one-step two-electron transfer unit.

The GPC chart of compounds 8 and 9 is shown in the lower part of FIG. As shown in the lower part of FIG. 2, the number average molecular weight M _n of the compound 8 before the step 3 which is a crosslinking reaction was 6969, whereas the M _n of the compound 9 after the step 3 was about 12940. It was found that the number increased twice. From this, it is presumed that the compound 9 has undergone a crosslinking reaction and the polyaniline derivatives (between the molecules of the compound 8) are crosslinked.

  Further, the same amount of ethylene carbonate was added to Compound 8 and Compound 9, and after standing, the visible ultraviolet spectrum of the supernatant was measured in the range of 250 nm to 800 nm. As a result, the absorbance of Compound 9 in the visible ultraviolet spectrum was higher than that of Compound 8. Diminished. From this, it can be seen that the solubility in the electrolytic solution is lower than that of the compound 5.

(Comparative Example 1)
Compound 10 of Comparative Example 1 is a commercially available polyaniline (manufactured by ALDRICH).

(Comparative Example 2)
Compound 11 of Comparative Example 2 is a polyaniline derivative represented by the following “Chemical Formula 11”. In producing the polyaniline derivative represented by “Chemical Formula 11”, anthraquinone (2.499 g, 12.0 mmol), 4,4′-ethylenedianiline (2.548 g, 12.0 mmol) and DABCO (12.75 g, 113.7 mmol) Was dissolved in monochlorobenzene (145 ml), and a monochlorobenzene solution (15 ml) of TiCl ₄ (2 ml, 18.1 mmol) was added dropwise, followed by reaction at 125 ° C. for 24 hours with stirring. After completion of the reaction, the precipitate was filtered, and the resulting solution was vacuum-dried, dissolved in a small amount of monochlorobenzene, and reprecipitated in ethyl acetate. (68% 3.408 g). According to GPC, the product had a number average molecular weight (Mn) of 9670 and a mass average molecular weight / number average molecular weight (Mw / Mn) = 1.626.

<Charge / discharge characteristics of battery>
Secondary batteries were produced using the compounds 3, 6, 9, 10, and 11 of Examples 1 to 3 and Comparative Examples 1 and 2 as positive electrode active materials as described below, and the battery performance was evaluated.

<Production of battery>
Compounds 3, 6, 9, 10, and 11 were used as positive electrode active materials, respectively. This positive electrode active material (2 mg, 20 wt%), Ketjen black (4 mg, 40 wt%), TAB (acetylene black and PTFE were 2 : 1 mixed, 4 mg, 40 wt%) was mixed to form a sheet, which was crimped to an aluminum mesh (14φ). It was dried at 120 ° C. under vacuum for 6 hours or more to obtain an electrode containing a polyaniline derivative. After that, it went in the glove box. This electrode was placed on a positive electrode current collector constituting a coin battery, and impregnated with an electrolytic solution [1M LiPF6 / EC: DEC (1: 1 by volume)]. A separator made of a polypropylene porous film and a glass filter were laminated on the electrode, and a lithium foil (14φ) serving as a negative electrode was further laminated. Then, the aluminum exterior of a coin battery was piled up in the state where insulating packing was arranged around. It was pressurized with a crimping machine to produce a sealed coin battery (lithium secondary battery) using each of the above compounds as the positive electrode active material and metallic lithium as the negative electrode active material.

<Charge / discharge test>
The charge / discharge test was carried out by passing a current density of 25 mA / g in the range of 4.0 V to 2.0 V through each manufactured battery. Since the active material did not have Li ion first, it was discharged to 2V, and then charged to 4V. Since the initial cycle did not show a plateau (flat part) corresponding to the redox (redox reaction) of the one-stage two-electron transfer unit, the subsequent step was designated as the first cycle.

  The charge / discharge curves of compounds 3, 6, and 9, which are crosslinking reaction products, are shown in FIG. As shown in FIG. 3, in the charge / discharge curve of Compound 3, a plateau corresponding to the redox of the one-step two-electron unit was not observed at about 3V. Compound 3 may have a high cross-linking ratio of ethynyl groups, and there may be no reaction space in which a battery reaction sufficiently works in a one-step two-electron unit. Moreover, there is a possibility that the electrolyte did not sufficiently penetrate into the crosslinked polymer.

  In the charge / discharge curves of compounds 6 and 9, redox derived from one-step two-electron unit was observed, and the capacity increased with each charge / discharge cycle.

  Table 1 shows the ratio of the theoretical capacity when the theoretical capacity of Example 1 is 1, and the measured capacity of Example 1 for the batteries using the compounds 3, 6, and 9 of Examples 1, 2, and 3. The ratio of the measured capacity when 1 is shown. The measured capacity was the discharge capacity at the first cycle. As shown in Table 1, the theoretical capacities of the batteries using compounds 3, 6, and 9 were almost equal. Regarding the measured capacity, the battery using the compounds 6 and 9 was about 1.4 times the battery using the compound 3.

  This is considered to be because compounds 6 and 9 have fewer ethynyl group cross-linked moieties than compound 3 and units in the polymer main chain easily move and one-step multi-electron transfer easily occurs.

  Moreover, the crosslinkable site (ethynyl group) of the crosslinked polyaniline derivative of Compound 3 is bonded to all of the anthracene skeleton units. The crosslinkable site (ethynyl group) of the crosslinked polyaniline derivative of compounds 6 and 9 is bonded to 20% of all anthracene units. The ratio of this crosslinkable site is determined by the ratio of anthraquinone with acetylene and anthraquinone without acetylene. Compound 3 in which the crosslinkable site was bonded to all units had a relatively low capacity, and the capacity of compounds 6 and 9 in which the crosslinkable site was bonded to some units was relatively high.

  Moreover, as shown in FIG. 3, the capacity | capacitances of the compounds 3, 6, and 9 increased each time charging / discharging repeated, and the capacity | capacitance became substantially constant from the 10th cycle. Similarly, the capacities of the compounds 10 and 11 of Comparative Examples 1 and 2 became almost constant from the 10th cycle. Therefore, Table 2 shows the capacity at the 50th cycle (relative capacity with respect to the capacity at the 10th cycle) when the capacity at the 10th cycle of each compound is 1. As shown in Table 2, in the battery using the compounds 3, 6, and 9 of Examples 1 to 3, the relative capacity at the 50th cycle was almost the same as that at the 10th cycle. On the other hand, the relative capacities of Compounds 10 and 11 of Comparative Examples 1 and 2 decreased. From this, it is considered that the cross-linked polyaniline derivative (compounds 3, 6, and 9) produced by performing Step 3 which is a cross-linking reaction is hardly dissolved in the electrolytic solution, and thus the cycle characteristics are improved.

<Battery rate characteristics>
A battery using Compound 9 as the positive electrode active material was charged at a current density of 25 mA / g, and discharged by changing the current density from 25 mA / g to 500 mA / g. As shown in FIG. 4, the capacity at a current density of 500 mA / g (discharged in 10 minutes) was 87.3 mAh / g, and the capacity of 96.4 mAh / g at a current density of 25 mA / g was maintained at 89%. From this, it can be seen that the compound 9 is capable of high-speed and large output and is excellent in rate characteristics. Regarding the rate characteristics of the compounds 3 and 6, the same results as those of the compound 9 were obtained.

Claims (8)

A crosslinked polyaniline derivative having a structure represented by the following general formula (1):
(In the general formula (1), R1 represents a group containing one or more selected from the group of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group, or a single bond; R2, R3, and R4 each independently represent a group containing one or more selected from the group consisting of a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, and a hydrogen group; R5 represents a group containing one or more selected from the group of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group, or a single bond, and X1 and X2 are each independently Represents a substituent or a hydrogen group, l represents an integer of 1 or more, and n represents an integer of 2 or more, R1 and R2 or / and R3 and R4 may be bonded to form a ring. Good.) The crosslinked polyaniline derivative according to claim 1, which has a structure represented by the following general formula (2).

(In the general formula (2), R1, R2, R3, R4, R5, X1, X2, 1, and n are R1, R2, R3, R4, R5, X1, in the general formula (1) of claim 1; Same as X2, l, n. In general formula (2), m is an integer of 1 or more.) The crosslinked polyaniline derivative according to claim 1, which has a structure represented by the following general formula (3).
(In the general formula (3), R5 represents a group containing one or more selected from the group consisting of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group, or a single bond; R6 represents a group containing one or more selected from the group of a substituted or unsubstituted aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group, or a single bond, and R7, R8, and R9 are substituted Or a group containing one or more selected from the group of an unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, and a hydrogen group, and X 1 and X 2 are each independently a substituent or Represents a hydrogen group, l represents an integer of 1 or more, and n represents an integer of 2 or more.) The crosslinked polyaniline derivative according to claim 3, which has a structure represented by the general formula (4).

(In the general formula (4), R5, R6, R7, R8, R9, X1, X2, 1, and n are R5, R6, R7, R8, R9, X1, in the general formula (3) of claim 3. Same as X2, l and n. In general formula (4), m is an integer of 1 or more.)   A positive electrode active material for a non-aqueous secondary battery, comprising the crosslinked polyaniline derivative according to any one of claims 1 to 4.   A positive electrode for a non-aqueous secondary battery, comprising the positive electrode active material according to claim 5.   A non-aqueous secondary battery comprising the positive electrode according to claim 6, a negative electrode, and an electrolyte.   A vehicle comprising the non-aqueous secondary battery according to claim 7.