JP2021181581A - Polymer, electrode, electric-storage device, and process for producing polymer - Google Patents

Abstract

To provide a polymer having excellent organic solvent solubility, an electrode including the polymer, an electric-storage device, and a process for producing the polymer.SOLUTION: The present invention discloses a polyamine polymer having a specific structure, for example. obtained by the reaction between an aromatic diamine (diphenyl amine) and an aromatic compound having two halogen atoms, (bis(4-bromophenyl)amine). There are also provided an electrode including the polymer, an electric-storage device, and a process for producing the polymer.SELECTED DRAWING: None

Description

The present invention relates to a polymer, an electrode, a power storage device, and a method for producing the polymer.

Aromatic amine-based polymers such as polyaniline are known as conductive polymers, and are being developed as hole transport materials used in organic ELs, organic transistors, solar cells, etc., and electrode materials such as lithium ion secondary batteries. It is expected. As such an aromatic amine-based polymer, in addition to polyaniline, for example, the linear polyarylene amine proposed in Patent Document 1 is known.

Further, it is known that aromatic diamine compounds such as N, N, N', N'-tetramethyl-benzidine are useful as an electrode active material for a power storage device (see Patent Document 2).

Japanese Unexamined Patent Publication No. 2008-45142 Japanese Unexamined Patent Publication No. 2014-222590

However, the conventionally proposed polyarylene amine has a problem that it is difficult to apply to a liquid phase process because it has poor solubility in an organic solvent and cannot be used as a hole transport material. Further, when the conventionally proposed aromatic diamine compound is used as an electrode active material of a power storage device, satisfactory characteristics may not be obtained in some cases.

Therefore, one embodiment of the present invention provides a novel aromatic amine-based polymer having excellent solubility in an organic solvent and a method for producing the same. Further, another embodiment of the present invention provides a novel aromatic amine-based polymer and a method for producing the same, which give satisfactory properties when used as an electrode active material of a power storage device.

In view of such circumstances, the present inventor has conducted diligent research and found that the above-mentioned problems can be solved by using a specific aromatic amine-based polymer having a branched chain structure or a network structure. It was completed.
The configuration example of the present invention is as follows.

One embodiment of the present invention
A polymer having at least one of the structures represented by the following formulas (1) and (2) (hereinafter, also referred to as “the present polymer 1”).
A polymer having a structure represented by the following formulas (3) and (R') and having a polystyrene-equivalent weight average molecular weight of 2,000 or more measured by gel permeation chromatography (hereinafter referred to as "the present polymer 2"). Also called) or
Provided is a polymer having a structure represented by the following formulas (1) and (6) (hereinafter, also referred to as “the present polymer 3”).
In addition, these polymers 1 to 3 are collectively referred to as the present polymer A.

Further, one embodiment of the present invention provides an electrode containing the present polymer A, and further provides a power storage device including the electrode as a positive electrode.

Further, one embodiment of the present invention is
A method for producing a polymer (hereinafter, also referred to as "method I"), which comprises a step of reacting a compound represented by the following formula (7) with a compound represented by the following formula (8) in the presence of a base. Or, a method for producing a polymer (hereinafter, also referred to as "method II"), which comprises a step of reacting a compound represented by the following formula (9) with a compound represented by the following formula (10) in the presence of a base. .)I will provide a.

According to one embodiment of the present invention, an aromatic amine-based polymer having excellent solubility in an organic solvent can be obtained. Therefore, the polymer is extremely useful as a positive electrode transport material or the like applied to a liquid phase process. Further, by using the polymer, it is possible to easily obtain a power storage device satisfying satisfactory characteristics, specifically, high discharge capacity, high cycle characteristics, and high rate characteristics. Therefore, the polymer is extremely useful as an electrode material for a power storage device.

This polymer A
The present polymer A is one of the following main polymers 1 to 3.
The present polymer 1 is represented by the following formula (1) (hereinafter, also referred to as “structure (1)”; other structures may be similarly expressed) and the following formula (2). A polymer having at least one of these structures.

The present polymer 1 having the structure (1) (hereinafter, also referred to as “the present polymer 1a”) has particularly excellent solubility in an organic solvent and is extremely useful as a positive electrode transport material or the like applied to a liquid phase process. Further, when the present polymer 1a is used as an electrode material, particularly an active material, a power storage device having excellent cycle characteristics can be easily obtained.

In formula (1), Ar ¹ is a mutually independently substituted or unsubstituted aromatic hydrocarbon group, and the binding agent that binds to ^{Ar 1 binds to N.}
Examples of the aromatic ring constituting the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a biphenyl ring and the like, and a benzene ring is preferable.
Examples of the substituent include a hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, a fluoro group, a carboxy group and the like.
As Ar ¹ , an unsubstituted aromatic hydrocarbon group is preferable, and a p-phenylene group is more preferable.

Y is a single bond independently represents a divalent linking group or two is two hydrogen atoms or a substituent bonded to Ar ¹ each.
Examples of the linking group include -O-, -NR- (R is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms), -S-, -CO-, an alkylene group having 1 to 4 carbon atoms, and the like. Examples of the substituent include a group similar to the substituent ^{in Ar 1.}
Y is preferably two hydrogen atoms bonded to each of a single bond, —S— or Ar ^1.
The plurality of Ys in the formula (1) may be the same or different. Similar statements herein have similar meanings.

n represents an integer of 4 or more, and is preferably an integer such that the weight average molecular weight of the obtained polymer is in the following range, and more preferably 10 to 100.

Specific examples of the present polymer 1a include the following polymers. N in the following polymer is synonymous with n in the formula (1).

The present polymer 1a may be the present polymer 3 having a structure represented by the above formula (1) and the following formula (6) from the viewpoint that a polymer having excellent solubility in an organic solvent can be obtained. preferable. In addition, "*" in the following formula (6) indicates a bond that binds to ^{Ar 1 in the formula (1).}

In formula (6), Ar ⁴ represents mutually independently substituted or unsubstituted aromatic hydrocarbon groups. Examples of aromatic rings and substituents constituting the aromatic hydrocarbon group in Ar ⁴ and preferable groups are the same as those in ^{Ar 1.}

R ² independently represents a hydrogen atom, a halo group, a nitro group, a hydroxyl group, a sulfo group, an amino group or an organic group.
Examples of the organic group include a hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and preferably an alkoxy group having 1 to 4 carbon atoms.
As the halo group, a fluoro group or a bromo group is preferable, and a fluoro group is more preferable.

When R ² is a polar group such as a halo group, a nitro group, a hydroxyl group, a sulfo group, an amino group or an alkoxy group, a polymer capable of swelling in a general electrolytic solution can be obtained. Therefore, the polymer is used as an electrode material. In particular, when used as an active material, a storage device exhibiting high rate characteristics and excellent cycle characteristics can be easily obtained.
When ^{the present polymer 3 in which R 2} is a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, particularly a hydrogen atom or a methoxy group, is used as an electrode material, particularly an active material, a power storage device having excellent cycle characteristics can be easily obtained. Obtainable.
When ^{the present polymer 3 in which R 2} is a hydrogen atom, a fluoro group or a hydrocarbon group, particularly a fluoro group or a methyl group is used as an electrode material, particularly an active material, a power storage device having a high discharge capacity can be easily obtained. be able to.
R ² is preferably a hydrogen atom, a fluoro group, a bromo group, a methyl group, or a methoxy group.

Z is a single bond, a divalent linking group or two is two hydrogen atoms or a substituent bonded to Ar ⁴ each. Examples of linking groups and substituents in Z, as well as preferred groups, are the same as in Y.

Specific examples of the structure (6) include the following structures. ^{R in the following structure is synonymous with R 2} in the formula (6), and is preferably a hydrogen atom, a methyl group, a methoxy group, a fluoro group or a bromo group.

Further, it is preferable that the structure (1) has a structure (R ¹ −N =) represented by the following formula (R) from the viewpoint of ease of production of the present polymers 1a and 3.
The formula (6) shows that R ¹ is bonded to N in the formula (1).

［式（Ｒ）において、Ｒ¹は水素原子、ハロ基、ニトロ基、水酸基、スルホ基、アミノ基又は有機基を示す。］

[In the formula (R), R ¹ represents a hydrogen atom, a halo group, a nitro group, a hydroxyl group, a sulfo group, an amino group or an organic group. ]

Examples of the organic group in R ^{1 include a group similar to the organic group in R 2} , as well as a substituted or unsubstituted aromatic hydrocarbon group, and the organic group includes "= N-Ar-**". [Ar indicates a substituted or unsubstituted aromatic hydrocarbon group, and ** indicates a bond that binds to N in the structure (1). ] It is preferable that the group is a group other than the group containing the structure represented by.
R ¹ is preferably a hydrogen atom or a substituted or unsubstituted aromatic hydrocarbon group, and particularly preferably a hydrogen atom.

Specific examples of the present polymer 1a and / or the present polymer 3 include the polymers of the following groups (a1) to (a4). N in the following polymer is synonymous with n in the formula (1).

The present polymer 1 may be a polymer having a structure represented by the following formula (2) (hereinafter, also referred to as “the present polymer 1b”).
When the present polymer 1b is used as an electrode material, particularly an active material, a power storage device having an excellent balance of discharge capacity and rate characteristics can be easily obtained.

In the above formula (2), Ar ² indicates a group containing an aromatic ring independently of each other (except when ^{all of a plurality of Ar 2} are biphenyl-4,4'-diyl), and Ar ³ are mutual. Independently indicates a group containing an aromatic ring.
Examples of the group containing an aromatic ring in Ar ² and Ar ^{3 include an aromatic hydrocarbon group exemplified in Ar 1} and a group in which a plurality of the aromatic hydrocarbon groups are linked by a divalent linking group. .. The divalent linking group includes -O-, -S-, -SO _2- , -NH-, -NHCO-, -COO-, substituted or unsubstituted divalent hydrocarbon group, -N (C). ₆ H ₅ )-etc. Examples of the substituent include a group similar to the substituent ^{in Ar 1.}
As Ar ² and Ar ³ , a group containing an unsubstituted benzene ring is preferable, and a group containing 1 to 5 unsubstituted benzene rings is particularly preferable.
The group bonded to N of ^{−Ar 3} − (N) _b ^{= may be bonded to Ar 2} to form a ring.

a represents an integer of 1 to 10.
b indicates 1 or 2 independently of each other.

The polymer 1b has a structure represented by the following formula (2') in that it has an excellent balance of discharge capacity and rate characteristics, and in particular, a power storage device having a large discharge capacity can be easily obtained. Polymers are preferred.

〔式（２'）におけるＡｒ²及びＡｒ³は相互に独立に、前記式（２）中のＡｒ²及びＡｒ³と同義である。〕

^{[Ar 2} and Ar ³ in the formula (2') are independently synonymous with ^{Ar 2} and Ar ³ in the formula (2). ]

Specific examples of the present polymer 1b include the following polymers.

The present polymer 2 has a structure represented by the following formulas (3) and (R'), and has a polystyrene-equivalent weight average molecular weight (Mw) of 2,000 or more measured by gel permeation chromatography (GPC). Is.
Such a present polymer 2 is particularly excellent in solubility in an organic solvent and is extremely useful as a positive electrode transport material or the like applied to a liquid phase process, and the present polymer 2 can be used as an electrode material, particularly active. When used as a substance, a power storage device having excellent cycle characteristics can be easily obtained.

In the formula (3), Ar ¹ and Y are independently synonymous with the ^{above Ar 1 and Y.}
m represents an integer of 2 or more.

In the formula (R'), R ¹ is a hydrogen atom, a halo group, a nitro group, a hydroxyl group, a sulfo group, an amino group or an organic group (however, from the organic group, "= N-Ar-**" [Ar is substituted. Alternatively, it indicates an unsubstituted aromatic hydrocarbon group, ** indicates a bond that binds to N in the following formula (3), excluding the group containing the structure represented by], and formula (R'). ^{Indicates that R 1} is bound to N in the above formula (3).
Examples of the organic group in R ^{1 include a group similar to the organic group in R 2} and a substituted or unsubstituted aromatic hydrocarbon group, and R ¹ is preferably a hydrogen atom or a substituted or unsubstituted group. It is an aromatic hydrocarbon group, particularly preferably a hydrogen atom.

The present polymer 2 has a repeating unit represented by the following formula (3-1) and a structure represented by the above formula (6) from the viewpoint that a polymer having excellent solubility in an organic solvent can be obtained. Is preferable. In addition, "*" in the formula (6) indicates a bond that binds to ^{Ar 1 in the following formula (3-1).}
The repeating unit represented by the following formula (3-1) is ^{between the core of the present polymer 2 represented by R 1} − and the end of the main polymer 2 represented by the above formula (6). It means a repeating unit derived from a monomer, which is located.
The present polymer 2 preferably has one or more structural units represented by the following formula (3-2) between the repeating units represented by the following formula (3-1).

In the formulas (3-1) to (3-2), Ar ¹ , Ar ⁴ , R ² , Y and Z are independently ^{synonymous with the above Ar 1} , Ar ⁴ , R ² , Y and Z. Further, in the formula (3-2), * 1 indicates a bond that binds to N in the repeating unit represented by the formula (3-1) or N in the structure (3-2). Further, in the formula (3-2), * 2 indicates ^{at least one of Ar 1 in} the repeating unit represented by the formula (3-1) or a bond that binds to ^{Ar 1} in the structure (3-2).

The present polymer 2 preferably contains 10 to 100 repeating units represented by the above formula (3-1).
Specific examples of the present polymer 2 include, for example, in the polymers represented by the groups (a1) to (a3), in addition to the polymers having n or more, the polymers represented by the groups (a1) to (a3). In the structural formula to be used, a polymer having one or more structural units represented by the above formula (3-2) between the repeating unit (structural unit enclosed in parentheses) and the repeating unit can be mentioned. Be done.

The Mw of the present polymer A is preferably 2. It is 000 to 100,000, more preferably 3,000 to 100,000, and particularly preferably 5,000 to 60,000.
Specifically, Mw is measured by the method described in the following Examples.

Method for Producing Polymer The method for producing the present polymer A is not particularly limited, but the present polymer A is described in the following method I or the present method from the viewpoint that a polymer having a desired structure can be easily produced. It is preferably manufactured by II.

In the present method I, in the presence of a base, a compound represented by the following formula (7) (hereinafter, also referred to as “compound (7)”; other compounds may be similarly expressed) and the following formula (8). ) Is a method including a step of reacting with the compound represented by.
According to this method, a polymer having a branched chain structure such as the present polymer 1a, the present polymer 2 and the present polymer 3, and particularly a hyperbranched polymer can be easily produced.

In the formula (7), Ar ¹ and Y are independently synonymous with ^{Ar 1} and Y in the formula (1).
X represents a chloro group, a bromo group or an iodine group independently of each other, and the bromo group is preferable from the viewpoint that the reaction proceeds more easily.
The compound (7) used in the method I may be one kind or two or more kinds.

The compound (7) may be obtained by using a commercially available product or by synthesizing it by a conventionally known method.
As the compound (7), the following compounds are preferable.

In the formula (8), Ar ⁴ , R ² and Z are independently synonymous with ^{Ar 4} , R ² and Z in the formula (6).
The compound (8) used in the method I may be one kind or two or more kinds.

As the compound (8), the following compounds are preferable.

The compound (8) may be a commercially available product or may be synthesized by a conventionally known method.
Examples of the conventionally known method, for example, a compound represented by R ² -Ar ⁴ -NH ₂ (wherein R ² and Ar ⁴ has the same meaning as R ² and Ar ⁴ in the formula (8).), R ² -Ar ⁴ -X (wherein R ² and Ar ⁴ has the same meaning as R ² and Ar ⁴ in the formula (8), X is a halo group.) and a compound represented by the following Pd (P (t -Bu) ₃ ) A method of reacting in the presence of a catalyst such as _{2) can be mentioned.}
In the present method I, instead of the compound (8), the compound represented by the precursor R ^2- Ar ^4- NH ₂ and the compound represented by the compound R ^2- Ar ^4- X are used. May be used.

The base is not particularly limited, and conventionally known bases can be used, but it is preferably a strong base, more preferably a base having low nucleophilicity, and specifically, a metal alkoxide. Examples thereof include metal amides, preferably sodium t-butoxide, potassium t-butoxide and the like.
The base used in the method I may be one type or two or more types.

It is preferable to use a catalyst for the reaction in the method I. As the catalyst, a conventionally known catalyst can be used, and specific examples thereof include the following compounds. Of these, a catalyst composed of trialkylphosphines and a palladium compound is preferable.
When a catalyst is used in the method I, the catalyst may be one kind or two or more kinds.

［前記化合物における、「Ｍｓ」はメシラート基を示し、「Ｃｙ」はシクロへキシル基を示し、「Ｌ」は配位子を示し、「ｉｐｒＯ」はイソプロポキシ基を示す。］

[In the compound, "Ms" indicates a mesylate group, "Cy" indicates a cyclohexyl group, "L" indicates a ligand, and "iprO" indicates an isopropoxy group. ]

The reaction in Method I is usually carried out in the presence of a solvent. As the solvent, a conventionally known solvent can be used, and the solvent is not particularly limited, but a solvent capable of dissolving the compounds (7) and (8) is preferable, and specifically, an ether solvent such as THF (tetrahydrofuran) is used. , Aromatic hydrocarbon solvents such as benzene, toluene, xylene and the like.
When a solvent is used in the method I, the solvent may be one kind or two or more kinds.

The reaction conditions in the method I are not particularly limited, but the reaction temperature is preferably 25 to 150 ° C., and the reaction time is preferably 0.5 to 10 hours. Further, in the present method I, the ratio of compound (7) to compound (8) used (compound (7): compound (8)) is preferably in the range of 100: 100 to 90: 100 in terms of molar ratio. ..

In the present method I, the structure is obtained by reacting "NH" in the polymer obtained by the above method with a compound containing ^{the above R 1 such as R 1} X (X is a halo group). ^{A polymer in which R 1} is bonded to N in (1) and (3) can be obtained. Examples of the compound represented by R ¹ X include chlorobenzene, bromonaphthalene, bromoanthracene, bromobenzoic acid and the like.

The method II is a method including a step of reacting a compound represented by the following formula (9) with a compound represented by the following formula (10) in the presence of a base.
According to this method, a network polymer such as the present polymer 1b can be easily produced.

In formula (9), Ar ⁵ represents a group containing an aromatic ring. Examples of groups containing an aromatic ring in Ar ⁵ , as well as preferred groups are the same as in Ar ² and Ar ³ .
As the compound (9), when the obtained polymer is used for the electrode, the aromatic ring is excellent in a good balance between the discharge capacity and the rate characteristics, and in particular, a power storage device having a large discharge capacity can be easily obtained. A compound in which an amino group is bonded to the para position of is preferable.

The compound (9) used in the method II may be one kind or two or more kinds.
The compound (9) may be obtained by using a commercially available product or by synthesizing it by a conventionally known method.
As the compound (9), the following compounds are preferable.

In formula (10), Ar ^{6 is synonymous with Ar 5 in} formula (9), and X represents a halo group independently of each other.
As the compound (10), when the obtained polymer is used for the electrode, the aromatic ring is excellent in a good balance between the discharge capacity and the rate characteristics, and in particular, a power storage device having a large discharge capacity can be easily obtained. A compound in which a halo group is bonded to the para position of is preferable.

The compound (10) used in the method II may be one kind or two or more kinds.
The compound (10) may be obtained by using a commercially available product or by synthesizing it by a conventionally known method.
As the compound (10), the following compounds are preferable.

The base used in the method II is not particularly limited, and conventionally known bases can be used, and examples thereof include the same bases as the base used in the method I.
The base used in this method II may be one kind or two or more kinds.

In the reaction in the method II, it is preferable to use the same catalyst and solvent as in the method I. The catalyst and the solvent may be one kind or two or more kinds, respectively.
As the reaction conditions in the method II, the same conditions as those in the method I can be mentioned. Further, in the present method II, the ratio of compound (9) to compound (10) used (compound (9): compound (10)) is preferably in the range of 50:90 to 50:110 in terms of molar ratio. ..

The present polymer A can be suitably used as a hole transport material for a power storage device, an organic EL, an organic transistor, a solar cell, etc. It is preferably used by a device, further preferably as an electrode material, and particularly preferably as a positive electrode material, specifically, a positive electrode active material.

Electrode The electrode according to the embodiment of the present invention (hereinafter, also referred to as “the present electrode”) is not particularly limited as long as it contains one or more kinds of the present polymer A, but the present polymer is placed on the current collector. An electrode having an active material layer containing A and a binder and the like is preferable.
The present polymer A used for the present electrode can be used as it is as an electrode material, but it can also be used as an electrode material after being composited with activated carbon, an inorganic substance, or the like. Further, the present polymer A can also be used as an electrode material together with a known positive electrode active material such as lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, and lithium iron phosphate.
In the following, the present polymer A, a composite of the present polymer A and activated carbon, or a mixture of the present polymer A and a known positive electrode active material is also referred to as a main active material.

The active material layer may be produced, for example, by preparing a slurry containing the main active material and a binder, applying the slurry onto a current collector, and drying the slurry, or using the main active material and the binder and the like. It may be produced by forming a film from the containing mixture in advance and arranging the film on the current collector by a (heat) press or an adhesive.

This electrode is preferably the positive electrode of a non-aqueous electrolyte secondary battery containing the main active material as the positive electrode active material, and contains a positive electrode active material in which the present polymer A is composited with activated carbon, a lithium ion capacitor or electricity. It is also preferable that it is the positive electrode of the double layer capacitor.

The content of the main active material in the present electrode is not particularly limited, but is preferably 10 to 90% by mass with respect to 100% by mass of the obtained active material layer.
The active material contained in the electrode of one embodiment of the present invention may be one kind or two or more kinds.

Examples of the material of the current collector include aluminum, stainless steel, copper, nickel and the like, but when the electrode according to the embodiment of the present invention is a positive electrode, aluminum, stainless steel and the like are preferable. The thickness of the current collector is usually 10 to 50 μm.

Examples of the binder include rubber-based binders such as styrene-butadiene rubber (SBR) and acrylonitrile-butadiene rubber (NBR); fluororesins such as polyvinylidene fluoride (PTFE) and polyvinylidene fluoride; polypropylene and polyethylene. In addition, a fluorine-modified (meth) acrylic binder disclosed in Japanese Patent Application Laid-Open No. 2009-246137 can be mentioned.
The binder may be one kind or two or more kinds.

The content of the binder is not particularly limited, but is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on 100% by mass of the obtained active material layer.

In the active material layer, carbon black (acetylene black, ketjen black, etc.), graphite, vapor-grown carbon fiber (VGCF), high-wall surface activated carbon (MAXSORB), carbon, as long as the effect of the present invention is not impaired. Conductive agents such as nanotubes (SWNT, MWNT, etc.), metal powder, etc .; increase in carboxylmethylcellulose, its Na salt or ammonium salt, methylcellulose, hydroxymethylcellulose, ethylcellulose, hydroxypropylcellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch or casein, etc. It may contain arbitrary components such as a slime.
Each of the optional components may be one kind or two or more kinds.

The thickness of the active material layer is not particularly limited, but is usually 5 to 500 μm, preferably 10 to 200 μm, and particularly preferably 10 to 100 μm.

Power storage device The power storage device according to an embodiment of the present invention (hereinafter, also referred to as “the power storage device”) includes the present electrode as a positive electrode. Examples of the power storage device include a non-aqueous electrolyte secondary battery, an electric double layer capacitor, and a lithium ion capacitor. The storage device includes at least a negative electrode and an electrolyte in addition to the main electrode normally used as a positive electrode.
The configuration and manufacturing method of the electrode according to the embodiment of the present invention used as the positive electrode are as described in the above-mentioned "electrode".

The basic configuration and manufacturing method of the negative electrode may be any conventionally known configuration and manufacturing method, and may be the same as that described in the above-mentioned "electrode" except for the type of the active material.
Examples of the negative electrode active material used include metallic lithium, lithium-doped carbon-based materials (graphite, activated carbon, etc.), lithium alloys, and the like. As these negative electrode active materials, one kind or two or more kinds can be used.

The electrolyte is usually used in the form of an electrolytic solution dissolved in a solvent. The electrolyte is not particularly limited, but one capable of generating lithium ions is preferable, and specifically, LiClO ₄ , LiAsF ₆ , LiBF ₄ , LiPF ₆ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiN (C 2 F 5 SO 2) 2, Examples thereof include LiN (CF ₃ SO ₂ ) ₂ and LiN (FSO ₂ ) _2. One type or two or more types of these electrolytes can be used.

The solvent for dissolving the electrolyte is preferably an aprotic organic solvent, specifically, ethylene carbonate, propylene carbonate, butylene carbonate, 1-fluoroethylene carbonate, 1- (trifluoromethyl) ethylene carbonate, dimethyl. Examples thereof include carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, acetonitrile, dimethoxyethane, diglime, tetraglime, dioxolane, methylene chloride, sulfolane and the like. One kind or two or more kinds of these solvents can be used.

As described above, the electrolyte is usually prepared and used in a liquid state, but a gel-like or solid-like electrolyte may be used for the purpose of preventing leakage or elution of the active material.

When the electrolyte is used in the state of an electrolytic solution, a separator is usually provided between the positive electrode and the negative electrode to prevent physical contact between the positive electrode and the negative electrode. As the separator, a conventionally known separator may be used, and examples thereof include non-woven fabrics or porous films made from cellulose rayon, polyethylene, polypropylene, polyamide, polyester, polyimide and the like, as well as paper and glass filters.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

[Example 1]
In a 100 ml eggplant flask, 3.27 g of bis (4-bromophenyl) amine (BPA), 1.69 g of diphenylamine (DPA), 2.88 g of sodium t-butoxide (NaOtBu), and bis (tri-tBu phosphine) as a catalyst. ) 5 mg of palladium (0) and 10 ml of toluene were added, and the mixture was heated at 100 ° C. for 6 hours. The contents were put into methanol, and the obtained white powder was washed with methanol and acetone to obtain 3.3 g of polymer A-1. ^{1 In 1} H-NMR (CDCl ₃ ), a peak was present only at 6.9 ppm (aromatic). The polystyrene-equivalent Mw measured by GPC (device name: HCL-8320GPC (manufactured by Tosoh Corporation), column: TSKgelsuperHM-H (manufactured by Tosoh Corporation), mobile phase: THF) was 10,000. Further, as a result of analysis by MALDI-TOFMS (matrix-assisted laser desorption / ionization time-of-flight mass spectrometer), a mass spectrum showing the existence of a structure in which ^{R 2 is a hydrogen atom in the following formulas (A) to (D).} Was obtained, and it was confirmed that the structure represented by the above formulas (1), (3), (3-1) to (3-2) and (6) was obtained.

[Example 2]
In a 100 ml eggplant flask, 3.27 g of BPA, 1.97 g of p, p'-ditrilamine (MPA), 2.88 g of NaOtBu, 51 mg of bis (tri-tBu phosphine) palladium (0) as a catalyst and 10 ml of toluene. In addition, it was heated at 100 ° C. for 6 hours. The contents were put into methanol, and the obtained white powder was washed with methanol and acetone to obtain 3.6 g of polymer A-2. Peaks were present at 6.9 ppm (aromatic) and 2.5 ppm (methyl group) in ¹ H-NMR (CDCl _3). The polystyrene-equivalent Mw measured under the same conditions as described above was 9,000. Further, as a result of analysis by MALDI-TOFMS, ^{mass spectra showing the existence of a structure in which R 2} is a methyl group in the above formulas (A) to (D) were obtained, and the above formulas (1) and (3), It was confirmed that it had the structures represented by (3-1) to (3-2) and (6).

[Example 3]
In a 100 ml eggplant flask, 3.27 g of BPA, 2.29 g of bis (methoxyphenyl) amine (MOPA), 2.88 g of NaOtBu, 51 mg of bis (tri-tBu phosphine) palladium (0) as a catalyst and 10 ml of THF. In addition, it was heated at 70 ° C. for 6 hours. The contents were put into methanol, and the obtained white powder was washed with methanol and acetone to obtain 3.7 g of polymer A-3. ^{Peaks were present at 1} H-NMR (CDCl ₃ ) at 6.7 ppm, 6.9 ppm (aromatic) and 3.8 ppm (methoxy group). The polystyrene-equivalent Mw measured under the same conditions as described above was 11,000. Further, as a result of analysis by MALDI-TOFMS, ^{mass spectra showing the existence of a structure in which R 2} is a methoxy group in the above formulas (A) to (D) were obtained, and the above formulas (1) and (3), It was confirmed that it had the structures represented by (3-1) to (3-2) and (6).

[Example 4]
In a 100 ml eggplant flask, 3.27 g of BPA, 2.05 g of bis (4-fluorophenyl) amine (FPA), 2.88 g of NaOtBu, 51 mg of bis (tri-tBu phosphine) palladium (0) as a catalyst and THF. Was added, and the mixture was heated at 70 ° C. for 6 hours. The contents were put into methanol, and the obtained white powder was washed with methanol and acetone to obtain 3.7 g of polymer A-4. Peaks were present at 6.7 ppm and 6.9 ppm (aromatic) in ¹ H-NMR (CDCl _3). The polystyrene-equivalent Mw measured under the same conditions as described above was 8,000. Further, as a result of analysis by MALDI-TOFMS, ^{mass spectra showing the existence of a structure in which R 2} is a fluoro group in the above formulas (A) to (D) were obtained, and the above formulas (1) and (3), It was confirmed that it had the structures represented by (3-1) to (3-2) and (6).

[Example 5]
(Production of Polymer with Structure (2))
In a 100 ml eggplant flask, 0.54 g of para-phenylenediamine (PDA), 2.35 g of 1,4-dibromobenzene, 2.88 g of NaOtBu, 51 mg of bis (tri-tBu phosphine) palladium (0) as a catalyst and toluene. Was added, and the mixture was heated at 100 ° C. for 6 hours. The contents were put into methanol, and the obtained white powder was washed with methanol and acetone to obtain 1.3 g of polymer B-1. It was confirmed by FT-IR that there was no vibration derived from the bond between NH and C-Br.

[Example 6]
(Production of Polymer with Structure (2))
In a 100 ml eggplant flask, 0.54 g of meta-phenylenediamine (MDA), 2.35 g of 1,3-dibromobenzene, 2.88 g of NaOtBu, 51 mg of bis (tri-tBu phosphine) palladium (0) as a catalyst and toluene. Was added, and the mixture was heated at 100 ° C. for 6 hours. The contents were put into methanol, and the obtained white powder was washed with methanol and acetone to obtain 1.3 g of polymer B-2. It was confirmed by FT-IR that there was no vibration derived from the bond between NH and C-Br.

[Example 7]
(Production of Polymer with Structure (2))
In a 100 ml eggplant flask, 0.54 g of PDA, 1.56 g of 4,4'-dibromobiphenyl, 1.2 g of 1,4-dibromobenzene, 2.88 g of NaOtBu, and bis (tri-tBu phosphine) palladium as a catalyst. 51 mg of (0) and 10 ml of toluene were added, and the mixture was heated at 100 ° C. for 6 hours. The contents were put into methanol, and the obtained white powder was washed with methanol and acetone to obtain 1.8 g of polymer B-3. It was confirmed by FT-IR that there was no vibration derived from the bond between NH and C-Br.

[Example 8]
(Production of Polymer with Structure (2))
To a 100 ml eggplant flask, add 2.48 g of 2,4-dibromoaniline, 2.88 g of NaOtBu, 51 mg of bis (tri-tBu phosphine) palladium (0) as a catalyst and 10 ml of toluene, and heat at 100 ° C. for 6 hours. bottom. The contents were put into methanol, and the obtained white powder was washed with methanol and acetone to obtain 0.88 g of polymer B-4. It was confirmed by FT-IR that there was no vibration derived from the bond between NH and C-Br.

[Comparative Example 1]
(Manufacturing of linear polyarylene amine)
To a 100 ml eggplant flask, add 1.23 g of paramethoxyaniline, 1.2 g of 1,4-dibromobenzene, 2.88 g of NaOtBu, 51 mg of bis (tri-tBu phosphine) palladium (0) as a catalyst, and 10 ml of toluene. , 100 ° C. for 6 hours. The contents were put into methanol, and the obtained white powder was washed with methanol and acetone to obtain 1.9 g of polymer C. It was confirmed by FT-IR that there was no vibration derived from the bond between NH and C-Br.

<Solubility in organic solvent>
The yields of polymers A-1 to A-4 and polymer C and their solubility in various solvents were confirmed at 25 ° C. The results are shown in Table 1. In Table 1, ⊚ means that 99 g or more of the polymer was dissolved in 100 g of the solvent, Δ means that 20 to 80 g of the polymer was dissolved in 100 g of the solvent, and × means that the polymer was dissolved in 100 g of the solvent. It means that less than 20 g was dissolved.

<Cycle characteristics>
Cycle characteristics were evaluated using Polymers A-1 to A-4 and Polymer C as follows.
In a polyethylene container, 0.4 g of each polymer as an active material, 0.5 g of acetylene black as a conductive agent, 0.1 g of an NMP solution of polyvinylidene fluoride (PVDF) in terms of solid content and 2 g of NMP are put and mixed. It was stirred. The obtained black slurry was applied onto an aluminum current collector using an applicator. At that time, the gap of the doctor blade was set to 150 μm. Then, it was dried on a hot plate at 100 ° C. for 10 minutes, and dried in a vacuum dryer at 100 ° C. for 3 hours to obtain an electrode sheet. The obtained electrode sheet was cut into a circle and used as a positive electrode of a battery. The obtained positive electrode, GA-100 (glass separator) and lithium foil (negative electrode) are set in a CR2032 type coin cell, and LiPF ₆ 1M ethylene carbonate / diethyl carbonate = 30/70 (volume ratio) solution (electrolyte solution). Was added and sealed using a caulking machine to prepare a coin cell.
The produced coin cell was subjected to a charge / discharge test using a TOSCAT-3100 manufactured by Toyo System Co., Ltd. as a charge / discharge tester at a current value of 0.1 C at room temperature and at the cutoff potential shown in Table 1. Table 1 shows the capacity retention rate (ratio of the discharge capacity at the 50th cycle to the discharge capacity at the first cycle) after 50 cycles of charging / discharging.

<Discharge capacity and rate characteristics>
Using polymers B-1 to B-4 and polymer C, the discharge capacity and rate characteristics were evaluated as follows.
Coin cells were produced in the same manner as in the above <cycle characteristics> except that polymers B-1 to B-4 were used instead of polymers A-1 to A-4.
The produced coin cell was charged / discharged using a TOSCAT-3500U manufactured by Toyo System Co., Ltd. as a charge / discharge tester at room temperature at current values of 0.1 C and 10 C at the cutoff potential shown in Table 2. .. Table 2 shows the discharge capacity at 0.1 C and the rate characteristics (discharge capacity at 10 C × discharge capacity at 100 / 0.1 C).

[Example 9]
A coin cell was prepared in the same manner as in the above <cycle characteristics> except _{that 0.08 g of polymer A-3 and 0.32 g of lithium iron phosphate (LiFePO 4} ) were used instead of polymers A-1 to A-4. Made. The cycle characteristics and the discharge capacity of the produced coin cell were evaluated in the same manner as in the above <cycle characteristics> and <discharge capacity and rate characteristics>. At this time, the cutoff potential was set to 3.8 to 2.8 V. As a result, the capacity retention rate after 50 cycles was 99%, the capacity retention rate after 5000 cycles was 84%, and the discharge capacity was 150 mAh / g.

[Comparative Example 2]
A coin cell was produced in the same manner as in the above <cycle characteristics> except that 0.4 g of _{lithium iron phosphate (LiFePO 4} ) was used instead of the polymers A-1 to A-4. The cycle characteristics and the discharge capacity of the produced coin cell were evaluated in the same manner as in the above <cycle characteristics> and <discharge capacity and rate characteristics>. At this time, the cutoff potential was set to 3.8 to 2.8 V. As a result, the capacity retention rate after 50 cycles was 95%, the capacity retention rate after 5000 cycles was 34%, and the discharge capacity was 150 mAh / g.

This polymer is considered to be extremely useful as an electrode material for a power storage device such as an electrode active material and an electrode binder, as well as a hole transport material used for an organic EL, an organic transistor, a solar cell, and the like.

Claims (6)

Polymer having at least one of the structures represented by the following formula (2):

In formula (2), Ar ² represents a group containing an aromatic ring independently of each other, except that ^{all of the plurality of Ar 2} are biphenyl-4,4'-diyl, and a is 1 to 10. ^{Ar 3} indicates an integer, Ar 3 indicates a group containing an aromatic ring independently of each other, b indicates 1 or 2 independently of each other, and the group bonded to N of ^{−Ar 3} − (N) _b ^{= becomes Ar 2} . They may be combined to form a ring. The polymer according to claim 1, wherein the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography is 2,000 to 100,000. The polymer according to claim 1 or 2, which is for an electrode material. An electrode containing the polymer according to claim 1 or 2. A power storage device including the electrode according to claim 4 as a positive electrode. A method for producing a polymer, which comprises a step of reacting a compound represented by the following formula (9) with a compound represented by the following formula (10) in the presence of a base:

In formula (9), Ar ⁵ represents a group containing an aromatic ring;

In formula (10), Ar ⁶ represents a group containing an aromatic ring, and X represents a halo group independently of each other.