WO2007111070A1

WO2007111070A1 - Composition for energy storage device electrode and method for producing same

Info

Publication number: WO2007111070A1
Application number: PCT/JP2007/053717
Authority: WO
Inventors: Mikio Kasai; Hitoshi Furusho
Original assignee: Nissan Chemical Industries, Ltd.
Priority date: 2006-03-29
Filing date: 2007-02-28
Publication date: 2007-10-04
Also published as: JPWO2007111070A1; TW200804453A

Abstract

Disclosed is a composition for energy storage device electrodes which contains a polyaminoquinoxaline compound represented by the formula (1) or (2) below and a carbon material. By using such a composition for energy storage device electrodes, there can be obtained an electrode which enables to increase the density of energy level of the device. (1) (2) (In the formulae, R1 and R2 independently represent a hydrogen atom, a hydroxyl group, a C1-C10 alkyl group, a C1-C10 alkoxy group or the like; R3 and R4 independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, a C1-C10 alkyl group, a C1-C10 alkoxy group or the like; X1 represents -NH-R5-NH- or -NH-R6-, wherein R5 and R6 independently represent a C1-C10 alkylene group, -C(O)CH2-, -CH2C(O)- or the like; and n represents an integer not less than 2.)

Description

Specification

Composition for electrode of energy storage device and method for producing the same

Technical field

The present invention relates to an energy storage device electrode composition and a method for producing the same, and more specifically, an energy storage device electrode composition comprising an electrode active material composed of polyaminoquinoxaline and a carbon material, and the same. It relates to a manufacturing method.

Background art

[0002] An electric double layer capacitor known as one of energy storage devices is generally composed of a pair of polarizable electrodes including a porous material, a separator, an electrolyte solution, and the like. This electric double layer capacitor is a device that uses the electric energy caused by the electric double layer generated by the movement of ions at the electrode interface as a charge / discharge mechanism and does not involve the electrochemical reaction of the electrode active material. It does not have a life like a battery, has excellent instantaneous charge / discharge characteristics, exhibits stable charge / discharge characteristics over a wide temperature range, and has low characteristics due to low performance degradation due to repeated operation.

[0003] Conventionally, the capacitance of an electric double layer capacitor is said to be proportional to the surface area of the polarizable electrode, and is increased by using a porous material having a large specific surface area for the polarizable electrode. Consideration has been made.

That is, the polarizable electrode is generally an electrode composition obtained by kneading a porous material such as a carbonaceous material, acetylene black as a conductive auxiliary material, and a fluorine-based polymer or rubber-based polymer as a binder. For example, as a carbonaceous material, activated carbon with a large specific surface area that exhibits high conductivity and is relatively stable electrochemically (porous carbon material) Attempts have been made to increase the capacitance by using).

Specifically, carbonaceous raw materials such as coal, coal coats, coconut shells, wood flour, and resin are added with oxidizing gases such as water vapor, air, oxygen, and CO, or chemicals such as zinc chloride and potassium hydroxide. A large specific surface area activated carbon obtained by applying an activation (porosification) treatment to form pores is used. [0004] On the other hand, studies have been made to increase the capacitance of the electric double layer capacitor by combining a conductive polymer and a carbon material.

For example, a combination of polyaniline and a carbon material, or a combination of a polymer of 1,5-diaminoanthraquinone and a carbon material is known (Patent Document 1: Japanese Patent Application Laid-Open No. 2002-25865). (Japanese Patent Laid-Open No. 2003-109875).

On the other hand, an electric double layer capacitor using a conductive polymer that can be used for both positive and negative electrodes and exhibits a wide potential activity has been developed (see Patent Document 3: International Publication No. 2005/076295 pamphlet).

For example, a polyaminoquinoxaline compound is known as a conductive polymer having characteristics that can be used for both positive and negative electrodes (Patent Document 4: International Publication No. 2005Z068439 Pamphlet, Patent Document 5: JP 2004-083563 A). reference).

An electric double layer capacitor using a polyaminoquinoxaline compound is advantageous in terms of productivity because it is not necessary to use different conductive polymers for the positive and negative electrodes, but its electrostatic capacity is not sufficient.

Patent Document 1: Japanese Patent Application Laid-Open No. 2002-25865

Patent Document 2: Japanese Patent Laid-Open No. 2003-109875

Patent Document 3: International Publication No. 2005/076295 Pamphlet

Patent Document 4: Pamphlet of International Publication No. 2005/068439

Patent Document 5: Japanese Unexamined Patent Application Publication No. 2004-083563

Disclosure of the invention

Problems to be solved by the invention

The present invention has been made in view of such circumstances, and provides an energy storage device electrode composition that provides an electrode capable of increasing the energy level of the device, and a method for producing the same. The purpose is to do.

Means for solving the problem

[0007] As a result of intensive studies to achieve the above object, the present inventors have made a conductive polymer obtained by polymerizing an aminoquinoxaline compound as an electrode active material, and a carbon material as a current collector. The electrode using the electrode can store higher capacity than the conventional electrode using the same active material. As a result, the present invention has been completed.

That is, the present invention

1. A composition for an energy storage device electrode comprising a polyaminoquinoxaline compound represented by the formula (1) and a carbon material,

[Chemical 1]

[Wherein R ¹ and R ² are each independently a hydrogen atom, a hydroxyl group, a CC alkyl group, C

~ C alkoxy group, phenyl group optionally substituted with Y, pyridyl group optionally substituted with Y, biphenyl group optionally substituted with Y, and optionally substituted with Y Phthyl group, Cenyl group that may be substituted with Y, Pyrrolylene group that may be substituted with Y, Furyl group that may be substituted with Y, or A condensed heteroaryl group that may be substituted with Y (When R ¹ and R ² are the phenyl group, pyridyl group, biphenyl group, naphthyl group, phenyl group, pyrrolyl group, furyl group, or condensed heteroaryl group, these groups are bonded by a single bond. Or R ¹ and R ² together, _CH CH CH-

, -CH CH0, -OCH CH, -CH OCH, -OCH O-, 1 CH CH S, -SCH CH, -CH SCH, -CH CH N (R)-, 1 N ( R) CH CH

-CH N (R) CH 1 -CH CH CH CH 1 -CH CH CH 0 1 -OCH CH

CH, -CH CH OCH, -CH OCH CH, -CH OCH 0, -OCH C

H〇, -SCH CH S—, -OCH CH S—, one SCH CH O—, one CH CH = CH one, -CH = CHCH one, one OCH = CH—, one CH = CH ○ one, one SCH = CH—,-

CH = CHS-, _N (R) CH = CH-, _CH = CHN (R)-, _〇CH = N-, _N = CHO— SCH = N— N = CHS— N (R) CH = N— N = CHN (R) N (R) N = CH— CH = N (R) N— CH = CHCH = CH— OCH

CH = CH—, -CH = CHCH Yes, N = CHCH = CH— CH = CHCH = N N = CHCH = NN = CHN = CH— or CH = NCH = N may be formed. At this time, the hydrogen atom bonded to the carbon atom of these groups may be substituted with Y. R Is a hydrogen atom, C-C alkyl group, C-C haloalkyl group, C-C

1 10 1 10 1 10 Cyanoalkyl group, phenyl group optionally substituted with Z, pyridyl group optionally substituted with Z, biphenyl group optionally substituted with Z, optionally substituted with Z A naphthyl group, a phenyl group optionally substituted with Z, a pyrrolyl group optionally substituted with Z, a ring substituted with Z, a ring, a furyl group or a ring substituted with Z Yo represents a condensed heteroaryl group.

R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, a C-C alkyl group, a C-C alkoxy group, or a phenyl group optionally substituted with Y.

1 10 1 10

Group, pyridyl group optionally substituted with Y, biphenyl group optionally substituted with Y, naphthyl group optionally substituted with Y, chenyl group optionally substituted with Y, substituted with Y A pyrrolyl group which may be substituted, a furyl group which may be substituted with Y, or a condensed heteroaryl group which may be substituted with Y (R ³ and R ⁴ are the phenyl group, pyridinole group, biphenyl group). R ^{3 group} , R ⁴ group, R ⁴ group, R ⁴ group, R ⁴ group, R ⁴ group, R ⁴ group, R ⁴ group, R ⁴ group, R ⁴ group, R ⁴ group, or R ⁴ group. 1 CH CH CH 1 -CH CH 0 1 1 0 CH 1 CH 1 CH OCH

2 2 2 2 2 2 2 2 2 1, -OCH 0, -CH CH S-, -SCH CH 1, CH SCH 1, CH CH

2 2 2 2 2 2 2 2 2

N (R) -N (R) CH CH -CH N (R) CH CH CH CH CH C

2 2 2 2 2 2 2 2

H CH CH〇1, -OCH CH CH CH CH OCH CH OCH CH

2 2 2 2 2 2 2 2 2 2 2 2 CH OCH O—, -OCH CH〇1, SCH CH S OCH CH S S

2 2 2 2 2 2 2 2

CH CH O—, -CH CH = CH—, -CH = CHCH one, ten CH = CH—, -CH

2 2 2 2

= CHO_, _SCH = CH―, _CH = CHS―, _N (R ') CH = CH―, _CH = C HN (R')-, one OCH = N-, _N = CHO-, one SCH = N-, _N = CHS-, 1 N (R ') CH = N―, _N = CHN (R') ―, _N (R ') N = CH―, _CH = N (R') N―,-CH = CHCH = CH-, -OCH CH = CH—, one CH = CHCH O—, -N = CHC

twenty two

H = CH, 1 CH = CHCH = N—, _N = CHCH = N—, _N = CHN = CH—, or 1 CH = NCH = N— Yui The combined hydrogen atom may be substituted with Y. R 'is a hydrogen atom, a C to C alkyl group,

1 10

c-c haloalkyl group, C-C cyanoalkyl group, a phenyl optionally substituted with Z

1 10 1 10

Nyl group, pyridyl group optionally substituted with Z, biphenyl group optionally substituted with Z, naphthyl group optionally substituted with z, chenyl group optionally substituted with z, substituted with z In this case, R represents a pyrrolyl group, substituted with z, represents a furyl group, or represents a condensed heteroaryl group substituted with z.

X ¹ represents _NH_R ⁵ _NH— or one NH—R ⁶ —,

R ⁵ and R ⁶ are each independently a C to C alkylene group, _C (◯) CH _, —CH C

1 10 2 2

(O)-, Y may be substituted, divalent benzene ring, Y may be substituted divalent pyridine ring, Y may be substituted, divalent biphenyl group , May be substituted with Y, divalent naphthalene ring, may be substituted with Y, divalent thiophene ring, may be substituted with Y, divalent pyrrole ring, substituted with Y It may be a divalent furan ring or a Y substituted with a Y, represents a condensed heterocycle.

Y is a halogen atom, cyan group, nitro group, amino group, epoxy group, vinyl group, C to C

1 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

1 10 1 10 1 10 group, phenyl group optionally substituted with Z, pyridyl group optionally substituted with Z, biphenyl group optionally substituted with Z, substituted with Z A naphthyl group that may be substituted with Z, a pyrrolyl group that may be substituted with z, a pyrrolyl group that may be substituted with z, a thiol substituted with z, a furyl group, or a thiol substituted with z However, it represents a condensed heteroaryl group (however, when γ is 2 or more, they may be the same or different from each other).

z is a halogen atom, cyan group, nitro group, amino group, epoxy group, vinyl group, c to

1 c 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

1 10 1 10 1 10 represents a phenyl group, a phenyl group, a biphenyl group, a naphthyl group, a chenyl group, a pyrrolyl group, a furyl group, or a condensed heteroaryl group (however, when Z is 2 or more, they are the same or different from each other) However, n represents an integer of 2 or more. ]

2. An energy storage device electrode composition comprising a polyaminoquinoxaline compound represented by the formula (2) and a carbon material.

[Chemical 2]

(In the formula, R ¹ , R ² , R ³ , R ⁴ and n are the same as above.)

3. The composition for an energy storage device electrode of 1 or 2, wherein R ¹ and R ² are each independently represented by the formula (3):

[Chemical 3]

(Wherein R ^{7 to} R ^U are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bur group, a C to C alkyl group, a C to C haloalkyl group, a C to

1 10 1 4 1

C alkoxy group, C-C cyanoalkyl group, phenyl group optionally substituted by Z, Z

10 1 4

Is substituted with R, maye, naphthyl or Z, substituted with R, maye, or chel, and Z is the same as above. )

4. The composition for an energy storage device electrode according to 1 or 2, wherein R ¹ and R ² are each independently represented by the formula (4):

[Chemical 4]

(In the formula, R "to R ^1S each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bur group, or C-C substituted at any position on the ring. Archi

1 10 group, C-C alkoxy group, phenyl group optionally substituted by Z, substituted by Z

1 10

Re, mayeole, naphthyl group or substituted with Z represents les, mayeole, or cheryl group. Z is the same. )

5. The composition for an energy storage device electrode of 1 or 2, wherein R ¹ and R ² are each independently represented by the formula (5):

[Chemical 5]

(In the formula, R ^{iy to} R are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bur group, or a C to C alkyl group substituted at any position on the ring.

1 10

Re, mayore, naphthyl group or substituted with Z represents le, mayole, or a cheryl group, and A ¹ represents NH, O, or S. Z is the same as above. )

6. Polyaminoquinoxaline compound strength 5 Energy storage device electrode composition represented by the following formula (21):

[In the formula, R ⁷⁵ and R ⁷⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, a C-C alkyl group, a C-C alkoxy group, or Y. Good

1 10 1 10

Phenyl group, pyridyl group optionally substituted with Y, biphenyl group optionally substituted with Y, naphthyl group optionally substituted with Y, cheenyl group optionally substituted with Y, γ Pyrrolyl group which may be substituted, furyl group which may be substituted with γ, or The phenyl group and is Teroariru group (R ⁷⁵ and R ⁷⁶ are the substituted condensed also be substituted by Y is, peak lysyl group, Bifue group, a naphthyl group, a thienyl group, a pyrrolyl group, heteroaryl group a furyl group or a condensed In this case, these groups may be bonded by a single bond.) R ^{77 to} R ⁸² each independently represents a hydrogen atom, a halogen atom, a cyan group, a nitro group, an amino group, an epoxy Substituted with xoxy group, bur group, C-C alkyl group, C-C alkoxy group, Z

1 10 1 10

Moe, phenyl, substituted with Z, maye, naphthyl, or substituted with Z, may represent a chain, Z and n are the same as above. ]

7. The composition for an energy storage device electrode according to 1 or 2, wherein R ¹ and R ² are each independently represented by the formula (6):

[Chemical 7]

(Wherein R ²² represents a halogen atom or a cyano group, and R ^{23 to} R ²⁶ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bur group, C ~ C

1 1 alkyl group, c to C alkoxy group, phenyl group optionally substituted with Z, substituted with Z

0 1 10

And is substituted with a naphthyl group or Z, represents a ret, maye or chel group. Z is the same as above. )

8. The composition for an energy storage device electrode of 1, wherein R ⁵ is represented by the formula (7):

[Chemical 8]

(In the formula, R ^{27 to} R ^3Q are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bur group, C-C substituted at an arbitrary position on the ring. Archi

1 10

9. The composition for an energy storage device electrode of 1, wherein R ⁵ is represented by formula (8):

[Chemical 9]

(In the formula, R "to R" each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bier group, or C-C substituted at any position on the ring. Archi

1 10

R, mayole, naphthyl group or substituted with Z represents le, mayole, or cheyl group, and W ¹ represents NH, O, or S. Z is the same as above. )

10. The composition for an energy storage device electrode of 1, wherein R ⁵ is represented by formula (9):

[Chemical 10]

(In the formula, R ^{33 to} R ³⁴ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bur group, C-C substituted at an arbitrary position on the ring. Archi

1 10

R, mayole, naphthyl group or substituted with Z represents le, mayole, or cheyl group, and Q ¹ represents NH, O, or S. Z is the same as above. )

11. The composition for an energy storage device electrode according to 1, wherein R ⁵ is represented by the formula (10):

(In the formula, each of ^ ⁵ to R is independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bier group, or a C to C alkyl group substituted at any position on the ring.

1 10

Re, mayeole, naphthyl group or substituted with Z represents les, mayeole, or cheryl group. Z is the same as above. )

12. The composition for an energy storage device electrode according to 1, wherein R ⁶ is represented by formula (11):

(In the formula, R ^{41 to} R ⁴⁴ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bur group, or C-C substituted at any position on the ring. Archi

1 10

13. The composition for an energy storage device electrode according to 1, wherein R ⁶ is represented by the formula (12):

(In the formula, R ^{4b to} R ^4b are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bier group, C-C substituted at any position on the ring. Archi

1 10

R, mayole, naphthyl group or substituted with Z represents le, mayole, or cheyl group, and W ² represents NH, O, or S. Z is the same as above. )

14. The composition for an energy storage device electrode according to 1, wherein R ⁶ is represented by the formula (13):

(Wherein R ⁴⁷ to! Each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bier group, a C to C alkyl group, which is substituted at any position on the ring.

1 10

Re, mayore, naphthyl group or substituted with Z represents le, mayole, or cheyl group, and Q ² represents NH, O, or S. Z is the same as above. )

15. The composition for an energy storage device electrode of 1, wherein R ⁶ is represented by the formula (14):

(In the formula, R ^{49 to} R ⁵⁴ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bur group, or C-C substituted at any position on the ring. Archi

1 10

16. The composition for an energy storage device electrode of 1 or 2 represented by the formula (15), wherein R ¹ and R ² form a ring,

[Chemical 16]

(In the formula, A ² represents C or N, R ^{55 to} R ⁵⁷ and R ^{6 to} R ⁶² , and when A ² is C, R ^{55 to} R ⁶² are each independently a hydrogen atom, a halogen atom, Ciano group, nitro group, amino group, epoxy Group, Bier group, C-C alkyl group, C-C alkoxy group, may be substituted with Z

1 10 1 10

Re, phenyl group, substituted with Z, ret, naphthyl group, or substituted with Z, ret or phenyl group. Z is the same as above. However, when A ² is N, R ⁵⁸ and R ⁵⁹ do not exist

. )

17. A basic force formed by combining R ¹ and R ² together 1 or 2 for an energy storage device electrode composition represented by formula (16):

[Chemical 17]

(In the formula, A ³ represents O or S, and R ^{63 to} R ⁶⁶ each independently represent a hydrogen atom, a halogen atom, a cyan group, a nitro group, an amino group, an epoxy group, a bur group, or a C to C alkyl group. Group, C ~ C

1 10 1 alkoxy group, phenyl group optionally substituted with Z, naphth optionally substituted with Z

Ten

A til group or a chain group optionally substituted by z is represented. z is the same as above. )

18. The composition for an energy storage device electrode according to 1 or 2, wherein the group formed by combining R ³ and R ⁴ together is represented by formula (17):

[Chemical 18]

(In the formula, A ⁴ represents O or S, and R ^{67 to} R ⁷ ° each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bur group, or c-kill. Group,

1c al

10 c ~

1 c alkoxy group, phenyl group optionally substituted with Z, naphtho optionally substituted with Z

Ten

19. The composition for an energy storage device electrode according to 1 or 2, wherein the group formed by combining R ³ and R ⁴ together is represented by formula (18): [Chemical 19]

(is)

(Wherein R ⁷¹ and R ⁷² are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bur group, a C-C alkyl group, a C-C alkoxy group, Z

1 10 1 10

Represents a phenyl group which may be substituted with, may be substituted with a phenyl group, may be substituted with Z, may be substituted with a naphthyl group, or may be substituted with. Z is the same as above. )

20. The composition for an energy storage device electrode according to any one of 1 to 19 wherein the carbon material is activated carbon, carbon black, or graphite,

21. The composition for an energy storage device electrode according to any one of 1 to 19 above, wherein the carbon material is a fibrous carbon material,

22. The composition for an energy storage device electrode according to 21, wherein the fibrous carbon material is carbon felt,

23. The energy storage device electrode composition according to 21 or 22, wherein the fibrous carbon material has a fiber diameter of 10 to 50 x m,

24. The composition for an energy storage device electrode according to 23, wherein the fibrous carbon material has a fiber diameter of 10 to 20 × m.

25. The composition for an energy storage device electrode according to 1, wherein a polyaminoquinoxaline compound represented by the formula (1) is attached to the surface of the carbon material,

26. The composition for an energy storage device electrode according to 2, wherein a polyaminoquinoxaline compound represented by the formula (2) is attached to the surface of the carbon material,

27. The composition for an energy storage device electrode according to 21, wherein the fiber surface constituting the fibrous carbon material is coated with a polyaminoquinoxaline compound represented by the formula (1),

28. The composition for an energy storage device electrode according to 21, wherein a fiber surface constituting the fibrous carbon material is coated with a polyaminoquinoxaline compound represented by the formula (2),

29 .: characterized by comprising the composition for electrode of energy storage device of any one of! -28 Electrodes for energy storage devices,

30. An energy storage device comprising at least a pair of positive and negative electrodes, a separator interposed between these electrodes, and an electrolyte, wherein at least one of the positive and negative electrodes is an electrode for 29 energy storage devices An energy storage device, characterized by

31. An energy storage device in which the positive and negative electrodes are both electrodes for 29 energy storage devices,

32. The energy storage device according to 30 or 31, wherein the electrolyte is a non-aqueous electrolyte including an electrolyte salt and a non-aqueous organic solvent,

33. The method for producing a composition for an energy storage device electrode according to 1, wherein the polyaminoquinoxaline compound represented by the formula (1) is applied to the surface of a carbon material,

34. The method for producing an energy storage device electrode composition according to 2, wherein the polyaminoquinoxaline compound represented by the formula (2) is applied to the surface of a carbon material,

35. The method for producing a composition for an energy storage device electrode according to 1, wherein the aminoquinoxaline compound represented by the formula (19) is electropolymerized on the surface of a carbon material,

[Chemical 20]

(In the formula, R ² , R ³ and R ⁴ are the same as above. X ² is _NH_R ⁷³ _NH or —NH—R ^74.

2

R ⁷³ is a C to C alkylene group, substituted with one C (〇) CH—, one CH C (〇) one, Y

1 10 2 2

Divalent benzene ring, may be substituted with Y, divalent pyridine ring, substituted with Y, may be, divalent biphenyl group, substituted with Y Les, mayole, divalent naphthalene ring, may be substituted with Y, divalent thiophene ring, divalent pyrrole ring optionally substituted with Y, substituted with Y Represents a divalent furan ring or a condensed heterocyclic ring that may be substituted with Y; R ⁷⁴ is a C to C alkyl group, a acetyl group, or Y

1 10

An optionally substituted phenyl group, a pyridyl group optionally substituted with Y, optionally substituted with Y A biphenyl group, a naphthyl group optionally substituted with Y, a phenyl group optionally substituted with Y, a pyrrolyl group optionally substituted with Y, a furyl group optionally substituted with Y, or Y Represents a condensed heteroaryl group which may be substituted with Y is the same as above. 36. The method for producing a composition for an energy storage device electrode according to 2, characterized by electropolymerizing an aminoquinoxaline compound represented by the formula (20) on the surface of a carbon material,

[Chemical 21]

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as above.)

I will provide a.

The invention's effect

The polyaminoquinoxaline compound represented by the above formulas (1) and (2) used as an electrode active material for an electrode for an energy storage device of the present invention has excellent heat resistance and is electrochemically accompanied by proton transfer. It is easy to control oxidation and reduction and has high cycleability.

In addition, since the polyaminoquinoxaline compound has both an electron accepting portion and an electroconductivity portion in one molecule, it can be used for both positive and negative electrodes, and has a wide conductivity and potential activity. It is a polymer compound.

A device configured to include an electrode for an energy storage device obtained from a composition comprising an electrode active material comprising a polyaminoquinoxaline compound and a carbonaceous material can be charged with a high capacity.

In particular, when used as an electrode for an electric double layer capacitor, both the redox reaction of the electrode active material and the electric double layer generated on the surface function as an energy source. Can be stored.

In addition, carbon materials are preferred as current collecting materials carrying polyaminoquinoxaline compounds. In addition, by using a fibrous carbon material, it is possible to store a higher capacity than a capacitor using a conventional platinum electrode.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail.

The composition for an energy storage device electrode according to the present invention comprises a polyaminoquinoxaline compound represented by the formula (1) or the formula (2) and a carbon material. First, the polyaminoquinoxaline compound represented by the formula (1) or the formula (2) will be described. In the above formulas, R ¹ and R ² are each independently a hydrogen atom, a hydroxyl group, a C to C alkyl group, a C to C alkoxy group, a phenyl group that may be substituted with Y, or a Y group. An optionally pyridyl group, a biphenyl group that may be substituted with Y, a naphthyl group that may be substituted with Y, a chenyl group that may be substituted with Y, a pyrrolyl group that may be substituted with Y, Furyl group optionally substituted with Y, or condensed heteroaryl group optionally substituted with Y (R ¹ and R ² are phenyl, pyridinole, biphenyl, naphthyl, chenyl, A pyrrolyl group, a furyl group or a condensed heteroaryl group, these groups may be bonded by a single bond.), Or R ¹ and R ² are taken together to form -CH

CH CH 1, -CH CH 01, -OCH CH 1, -CH OCH 1, -OCH 01,-

CH CH S—, -SCH CH 1, -CH SCH 1, 1 CH CHN (R) —, 1 N (R) C

H CH, -CH N (R) CH, CH 1 CH CH CH CH 1, CH CH CH 0 1,-

OCH CH CH, -CH CH OCH, -CH OCH CH, -CH OCH O-,

-OCH CH〇-1, -SCH CH S—, -OCH CH S—, one SCH CH〇1, one CH

CH = CH—, -CH = CHCH, 1 OCH = CH—, 1 CH = CH 0, -SCH =

CH―, _CH = CHS―, _N (R ') CH = CH―, _CH = CHN (R') ―, _OCH = N-, _N = CH 0, 1 SCH = N-, _N = CHS-, 1 N (R ') CH = N-, _N = CHN (R')-, one N (R ') N = CH-, one CH = N (R') N-, one CH = CHCH = CH-, OCH CH = CH— CH = CHCHO— N = CHCH = CH— CH = CH

CH = N— N = CHCH = N— N = CHN = CH— or CH = NCH = N— may be formed. In this case, the hydrogen atom bonded to the carbon atom of these groups is replaced with Y. R may be a hydrogen atom, a C-C alkyl group, a C-C haloalkyl group, C to C cyanoalkyl group, phenyl group optionally substituted with Z, substituted with Z

1 10

An optionally pyridyl group, a biphenyl group optionally substituted with Z, a naphthyl group optionally substituted with Z, a chenyl group optionally substituted with Z, or a pyrrolyl optionally substituted with Z A group, substituted with Z, les, maye, furyl, or substituted with Z, ret, maye, a condensed heteroaryl group;

Suitable R ¹ and R ² include those represented by the following formulas (3) to (6), (15) and (16).

[0012] [Chemical 22]

(In the formula, R ^{7 to} R ^2D , R ^{55 to} R ⁶⁶ and AA ³ are the same as above.)

[0013] Further, in consideration of the solubility of the aminominooxaline compound, it is preferable that R ¹ and R ² are further substituted with a substituent Y. In this case, the substituent Y is C to C alkyl

1 10 groups or c-c alkoxy groups are preferred, c-c alkyl groups or c-c alkoxys.

The 1 10 1 5 1 5 group is preferred.

On the other hand, R ³ and R ⁴ are each independently substituted with a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, a C to C alkyl group, a C to C alkoxy group, or Y. Good

1 10 1 10

A phenyl group, a pyridyl group optionally substituted with Y, a biphenyl group optionally substituted with Y, a naphthyl group optionally substituted with Y, a cheenyl group optionally substituted with Y, Pyrrolyl group which may be substituted, furyl group which may be substituted with Y, or Is a condensed heteroaryl group optionally substituted with Y (when R ³ and R ⁴ are a phenyl group, a pyridinole group, a biphenyl group, a naphthyl group, a chenyl group, a pyrrolyl group, a furyl group, or a condensed heteroaryl group, These groups may be bonded by a single bond.), Or R ³ and R ⁴ are combined together to form _CH CH CH- -CH CH〇_, _〇CH CH- -CH OCH

2 2 2 2 2 2 2 2 1, -OCH O—, -CH CH S—, -SCH CH 1, CH 1 SCH 1, -CH CH

2 2 2 2 2 2 2 2 2 2

N (R) —, -N (R) CH CH, -CH N (R) CH, -CH CH CH CH, _C

2 2 2 2 2 2 2 2

H CH CH〇一、 -OCH CH CH 一、 -CH CH OCH 一、 -CH OCH CH-

2 2 2 2 2 2 2 2 2 2 2 2

, -CH OCH O—, -OCH CH 0-,-SCH CH S—, 1 OCH CH S—, 1 S

2 2 2 2 2 2 2 2

CH CH O—, -CH CH = CH—, -CH = CHCH one, ten CH = CH—, -CH

2 2 2 2

= CHO_, _SCH = CH―, _CH = CHS―, _N (R ') CH = CH―, _CH = C HN (R')-, one OCH = N-, _N = CHO-, one SCH = N-, _N = CHS-, 1 N (R ') CH = N-, _N = CHN (R')-, _N (R ') N = CH-, _CH = N (R') N-,-CH = CHCH = CH OCH CH = CH CH = CHCH ON = CHC

twenty two

H = CH CH = CHCH = NN = CHCH = NN = CHN = CH or CH = NCH = N— may be formed. At this time, the hydrogen atom bonded to the carbon atom of these groups is replaced with Y. It may be. R represents the same meaning as above.

[0015] When R ³ and R ⁴ are an alkyl group or an alkoxyl group, the carbon number thereof is preferably 15 in view of conductivity.

From the viewpoint of improving the redox potential, R ³ and R ⁴ are preferably a phenyl group, a naphthyl group, or a chenyl group. Furthermore, it is preferable that these groups are further substituted with the substituent Y from the viewpoint of electrical characteristics. As the substituent Y, a C to C alkyl group,

1 10

c to c alkoxy groups are preferred c to c alkyl groups or c to c alkoxy groups are more preferred

1 10 1 5 1 5

preferable.

Suitable R ³ and R ⁴ include, for example, the following (17) and (18) in addition to those shown in (3) to (6) and (15) exemplified for R ¹ and R ² above. And the like.

[0016] [Chemical 23]

(In the formula, R ^{67 to} R ⁷² and A ⁴ are the same as above.)

In the above formula (1), R ⁵ and R ⁶ are each independently a C to C alkylene group, —C

1 10

(O) CH CH C (O) —, optionally substituted with Y, divalent benzene ring, substituted with Y

twenty two

A divalent pyridine ring, which may be substituted with Y, a divalent biphenyl group, which may be substituted with Y, or a divalent naphthalene ring, which is substituted with Y, Divalent thiofone ring, optionally substituted with Y divalent pyrrole ring, optionally substituted with Y, divalent furan ring, or substituted with Y It's a condensed heterocycle.

In the above formula (19), R ⁷³ is a C to C alkylene group, -C (0) CH-, -C

1 10 2

H C (〇) _, may be substituted with Y, divalent benzene ring, may be substituted with Y

2

Divalent pyridine ring, optionally substituted with Y, divalent biphenyl group, optionally substituted with Y, divalent naphthalene ring, optionally substituted with Y, divalent thiophene Ring, substituted with Y, may be, divalent pyrrole ring, substituted with Y, may be, divalent furan ring, or condensed heterocycle optionally substituted with Y R ⁷⁴ is a C to C alkyl group, acetyl

1 10

Group, phenyl group optionally substituted with Y, pyridyl group optionally substituted with Y, biphenyl group optionally substituted with Y, naphthyl group optionally substituted with Y, Y A phenyl group that may be substituted with Y, a pyrrolyl group that may be substituted with Y, a ring that is substituted with Y, a ring, a furyl group, or a ring that is substituted with Y Heteroaryl group. Specific examples of these groups include groups represented by the following formulas (7) to (: 14).

[0018] [Chemical 24] (9)

, 74,

Among these, R ⁷³ and are preferably a divalent benzene ring, a divalent naphthalene ring or a divalent thiophene ring from the viewpoint of improving the redox potential. In addition, these cyclic substituents are preferably further substituted with a substituent Y from the viewpoint of maintaining stable electrical characteristics of a film made of a polyaminoquinoxaline compound.

R ⁶ is preferably a phenyl group, a naphthyl group, or a phenyl group from the viewpoint of improving the redox potential.

These R ⁶ , R ^73, and R ⁷⁴ are preferably further substituted with a substituent Y from the viewpoint that the amorphous nature of a film made of a polyaminoquinoxaline compound is kept stable. Sile,. Also in these cases, the substituent Y is a C-C alkyl group, a C-C alkoxy group.

1 10 1 10

C to alkoxy groups are more preferable.

1 c alkyl group or

5 c ~

1 c 5

In the above formula (21), R ⁷⁵ and R ⁷⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, a C 1 -C alkyl group, a C 1 -C alkoxy group, Set with Y

1 10 1 10

A phenyl group that may be substituted, a pyridyl group that may be substituted with Y, a biphenyl group that may be substituted with Y, a naphthyl group that may be substituted with Y, and a substituent substituted with Y A phenyl group which may be substituted with Y, a furyl group which may be substituted with Y, or a condensed heteroaryl group which may be substituted with Y (R ⁷⁵ and R ⁷⁶ are Enyl, pyridyl, biphenyl, naphthyl, chenyl, pyrrolyl, furyl Or when it is a condensed heteroaryl group, these groups may be bonded by a single bond. However, a hydrogen atom and a chenyl group optionally substituted by Y are preferred.

R ^{77 to} R ⁸² are each independently a hydrogen atom, halogen atom, cyano group, nitro group, amino group, epoxy group, bur group, C to C alkyl group, C to C alkoxy group, or Z.

1 10 1 10

Substituted les, mayeles, phenyl groups, Z substituted with les, mayeles, naphthyl groups, or chenyl groups optionally substituted with Z (Z is the same as above) ) Is replaced with a hydrogen atom, Y, or even a chenyl group is preferred.

[0021] The molecular weight of the polyaminoquinoxaline compound represented by the formula (1) or the formula (2) is not particularly limited, and the repulsive force is the weight average molecular weight force S1, 000 to 100,000, in particular, 1,000 to 50, 000 is preferred. For this reason, η in the above formulas (1) and (2) is a force that is an integer of 2 or more. It is preferable that the polyaminoquinoxaline compound is a number within the range of the weight average molecular weight. For example, η = 2 to Can be set to 400.

In each of the above formulas, the C 1 -C alkyl group is a straight-chain, branched or cyclic group.

1 10

For example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, sbutyl, n pentyl, n-hexyl, 2-ethylpropyl, 2, 2-dimethyl Propyl, 1,2-dimethylpropyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3- Methyl butyl, 1,1-dimethylbutinole, 1,2 dimethylenobutinole, 1,3 dimethylenobutinore, 2,2 dimethylenobutynole, 2,3-dimethylbutyl, 3,3 dimethylbutyl, 1-ethylbutyl, 2 ethylbutyl, 1 -Methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl and the like. The C to C alkylene group includes a hydrogen atom of each of the above alkyl groups.

1 10

A group formed by removing one child.

[0023] As the C 1 -C haloalkyl group, at least one hydrogen atom of each of the above alkyl groups is

1 10

And a group substituted with a halogen atom. Note that the halogen atom may be any of chlorine, fluorine, iodine, and fluorine.

The C to C cyanoalkyl group includes at least one hydrogen atom of each alkyl group.

1 10

Examples include groups substituted with a force cyano group. Condensed heteroaryl groups include thieno [3,4-b] pyrazine-5-yl, furo [3,4-b] pyrazine-5-yl and 6H-pyro-mouth [3,4-b] pyrazine-5 —Ill.

[0024] The C to C alkoxy group may be linear, branched or cyclic.

1 10

Xoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentyloxy, n-hexyloxy, 1, 1-dimethylpropoxy, 1, 2 —Dimethylpropoxy, 2, 2-dimethylpropoxy, 1_ethylpropoxy, 1,1,2 _trimethylpropoxy, 1,2,2 _trimethylpropoxy, 1_ethyl_1_methylolpropoxy, 1 _ethyl _2 _Methylpropoxy, 1_Methylbutoxy, 2_Methylbutoxy, 3_Methylbutoxy, 1_Ethylbutoxy, 2_Ethylbutoxy, 1,1_Dimethylolbutoxy, 1,2-Dimethylbutoxy, 1,3-Dimethylbutoxy, 2, 2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-methylpentyloxy, 2-methylpentyloxy, 3_methylpentyloxy And 4_methylpentyloxy and the like.

In the above, n represents normalore, i represents iso, s represents secondary, and t represents tertiary.

[0025] Examples of the compound represented by the formula (1) include, but are not limited to, the following.

[0026] [Chemical 25]

[0028] [Chemical 27]

[0029] [Chemical 28]

[0030] [Chemical 29]

[0032] Examples of the compound represented by the above formula (2) include, but are not limited to, the following.

[0033] [Chemical 31]

[0034] [Chemical 32]

[0035] [Chemical 33]

[0036] [Chemical 34]

[0037] [Chemical 35]

[0038] [Chemical 36]

Of these, polyaminoquinoxaline represented by the following formula is particularly preferable.

[0040] [Chemical 37]

[0041] Next, a method for synthesizing the aminoquinoxaline compound represented by the formula (19) will be described. This compound is synthesized using a 5-aminoquinoxaline compound represented by the following formula (20) as a raw material. That power S.

[0042] [Chemical 38]

(In the formula, R ^ R ⁴ is the same as above.)

[0043] The specific synthesis method is not particularly limited. Journal of the Chemical Society Society Perkin Transactions ια Chem. Soc. Perkin Trans. I), 1988, 1331—1335, Chem. Lett., 1997, 118

The method described in pages 5-1186 can be used.

For example, the corresponding 5-aminoquinoxaline compound is dissolved in a suitable solvent, reacted with nitrofluorobenzene at room temperature in the presence of a suitable base, and then hydrogenated in the presence of PdZC. A target compound having a phenyl ring introduced into ⁵ can be synthesized. In addition, the target compound having a chain group is prepared by dissolving a 5-aminoquinoxaline compound in an appropriate solvent, adding Pd (dba) and BINAP in catalytic amounts, respectively, and adding 2-butyl in the presence of an appropriate base. It can be synthesized by reacting with mothiophene.

[0044] The method for synthesizing the 5-aminoquinoxaline compound of the above formula (20) is not particularly limited. For example, Journal 'Ob' American 'Chemical' Society Ci. Am. Chem So), 1957, 79, 2245-2248, Giananoreb 'Organic' Chemistry (J. Org. Chem.), 1966, 31-3, 3384-3390. You can use the power S.

[0045] The production method of the polyaminoquinoxaline compound represented by the formula (1) or (2) is not particularly limited, and the aminoquinoxaline compound (monomer) of the above formula (19) or (20) It can be produced by polymerizing by the above method. As the polymerization method, chemical oxidative polymerization, electrolytic oxidative polymerization, catalytic polymerization, and the like can be used. In many cases, chemical oxidative polymerization and electrolytic oxidative polymerization are particularly preferable because a polymer can be formed on the electrode surface. Electrolytic oxidation polymerization is preferred.

Examples of the oxidizing agent used for the chemical oxidative polymerization include, but are not limited to, ammonium persulfate, tetraammonium peroxide, iron chloride, cerium sulfate, and the like.

[0046] As a specific method of electrolytic oxidation polymerization, for example, an oxidant is added to the monomer represented by the formula (19) or (20) and sufficiently stirred, and then an organic solvent is added to obtain a uniform solution. Electropolymerization can be performed using a tripolar beaker-type cell equipped with a white metal mesh counter electrode.

Examples of the oxidizing agent used for the electrolytic oxidation polymerization include hydrochloric acid, sulfuric acid, perchloric acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, and the like. Among them, perchloric acid is preferable. Is suitable.

Examples of the organic solvent include N, N-dimethylformamide, tetrahydrofuran, acetonitrile, dichloromethane, dimethyl sulfoxide, methanol, ethanol, and the like. In particular, N, N-dimethylformamide is preferably used.

[0047] The carbon material constituting the composition for an energy storage device electrode of the present invention is not particularly limited, and examples thereof include activated carbon, carbon black, and graphite. In addition, the shape is not particularly limited, and various shapes such as powder, granule, and fiber can be adopted. Of these, fibrous carbon materials are preferred, and graphite materials such as carbon felt are particularly preferred. .

Regarding the fiber diameter of the fibrous carbon material, the specific surface area increases as the fiber diameter decreases. Specifically, the fiber diameter is preferably 10 to 50 × m, more preferably 10 to 20 μπι.

[0048] Although the composite ratio of the polyaminoquinoxaline compound represented by the formula (1) or (2) and the carbon material is arbitrary, preferably, the polyaminoquinoxaline compound / carbon-based material = 3/97 to 35/65 (Mass ratio), more preferably 3/97 to 7/93 (mass ratio).

The composition for the energy storage device electrode of the present invention is arbitrary, and is a composition obtained by mixing the polyaminoquinoxaline compound represented by the formula (1) or (2) and a carbon material in the form of a powder. Or a polyaminoquinoxaline compound represented by the formula (1) or (2) adheres to the surface of a powdered or fibrous carbon material (in an easily peelable state) Examples include compositions. In particular, a composition in which the polyaminoquinoxaline compound represented by the formula (1) or (2) is attached in a state where the fiber surface constituting the fibrous carbon material is coated is preferable. When this composition is used as an electrode for an energy storage device, the energy density of the device can be improved.

[0049] A composition in which polyaminoquinoxaline is adhered to a carbon material is such that the polyaminoquinoxaline compound can be easily formed into a thin film by vapor deposition, spin coating, dating, casting, screen printing, or the like. Therefore, the carbon material surface can be prepared by coating the surface of the carbon material with a polyaminoquinoxaline compound-containing thin film using these techniques. In particular, by preparing a coating composition containing a polyaminoquinoxaline compound represented by the formula (1) or (2) and applying it to a carbon material, the polyaminoquinoxaline compound is a carbon material. Can easily and easily prepare a composition adhered to

[0050] Here, the component of the coating composition containing the polyaminoquinoxaline compound is not particularly limited. For example, the polyaminoquinoxaline compound, a polymer material for improving film-forming properties, and a dispersant The composition containing etc. can be used. The content of the polyaminoquinoxaline compound in the composition can be, for example, about 50 to 90% by mass.

In the coating composition, additives such as a heat stabilizer, a light stabilizer, a filler, and a reinforcing agent can be appropriately blended as necessary.

[0051] A composition in which polyaminoquinoxaline is attached to a carbon material can also be prepared by electrolytic oxidation polymerization of a monomer represented by the formula (19) or (20) on the surface of the carbon material. For electrolytic oxidation polymerization, for example, activated carbon, carbon black, or fibrous carbon material may be used as a test electrode substrate, and Ag / Ag ⁺ may be used as a reference electrode, and electrolytic polymerization may be performed using an electrochemical measurement system. As a specific technique for electrolytic polymerization, potential sweeping method, constant potential method, etc. can be used. In this case, p-phenylenediamine may be added as an additive for promoting the polymerization reaction.

As a result, the target polyaminoquinoxaline compound is deposited so as to cover the surfaces of the activated carbon, carbon black, and fibrous carbon material, and a composition in which the carbon material and polyaminoquinoxaline are adhered is obtained.

[0052] Since the polyaminoquinoxaline compound represented by the above formula (1) or (2) has conductivity, it has excellent electrochemical characteristics such as an effect of reducing contact resistance at the electrode interface. Since it has, it can utilize suitably as an electrode active material.

For this reason, the composition containing the polyaminoquinoxaline compound represented by the formula (1) or (2) and the carbon material can be suitably used for an electrode for an energy storage device. An electrode for an energy storage device is prepared by mixing a polyaminoquinoxaline compound, a carbon material, and, if necessary, a binder resin to prepare an electrode composition. It can be formed into a shape. The binder resin can be appropriately selected from known materials such as polyvinylidene fluoride.

Moreover, the composition obtained by adhering the polyaminoquinoxaline compound to the carbon material surface described above can be used as an electrode of an energy storage device as it is.

[0053] An energy storage device according to the present invention is an energy storage device including at least a pair of positive and negative electrodes, a separator interposed between these electrodes, and an electrolyte. It is comprised from the electrode for energy storage devices of this invention. As already described, since the polyaminoquinoxaline compound is a conductive polymer that can be used for both positive and negative electrodes, both the positive and negative electrodes can be constituted by the energy storage device electrode of the present invention.

Examples of energy storage devices include electric double layer capacitors, lithium ion batteries, lithium polymer batteries, nickel metal hydride batteries, lead storage batteries, and other energy storage devices. Among them, electric double layer capacitors, lithium ion batteries, proton polymers One battery is preferable.

[0054] In particular, when the electrode for an energy storage device of the present invention is used as an electrode for an electric double layer capacitor, the oxidation-reduction reaction of the polyaminoquinoxaline compound and the electric double layer generated on the surface thereof Since both can be used as energy sources, it is possible to store higher capacity than conventional activated carbon-only electric double layer capacitors.

[0055] Since the energy storage device of the present invention is characterized by the use of the above-mentioned electrode for energy storage device as an electrode, other device constituent members such as a separator, an electrolyte, etc. are appropriately selected from known materials. It can be selected and used.

Examples of the separator include a cellulose-based separator and a polyolefin-based separator.

The electrolyte may be either liquid or solid, and may be either aqueous or non-aqueous. However, the electrode for an energy storage device of the present invention is practically sufficient even when applied to a device using a non-aqueous electrolyte. Performance can be demonstrated.

[0056] Examples of the non-aqueous electrolyte include a non-aqueous electrolyte obtained by dissolving an electrolyte salt in a non-aqueous organic solvent. Examples of the electrolyte salt include lithium salts such as lithium tetrafluoroborate, lithium hexafluorophosphate, lithium perchlorate, and lithium trifluoromethanesulfonate; tetramethyl ammonium hexaphosphate, tetraethyl ammonium Umhexafluorophosphate, Tetrapropynoleammoum Hexafnoreo Mouth Phosphate, Methinoretrechinoreammonum Hexafluophosphate, Tetraethylammonium Tetrafluoroborate, Tetraethyl Ruammonium Park Examples include quaternary ammonium salt such as mouth rate.

Examples of non-aqueous organic solvents include propylene carbonate, ethylene carbonate, butylene carbonate and other aralkylene carbonates; And amides.

Example

Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples and comparative examples. However, the present invention is not limited to the following examples.

[0058] [Synthesis Example 1] Synthesis of 2,3 dihydroxy-5-aminoquinoxaline

It was synthesized by the following methods (1) to (3).

(1) Synthesis of 2, 3-Diaminonitrobenzene

[Chemical 39]

Dissolve 14 g of commercially available 1-amino-2,5 dinitrobenzene in 225 ml of methanol, dissolve 60 g of sodium sulfide and 21 g of sodium bicarbonate in 240 g of water, and maintain the reaction temperature at 60 ° C using a dropping funnel. It was added as it was. After the addition, the mixture was further stirred at 60 ° C for 1 hour. After completion of the reaction, it was cooled to room temperature and filtered.

m / z: (FD +) 153 (calculated value 153.1396)

— NMR: 7. 7228, 7. 7203, 7. 7026, 7. 2433, 6. 9245, 6. 6209, 6. 6 063, 6. 6038, 6. 5886, 5. 9210, 3. 3978 ppm.

Yield: 7. 79g (66.5%) Properties: Reddish brown fine crystals

Melting point: 140 ° C

[0060] (2) Synthesis of 2, 3 dihydroxy 5 troquinoxaline

[Chemical 40]

[0061] 50 of 2,3 diaminonitrobenzene 4 g (26.12 mmol) and commercially available oxalic acid dihydrate 6.59 g (52.24 mmol). It was dissolved in / o acetic acid and reacted at the boiling point for 3 hours under an argon stream. After completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitated crystals were filtered.

Yield: 3. 01g (55. 6%)

Properties: Yellow fine crystals

m / z: 207 (calculated value 207.144)

[0062] (3) Synthesis of 2, 3-dihydroxy _ 5-aminoquinoxaline

[Chemical 41]

2,3-dihydroxy-5_nitroquinoxaline 2. After dissolving OOg in 100 g of methanol / dioxane 1: 1 solvent, the reaction system was thoroughly purged with argon, and 5% PdZC (containing water) 1. OOg was added thereto. . Thereafter, the system was replaced with hydrogen and reacted at room temperature for 20 hours. After completion of the reaction, the reaction product was dispersed in a solution of 6.OOg of potassium carbonate in 130 ml of water to dissolve the product. 35% hydrochloric acid was gradually added to the solution obtained after filtration to obtain a precipitate.

Yield: 1. 10g

Properties: pale yellow fine crystals

m / z (FD +): 177 (calculated value 177.1616)

¹³ C-NMR: 155. 8030, 155. 6504, 135. 9570, 126. 8390, 124. 1303, 112. 3265, 109. 6025, 103. 8418 ppm. [0064] [Synthesis Example 2] Synthesis of 2,3-Diphenylinole 5-aminoquinoxaline

It was synthesized by the following methods (1) and (2).

(1) Synthesis of 2,3-Diphenenole 5 troquinoxaline

[Chemical 42]

[0065] 2,3-Diaminonitrobenzene 1.53 g (10 mmol) and benzil 2.00 g (9.6 mmol) were placed in a four-necked flask and dissolved in acetic acid: methanol = 1: 1 solvent 30 g. Thereafter, the reaction was carried out at a reaction temperature of 70 ° C for 2 hours. After the reaction, the solvent was removed, and the product was extracted with a silica gel column (ethyl acetate: hexane = 1: 1).

Yield: 2. llg

Properties: Yellow fine crystals

m / z: 327 (calculated value 327.24)

[0066] (2) Synthesis of 2,3-diphenyl-2-ruminoquinoxaline

[Chemical 43]

[0067] 1,4-g of 2,3-diphenyl-1-nitroquinoxaline was dissolved in 30 g of dioxane and substituted with argon, and then 0.5 g of 5% Pd / C (containing water) was added. After sufficiently replacing with argon again, hydrogen was added and reacted at room temperature for 30 hours. After completion of the reaction, the reaction solvent was removed by filtration, followed by separation and purification on a silica gel column (ethyl acetate: hexane = 1: 3).

Yield: 0.73g

Properties: Yellow fine crystals

m / z: 297 (calculated value M: 297.36)

¹³ C-NMR: 153.56055, 150. 1185, 144.2280, 141.9619, 139.4516, 139.3524, 131.1348, 130.0894, 129.9368, 128.7694, 128.6473, 1 28. 3497, 128. 1743, 117. 2098, 110. 2511 ppm.

[0068] [Synthesis Example 3]

Synthesis of 2, 3 di (4 methylphenyl) -5 aminoquinoxaline

It was synthesized by the following methods (1) and (2).

(1) Synthesis of 2, 3-di (4 methylphenyl) _5_nitroquinoxaline

[Chemical 44]

[0069] 2,3 Diaminonitrobenzene 1. 84 g (12 mmol), 4, 4 'Dimethenolevenzinole 2. 38 g (10 mmol) was dissolved in 40 g of a mixed solvent of acetic acid and methanol (1: l), and the reaction temperature was 80 The reaction was performed at ° C for 4 hours. After completion of the reaction, the solvent was removed and the reaction product was extracted with a silica gel column.

Yield: 1. 30g

Properties: Yellow fine crystals

m / z: 355 (calculated value 355. 39)

¹³ C-NMR: 154. 8950, 154. 8339, 147. 0894, 140. 7563, 140. 1307, 139. 8636, 135. 5984, 135. 1253, 133. 7061, 133. 2254, 130. 2725, 1 29. 7003, 129. 3188, 129. 1204, 128. 4108, 127. 7470, 124. 2142 pp m.

[0070] (2) Synthesis of 2, 3-di (4 methylphenyl) -1-5-aminoquinoxaline

[Chemical 45]

[0071] 2.02 g of 2,3 di (4 methylphenyl) 1-5 nitroquinoxaline was dissolved in 30 g of dioxane and substituted with argon, and then 6 g of 5% Pd / C (containing water) was added. After substituting with argon again, it was replaced with hydrogen and reacted at room temperature for 18 hours. After the reaction is complete, filter and filter Was further washed with acetone and dioxane and filtered again. After removing the solvent from the obtained filtrate, the reaction product was extracted with a silica gel column.

Yield: 1. 36g

Properties: Yellow fine crystals

m / z: 325 (calculated value 325. 14)

¹³ C-NMR: 153. 6131, 150. 1643, 144. 0907, 141. 8551, 138. 6581, 138. 5894, 136. 7047, 136. 6666, 131. 2721, 130. 7761, 129. 9292, 1 29. 7766, 129. 0365, 128. 9815, 117. 2403, 110. 0603 ppm.

[0072] [Synthesis Example 4] Synthesis of 2,3-di (4-methoxyphenyl) -1-5-aminoquinoxaline

It was synthesized by the following methods (1) and (2).

(1) Synthesis of 2, 3- (4-dimethoxyphenyl) _5_nitroquinoxaline

[Chem 46]

[0073] 2, 3-Diaminonitrobenzene 1. 54 g (10 mmol), 4, A '— Dimethoxybenzyl 2. 25 g (8.3 mmol) was dissolved in a solvent (methanol: acetic acid = 1: 1, 100 g). And allowed to react at room temperature for 20 hours. After completion of the reaction, the mixture was filtered, and the filter was further washed with acetone and dioxane and filtered again. After removing the solvent from the resulting filtrate, extract the reaction product with a silica gel column.

Yield: 1. 24g

Properties: Yellow fine crystals

m / z: 387 (calculated value: 387. 39)

¹³ C-NMR: 161. 0983, 160. 9075, 154. 3303, 154. 2464, 146. 9520, 140. 6495, 133. 5993, 133. 1415, 131. 9207, 130. 8448, 130. 4099, 1 27. 5104, 124. 0998, 114. 1043, 113. 8830 ppm.

[0074] (2) Synthesis of 2,3-di (4-methoxyphenyl) -1-5-aminoquinoxaline

[Chemical 47]

[0075] 0.53 g of 2,3- (4-dimethoxyphenyl) 15 nitroquinoxaline was dissolved in 30 g of dioxane and sufficiently substituted with argon. Thereafter, 0.5 g of 5% Pd / C (containing water) was added, and then sufficiently replaced with argon again. This system was replaced with hydrogen and reacted at room temperature for 24 hours. After completion of the reaction, the mixture was filtered, and the filter was further washed with acetone and dioxane and filtered again. After removing the filtrate power solvent obtained, the reaction product was extracted with a silica gel column.

Yield: 0.37g

Properties: Yellow fine crystals

m / z: 325 (calculated value: 325.43)

13C-NMR: 160. 1369, 160. 0606, 153. 1324, 149. 7370, 144.0144, 141. 7483, 131. 3942, 131. 2874, 130.6235, 117. 1640, 113. 8296, 113. 6618, 110.0145, 55. 3828 ppm.

[0076] [Synthesis Example 5] Synthesis of 2, 3 di (4 bromophenyl) 5 aminoquinoxaline

It was synthesized by the following methods (1) and (2).

(1) Synthesis of 2,3-di (4 bromophenyl) _5_nitroquinoxaline

[Chemical 48]

[0077] 2,3 Diaminonitrobenzene 1 · 53 g (10 mmol), 4, 4 ′ —Dibromobenzyl 3.6 · 8 g (10 mmol) was dissolved in 80 g of a mixed solvent of acetic acid and methanol (1: 1), and the reaction temperature was 70 The reaction was carried out at ° C for 30 hours. After completion of the reaction, the solvent is removed and the reaction product is extracted with a silica gel column.

Yield: 1. 89g

Properties: Yellow fine crystals

m / z: 485 (calculated value 485. 12) C-NMR: 153. 4453, 153. 3613, 147. 0065, 140. 7945, 136. 8116 136. 3766, 133. 7824, 133. 2635, 132. 0504, 131. 8749, 131. 8215, 31. 3789 , 128. 5787, 124. 9849, 124. 8780, 124. 7102 ppm.

[0078] (2) Synthesis of 2,3-di (4_bromophenyl) -1-5-aminoquinoxaline

[Chemical 49]

[0079] 2,3-Di (4-bromophenyl) 15-nitroquinoxaline 1 · Olg (mol) was dissolved in dioxane 3 Og and sufficiently substituted with argon. Thereafter, 0.3 g of 5% Pd / C (containing water) was added, and the atmosphere was sufficiently replaced with argon again. This system was replaced with hydrogen and reacted at room temperature for 24 hours. After completion of the reaction, the mixture was filtered, and the filter was further washed with acetone and dioxane and filtered again. After removing the solvent from the obtained filtrate, the reaction product was extracted with a silica gel column.

Yield: 0.66g

Properties: Yellow fine crystals

m / z: 455 (calculated value: 455. 12)

[0080] [Synthesis Example 6] Synthesis of 2, 3-Dicenyl _ 5-aminoquinoxaline

It was synthesized by the following methods (1) and (2).

(1) Synthesis of 2, 3-Dicenyl-5_nitroquinoxaline

[Chemical 50]

[0081] 2,3-Diaminonitrobenzene 0.022g (0.144mmol), 2,2'-Chechinolere 0.019 19g (0: 1 087mmol) in acetic acid / methanol mixed solvent (1: 1) to 3g It was dissolved and reacted at a reaction temperature of 70 ° C for 30 hours. After completion of the reaction, the solvent was removed, and the reaction product was extracted with a silica gel column.

Yield: 0.04g Properties: Yellow fine crystals

m / z: 339 (calculated value: 339. 40)

[0082] (2) Synthesis of 2, 3-Diciniru 5-aminoquinoxaline

[Chemical 51]

[0083] 2,3-Dicenyl-5-nitroquinoxaline 1. Olg (mol) was dissolved in 30 g of dioxane and sufficiently substituted with argon. Thereafter, 0.3 g of 5% Pd / C (containing water) was added, and the mixture was sufficiently replaced with argon again. This system was replaced with hydrogen and reacted at room temperature for 24 hours. After completion of the reaction, the mixture was filtered, and the filter was further washed with acetone and dioxane and filtered again. After removing the solvent from the obtained filtrate, the reaction product was extracted with a silica gel column.

Yield: 0.40g

Properties: Yellowish brown fine crystals

m / z: 309 (calculated value 309. 42)

[0084] [Synthesis Example 7] Synthesis of 10-aminodibenzo (A, C) phenazine

It was synthesized by the following methods (1) and (2).

(1) Synthesis of 1, 2, 3-triaminobenzene

[Chemical 52]

[0085] After dissolving 15.0 g (82 mmol) of 2,6-dinitroaniline in 150 g of tetrahydrofuran, the reaction system was sufficiently purged with nitrogen, and 7.6 g of 5% Pd / C (containing water) was added thereto. Thereafter, the atmosphere was replaced with hydrogen and reacted at room temperature for 15 hours. After completion of the reaction, the reaction solution was filtered to remove Pd, and the filtrate was concentrated as it was to obtain the desired product. Since the obtained compound was unstable, it was used in the next reaction as it was.

[0086] (2) Synthesis of 10-aminodibenzo (A, C) phenazine

[Chemical 53]

[0087] 1,2,3_triaminobenzene (82 mmol), 9,10 Phenanthrenequinone 14.6 g (70 mmol) was put into a four-necked flask, and acetic acid: methanol = 1: 1 solvent 350 g was added thereto. Dissolved. Thereafter, the reaction was conducted at a reaction temperature of 70 ° C. for 2 hours. After the reaction, the solvent was removed, and the product was washed with methanol to obtain the desired product.

Yield: 17. lg

Appearance: Ocher solid

m / z: 295 (calculated value 29511)

[Synthesis Example 8] Synthesis of 2,3-diphenylenoyl 5- (4-aminophenyl) aminoquinoxaline The compound was synthesized by the following methods (1) and (2).

(1) Synthesis of 2,3-Diphenyl 2-5- (4-Nitrophenyl) aminoquinoxaline [Chemical Formula 54]

[0089] 2,3 Diphenyl nitro 5 Aminoquinoxaline 4.0 g (13.4 mmol), 4 Fluoronitrobenzene 2 lg (14.9 mmol), 100 ml of dimethyl sulfoxide were stirred, and 5.0 g (44. 6 mmol) was added slowly. After the addition was complete, the reaction vessel was purged with nitrogen and stirred at room temperature for 24 hours. After completion of the reaction, 100 ml of water was added while cooling, and then the organic layer was extracted using a chloroform solvent, and the solvent was concentrated to obtain the desired product. Yield: 5.4g

[0090] (2) Synthesis of 2,3 diphenyl-2-ru-5- (4 aminophenyl) aminoquinoxaline

[Chemical 55]

[0091] 5.4 g (2.9 mmol) of 2,3-diphenyl-5_ (4_nitrophenyl) aminoquinoxaline was dissolved in 100 ml of tetrahydrofuran, and the inside of the reaction vessel was purged with nitrogen. Thereafter, 5% Pd / C (containing water) 5. Og was added, and the gas was sufficiently replaced with nitrogen again. This system was purged with hydrogen and reacted at room temperature for 10 hours. After completion of the reaction, the mixture was filtered, and the filter was further washed with tetrahydrofuran and filtered again. After removing the solvent from the obtained filtrate, the reaction product was recrystallized from a tetrahydrofuran / heptane mixed solvent.

Yield: 3.9g

Property: Orange solid

m / z: 388 (calculated value 388. 17)

¹³ C-NMR: 153. 597, 149. 658, 142. 978, 142. 887, 142. 009, 139. 3 06, 139. 199, 132. 290, 131. 283, 130. 008, 129. 825, 128. 680, 128. 588, 128. 267, 128. 130, 124. 794, 116. 198, 116. 114, 106. 648 ppm

[0092] [Synthesis Example 9] Synthesis of 2, 3-di (4-methylphenyl) -5_ (4-aminophenyl) aminoquinoxaline

It was synthesized by the following methods (1) and (2).

(1) Synthesis of 2, 3-di (4-methylphenyl) _ 5_ (4-nitrophenyl) aminoquinoxaline

[Chemical 56]

[0093] 2,3-di (4-methylphenyl) 5-5-aminoquinoxaline 3 · 0 g (9.2 mmol), 4-fluoronitrobenzene 1 · 4 g (9.9 mmol) and 100 ml of dimethyl sulfoxide were stirred. However, 3.4 g (30.3 mmol) of t-butoxypotassium was slowly added. After completion of the addition, the reaction vessel was purged with nitrogen and stirred at room temperature for 20 hours. After completion of the reaction, 100 ml of water was added while cooling, and then the organic layer was extracted using a chloroform solvent, and the solvent was concentrated to obtain the desired product.

Yield: 5.9g

m / z: 446 (calculated value 446. 17)

[0094] (2) Synthesis of 2, 3-di (4-methylphenyl) -5_ (4-aminophenyl) aminoquinoxaline

[Chemical 57]

[0095] 2,3-Di (4-methylphenyl) 1-5- (4-nitrophenyl) aminoquinoxaline 5. 9 g (13.2 mmol) was dissolved in 70 ml of tetrahydrofuran, and the inside of the reaction vessel was purged with nitrogen. Thereafter, 2 g of 5% Pd / C (containing water) was added, and the gas was sufficiently replaced with nitrogen again. This system was purged with hydrogen and reacted at room temperature for 13 hours. After completion of the reaction, the mixture was filtered, and the filter was further washed with tetrahydrofuran and filtered again. After removing the solvent from the obtained filtrate, the reaction product was extracted with a silica gel column.

Yield: 1. lg

Property: Orange solid

m / z: 416 (calculated value 416.20)

¹³ C-NMR: 153. 605, 149. 711, 142. 719, 141. 917, 138. 573, 136. 5 43, 132. 542, 130. 977, 129. 863, 129. 703, 128. 970, 128. 870, 124. 664, 116. 198, 106. 480, 21. 352 ppm.

[0096] [Synthesis Example 10] 2,3-Di (4-methoxyphenyl) -5_ (4-aminophenyl) aminoquinoxa Synthesis of phosphorus

It was synthesized by the following methods (1) and (2).

(1) Synthesis of 2, 3 di (4-methoxyphenyl) 5- (4-12 tropenyl) aminoquinoxaline

[Chemical 58]

[0097] 2,3 Di (4-methoxyphenyl) one 5 aminoquinoxaline 5.0 g (14. Ommol), 4-fluoronitrobenzene 2.4 g (17. Ommol), 120 ml of dimethyl sulfoxide were stirred. T-butoxypotassium 5.7 g (50.8 mmol) was slowly added. After completion of the addition, the reaction container was purged with nitrogen and stirred at room temperature for 8 hours. After completion of the reaction, 10 Oml of water was added while cooling, and then the organic layer was extracted using a chloroform solvent, and the solvent was concentrated to obtain the desired product.

Yield: 8.3g

Property: Brown solid

[0098] (2) Synthesis of 2, 3-di (4 methoxyphenyl) -5_ (4-aminophenyl) aminoquinoxaline

[Chemical 59]

2,3 di (4 methoxyphenyl) 1-5- (4 nitrophenyl) aminoquinoxaline 8.3 g (17.3 mmol) was dissolved in 100 ml of tetrahydrofuran, and the inside of the reaction vessel was purged with nitrogen. Thereafter, 5 g of 5% Pd / C (containing water) was added, and the gas was sufficiently replaced with nitrogen again. This system was replaced with hydrogen, The reaction was allowed to proceed at room temperature for 10 hours. After completion of the reaction, the mixture was filtered, and the filter was further washed with tetrahydrofuran and filtered again. After removing the solvent from the obtained filtrate, the desired product was obtained by recrystallizing the reaction product in hexane.

Yield: 4.5g

Property: Orange solid

m / z: 448 (calculated value 448. 19)

¹³ C-NMR: 163. 766, 159. 994, 153. 131, 148. 872, 142. 940, 142. 6 88, 141. 803, 132. 420, 131. 947, 131. 329, 131. 206, 130. 779, 124. 725, 116. 076, 113. 755, 113. 625, 106. 411, 98. 953, 55. 324 ppm.

[0100] [Synthesis Example 11] Synthesis of 2, 3-Di (2-Chenyl) -5_ (4-Aminophenyl) aminoquinoxaline

It was synthesized by the following methods (1) and (2).

(1) Synthesis of 2, 3-di (2-chenyl) -5- (4-12 trophenyl) aminoquinoxaline

[0101] 2,3-Di (2-Chenyl) -5-Aminoquinoxaline 3. lg (9.9 mmol), 4_fluoro nitrobenzene 1.4 g (9.9 mmol) and dimethyl sulfoxide 15 g with stirring Then, 3.3 g (29.6 mmol) of t-butoxypotassium was slowly added. After the addition was complete, the reaction vessel was purged with nitrogen and stirred at room temperature for 14 hours. After completion of the reaction, 100 ml of water was added while cooling, and the resulting compound was filtered, dried and purified by a silica gel column.

Yield: 2.6 g

Property: Yellow solid

[0102] (2) Synthesis of 2, 3-di (2-chenyl) _ 5_ (4-aminophenyl) aminoquinoxaline

[0103] 2,3-Di (2_chenyl) _5_ (4_nitrophenyl) aminoquinoxaline (2.2 g, 5. lm mol) was dissolved in tetrahydrofuran (50 ml), and the inside of the reaction vessel was purged with nitrogen. Thereafter, 0.7 g of 5% Pd / C (containing water) was added, and the mixture was sufficiently replaced with nitrogen again. This system was replaced with hydrogen and reacted at room temperature for 5 hours. After completion of the reaction, the mixture was filtered, and the filter was further washed with tetrahydrofuran and filtered again. After removing the solvent from the obtained filtrate, the reaction product was extracted with a silica gel column.

Yield: 1.9g

Property: Orange solid

m / z: 399 (calculated value 400.08)

¹³ C-NMR: 146. 665, 143. 161, 143. 009, 142. 619, 142. 009, 141. 4 13, 132. 084, 131. 535, 130. 443, 129. 061, 128. 840, 128. 603, 128. 473, 127. 618, 127. 512, 124. 878, 116. 068, 115. 931, 106. 930 ppm

[0104] [Synthesis Example 12] Synthesis of N_4_aminophenyl-10-dibenzo (A, C) phenazine

It was synthesized by the following methods (1) to (3).

(1) Synthesis of N _ 4 -nitrophenyl-10-dibenzo (A, C) phenazine

[Chemical 62]

While stirring 10-aminodibenzo (A, C) phenazine 10.0 g (34 mmol), 4-fluoronitrobenzene 4.8 g (34 mmol) and dimethyl sulfoxide 500 ml, t-butoxykari 19.4 g (173 mmol) of um was slowly added. After completion of the addition, the reaction vessel was purged with nitrogen and stirred at room temperature for 24 hours. After completion of the reaction, 500 ml of water was added while cooling, and the reaction solution was filtered to obtain a residue. The obtained filtrate was washed with methanol to obtain the desired product. (2) Synthesis of N-4-aminophenyl 1-dibenzo (A, C) phenazine

[Chemical 63]

[0107] 4.5 g (10.8 mmol) of N-4-nitrophenyl mono 10-dibenzo (A, C) phenazine was dissolved in 200 ml of tetrahydrofuran, and the inside of the reaction vessel was purged with nitrogen. Thereafter, 4.6 g of 5% PdZC (containing water) was added, and the gas was sufficiently replaced with nitrogen again. This system was replaced with hydrogen and reacted at room temperature for 10 hours. After completion of the reaction, the mixture was filtered, and the filter cake was further washed with tetrahydrofuran and then purified with a column to obtain the desired product.

Properties: Purple crystals

m / z: 386 (calculated value 386. 15)

[0108] [Example 1] Preparation of poly {10-aminodibenzo (A, C) phenazine} / carbon felt composite electrode

A composite electrode was prepared by electrolytic oxidation using a tripolar beaker type cell. 10-aminodibenzo (A, C) phenazine obtained in Synthesis Example 7 0 · 15 g (0.5 mmol) and perchloric acid (70%) 1 · 6 g (l lmmol) were mixed with Ν, N-dimethylformamide. A solution dissolved in 6 · 5 g was prepared.

Next, in the resulting solution, a 2 mm thick carbon felt (Model number e_4_ l, fiber diameter: 12-: 14 xm) as a test electrode substrate is formed into a square with one side of lcm. The cut out was installed. A platinum mesh electrode was used as the counter electrode and an AgZAg + electrode was used as the reference electrode. Electrochemical polymerization using an electrochemical measurement system (ALS-660B manufactured by BAS Co., Ltd.) with a polymerization time of 300 seconds by the 0.7V constant potential method Went. After the end, the voltage was lowered from 0.7V to 0V at a rate of 0.OOlV / s, and kept for 300 seconds when it reached 0V. A black aminoquinoxaline polymer film was formed on the test electrode surface. The obtained electrode was carefully washed with acetonitrile and vacuum dried at 100 ° C for 1 hour. About 5. lmg of polymer was obtained on the surface of the carbon electrode.

The fiber diameter of the carbon felt was analyzed by a scanning electron microscope (SEM, JSM_7400F, manufactured by JEOL Ltd.).

[Example 2] Production of bipolar capacitor cell and charge / discharge test

The poly {10_aminodibenzo (A, C) phenazine} / carbon felt composite electrode obtained in Example 1 was cut into a 1 cm diameter circle, and this was further bonded to an aluminum plate using a carbon paste. It was created. Two capacitors were prepared as electrodes, and a capacitor cell was constructed so as to face each other through a separator (ADVANTEC GB-100R manufactured by Toyo Roshi Kaisha, Ltd.). At this time, a 0.5 mol / L acetonitrile solution of tetraethyl ammonium tetrafluoroborate was used as the electrolytic solution.

The constructed cell was subjected to charge / discharge measurement for 20 cycles by a constant current method with a current of 2 mA and a voltage of 2.8 V using a charge / discharge measurement system (HJ1001S M8A manufactured by Hokuto Denko Corporation). From the results at this time, the discharge specific capacity per aminoquinoxaline polymer film in the first cycle was 40.3 F / g (this discharge specific capacity is a value per unit active material).

[0110] [Example 3] Preparation of tripolar electrochemical cell and charge / discharge test

The poly {10-aminodibenzo (A, C) phenazine} / carbon felt composite electrode obtained in Example 1 was used as a test electrode. Using platinum mesh as the counter electrode and Ag wire as the reference electrode, immerse each electrode in a beaker containing 20 ml of a 0.5 mol / L acetonitrile solution of tetraethylammonium tetrafluoroborate. A polar electrochemical cell was constructed. Then, using an electrochemical measurement system (HZ-5000, manufactured by Hokuto Denko Co., Ltd.), a cyclic voltammetry test was performed under the conditions of a potential range from 0.8 V to 1.5 V and a sweep speed of 50 mVZs. From this area, the discharge specific capacity per single electrode was calculated. The discharge specific capacities obtained at this time were 1st cycle 65.lFZg, 100th cycle 71.9F / g, 200th cycle 74.4F / g, 300th cycle 75.0F / g, 400th cycle 44.8F / g, 500th cycle 26.6 FZg (This discharge specific capacity is the value per unit active material) [0111] [Synthesis Example 13] Preparation of poly (2,3-dicenyl-5-aminoquinoxaline)

Poly (2,3-dicenyl-5-aminoquinoxaline) was prepared on a platinum electrode by electrolytic oxidation using a tripolar beaker type cell. 2,3-Dicenyl-5-aminoquinoxaline obtained in Synthesis Example 6 0.47 g (l. 511111101), perchloric acid (70%) 3.2 g (22.4 mmol), and p-phenylene diene A solution was prepared by dissolving 1.5 mg (0.015 mmol) of amine in 9.8 g of N, N-dimethylformamide.

Next, in the obtained solution, a platinum plate cut into a square of 1 cm on each side was placed as a test electrode substrate. A platinum mesh electrode was used as the counter electrode and an AgZAg + electrode was used as the reference electrode. Using an electrochemical measurement system (ALS-660B manufactured by BAS Co., Ltd.), electrolytic polymerization was performed by a 0.5 V constant potential method with a polymerization time of 300 seconds. Test A black aminoquinoxaline polymer film was formed on the surface of the test. The resulting electrode was carefully washed with acetonitrile and vacuum dried at 100 ° C for 1 hour. Mass of polymer obtained: 0.3 mg. By scraping off the deposit on the platinum plate and measuring the mass spectrum, we confirmed that it was the target. Obtained mass spectral peaks: 309, 632, 925, 1231, 1538, 1839 (m / z).

[0112] [Example 4] Fabrication of poly (2,3-diphenyl-2-ruaminoquinoxaline) / carbon felt composite electrode

A composite electrode was prepared by electrolytic oxidation using a tripolar beaker type cell. 2,3-Dicenyl 5-Ominoquinoxaline 0 · 47g (l.5mmol), Perchloric acid (70%) 3.2g (22.4mmol) obtained in Synthesis Example 6 and p-phenylenediamine A solution was prepared by dissolving 1.5 mg (0.01 5 mmol) in 9.8 g of N, N-dimethylformamide.

Next, in the obtained solution, a 2 mm thick carbon felt (Tsukuba Material Information Laboratory Model No. e_4_l) cut into a 1 cm square was installed as a test electrode substrate. A platinum mesh electrode was used as the counter electrode and an AgZAg + electrode was used as the reference electrode. Using an electrochemical measurement system (ALS-660B, manufactured by BAS Co., Ltd.), electrolytic polymerization was performed with a polymerization time of 300 seconds by a 0.5 V constant potential method. A black aminoquinoxaline polymer film was formed on the test electrode surface. The obtained electrode was inserted with acetonitrile. It was washed carefully and vacuum dried at 100 ° C for 1 hour. 1.06 mg of polymer was obtained on the surface of the carbon felt.

[0113] [Example 5] Production of tripolar electrochemical cell and charge / discharge test

The poly (2,3-diphenyl-5-aminoquinoxaline) / carbon felt composite electrode obtained in Example 4 was used as a test electrode. Using platinum mesh as the counter electrode and Ag wire as the reference electrode, immerse each electrode in a beaker containing 20 ml of a 0.5 mol / L acetonitrile solution of tetraethylammonium tetrafluoroborate. A tripolar electrochemical cell was constructed. Then, using an electrochemical measurement system (HD-5000 manufactured by Hokuto Denko Co., Ltd.), a cyclic voltammetry test was performed at a potential range of 0.8V to 1.5V and a sweep speed of 50mVZs. The discharge specific capacity per single electrode was calculated from the area of the curve. The discharge specific capacities obtained at this time were 219.8F / g for the first cycle, 20.8F / g for the 100th cycle, 23.7F / g for the 200th cycle, 37.4F / g for the 500th cycle, 31.4F / g for the 1000th cycle, 64. lF / g, 1500 cyclonoles 89.7F / g, 2000 cyclonoles 122.3F / g, 2500 cyclonoles 168.7F / g, 3000 cyclonoles 197.4 4F / g, 3500 cyclonoles 208. 1F / g, 4000 Cycle No. 207.2 2F / g, 4500 Cynoles 203.9 9F / g, 5000 Cynoles 197. lF / g, 5500 Cynoles 187. 9F / g, 6000 Cynoles 177. lF / g Capacity is the value per unit active material).

[0114] [Comparative Example 1] Preparation of poly {10-aminodibenzo (A, C) phenazine} / platinum composite electrode

A composite electrode was prepared by electrolytic oxidation using a tripolar beaker type cell. 10-aminodibenzo (A, C) phenazine obtained in Synthesis Example 7 0 · 15 g (0.5 mmol) and perchloric acid (70%) 1.6 g (l lmmol) were mixed with N, N-dimethylformamide 6 A solution dissolved in 5 g was prepared.

Next, in the obtained solution, a platinum plate cut into a square of 1 cm on each side was placed as a test electrode substrate. A platinum mesh electrode was used as the counter electrode and an AgZAg + electrode was used as the reference electrode. Electrochemical measurement system (made by BAS Co., Ltd.

Using ALS-660B), electrolytic polymerization was carried out with a polymerization time of 300 seconds by the 0.7 V constant potential method. After completion, the voltage was reduced from 0.7V to 0V at a rate of 0.OOlVZs, and when it reached 0V, it was kept for 300 seconds. A black aminoquinoxaline polymer film is formed on the test electrode surface. It was. The obtained electrode was carefully washed with acetonitrile and vacuum-dried at 100 ° C for 1 hour. About 1 mg of polymer was obtained.

[0115] [Comparative Example 2] Fabrication of capacitor cell

Two poly {10-aminodibenzo (A, C) phenazine} Z platinum composite electrodes obtained by the above method were cut out in a circular shape with a lcm diameter, and a separator (ADVANTEC GB-100R manufactured by Toyo Roshi Kaisha, Ltd.) was prepared. The capacitor cell was constructed so as to face each other. At this time, a 0.5 mol ZL acetonitrile solution of tetraethyl ammonium tetrafluoroborate was used as the electrolyte. The constructed cell was subjected to 20 cycles of charge / discharge measurement by a constant current method with a current of 2 mA and a voltage of 2.8 V using a charge / discharge measurement system (HJ1001SM8A manufactured by Hokuto Denko Corporation). From the results at this time, the discharge specific capacity per aminoquinoxaline polymerized film in the first cycle was 13.5 F / g (this discharge specific capacity is a value per unit active material).

[0116] From the results of Example 2 and Comparative Example 2 above, the discharge specific capacity of the poly {10 aminodibenzo (A, C) phenazine} / carbon felt composite electrode was determined to be poly {10-aminodibenzo (A, C). It can be seen that it is significantly higher than that of the phenazine} / platinum composite electrode.

[0117] [Comparative Example 3] Fabrication of polyaniline / carbon felt composite electrode

A composite electrode was prepared by electrolytic oxidation using a tripolar beaker type cell. A solution was prepared by dissolving 0 · 50 g (5.3 mmol) of aniline purified by distillation and 1 · 6 g (l lm mol) of perchloric acid (70%) in 6 · 5 g of N, N dimethylformamide.

Next, in the obtained solution, a 2 mm thick carbon felt (Model number e- 4 1) (Tsukuba Material Information Laboratory) cut into a 1 cm square was installed as a test electrode substrate. . A platinum mesh electrode was used as the counter electrode and an AgZAg + electrode was used as the reference electrode, which was installed in the solution just like the test electrode. Electrolytic polymerization using an electrochemical measurement system (ALS-660 B manufactured by BSS Co., Ltd.) and a polymerization time of 300 seconds using a 0.7V constant potential method S, black polymer is a carbon felt electrode Although it was obtained on the surface, it was not immobilized on the electrode surface and deposited in a liquid state below the solution, and a composite electrode was not formed.

[0118] [Comparative Example 4] Preparation of polyaniline / carbon felt composite electrode

A composite electrode was prepared by electrolytic oxidation using a tripolar beaker type cell. A solution prepared by dissolving 0 · 50 g (5.3 mmol) of aniline purified by distillation and 1 · 6 g (l lm mol) of perchloric acid (70%) in 6 · 5 g of N, N-dimethylformamide was prepared.

Next, in this solution, a 2 mm thick carbon felt (Tsukuba Material Information Laboratory Model No. e_4_ l) cut into a 1 cm square is used as a test electrode substrate. installed. A platinum mesh electrode was used as the counter electrode and an Ag / Ag + electrode was used as the reference electrode. Using an electrochemical measurement system (ALS-660B manufactured by BAS Co., Ltd.), electropolymerization was performed by a potential sweep method with a potential range of 0.8 to: 1. 2V. The sweep speed was 0.05 VZs and 25 cycles were performed. However, although the black polymer was obtained on the surface of the bonfelt electrode, it was not fixed on the electrode surface and deposited in a liquid state below the solution, so that a composite electrode was not formed.

Claims

An energy storage device electrode composition comprising a polyaminoquinoxaline compound represented by the formula (1) and a carbon material.

[Chemical 1]

[Wherein, R ¹ and R ² are each independently a hydrogen atom, a hydroxyl group, a C to C alkyl group, C

1 10

~ C alkoxy group, phenyl group optionally substituted with Y, optionally substituted with Y

1 10

Pyridinore group, biphenyl group optionally substituted with γ, naphthyl group optionally substituted with γ, chenyl group optionally substituted with Y, pyrrolinole group optionally substituted with Y , A furyl group optionally substituted with Y, or a condensed heteroaryl group optionally substituted with Y (wherein R ¹ and R ² are the phenyl group, pyridyl group, biphenyl group, naphthyl group, phenyl group) , A pyrrolyl group, a furyl group or a condensed heteroaryl group, these groups may be bonded by a single bond, or R ¹ and R ² are combined together, and _CH CH CH-

2 2 2

, -CH CH 0, -OCH CH 1, -CH OCH 1, -OCH O, 1 CH CH S

2 2 2 2 2 2 2 2 2 1, -SCH CH 1, -CH SCH 1, -CH CH N (R)-, 1 N (R) CH CH 1,

CH N (R) CH-CH CH CH CH-CH CH CH 01, OCH CH

2 2 2 2 2

CH CH OCH, one CH OCH CH-CH OCH〇-, -OCH C

2 2 2 2 2 2

SCH CH S— OCH CH S— SCH CH O— CH CH = CH 1 -CH = CHCH 1 OCH = CH 1 CH = CH 0 1 SCH = CH 1

2

CH = CHS-, — N (R) CH = CH—, — CH = CHN (R) —, —〇 CH = N—, — N = CHO, 1 SCH = N, 1 N = CHS, 1 N (R ) CH = N, One N = CHN (R) One, One N (R) N = CH, One CH = N (R) N, One CH = CHCH = CH, One OCH

CH = CH- CH = CHCH ○-N = CHCH = CH- CH = CHCH = N

N = CHCH = N- -N = CHN = CH— or CH = NCH = N— At this time, the hydrogen atom bonded to the carbon atom of these groups may be substituted with Y. R is a hydrogen atom, C-C alkyl group, C-C haloalkyl group, C- C

1 10 1 10

2 2 2 2 2 2 2 2 2 1, -OCH 0, -CH CH S-, -SCH CH 1, CH SCH 1, CH CH

2 2 2 2 2 2 2 2 2

N (R) —, -N (R) CH CH, -CH N (R) CH, CH CH CH CH, C

2 2 2 2 2 2 2 2

H CH CH 0-1, -OCH CH CH 1, CH CH OCH 1, CH OCH CH

2 2 2 2 2 2 2 2 2 2 2 2

, 1 CH OCH O—, -OCH CH 0, 1 SCH CH S, 1 OCH CH S, 1 S

2 2 2 2 2 2 2 2

CH CH O, 1 CH CH = CH, 1 CH = CHCH—, 10 CH = CH, 1 CH

2 2 2 2

= CHO_, _SCH = CH―, _CH = CHS―, _N (R) CH = CH―, _CH = C HN (R ')-, one OCH = N-, _N = CHO-, one SCH = N-, _N = CHS-, 1 N (R ') CH = N―, _N = CHN (R') ―, _N (R ') N = CH―, _CH = N (R') N―,-CH = CHCH = CH -, -OCH CH = CH—, one CH = CHCH O—, -N = CHC

twenty two

H = CH, 1 CH = CHCH = N—, _N = CHCH = N—, _N = CHN = CH—, or 1 CH = NCH = N— The hydrogen atom bonded to may be substituted with Y. R is a hydrogen atom, a C to C alkyl group,

1 10 C-C haloalkyl group, C-C cyanoalkyl group, phenyl optionally substituted with Z

1 10 1 10

Nyl group, pyridyl group optionally substituted with Z, biphenyl group optionally substituted with Z, naphthyl group optionally substituted with Z, chenyl group optionally substituted with Z, substituted with Z In this case, R, mayore, pyrrolyl group, substituted with Z, may, le, furyl group, or substituted with Z, may represent, condensed heteroaryl group.

X ¹ represents _NH_R ⁵ _NH— or one NH—R ⁶ —,

R ⁵ and R ⁶ are each independently a C to C alkylene group, —C (◯) CH—, —CH C

1 10 2 2

1 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

1 10 1 10 1 10 group, phenyl group optionally substituted by z, pyridyl group optionally substituted by z, biphenyl group optionally substituted by z, substituted by z A naphthyl group which may be substituted with z, a pyrrolyl group which may be substituted with z, a pyrrolyl group which may be substituted with z, a les which may be substituted with z, a fluoryl group or a pyrrolyl group which is substituted with z, However, it represents a condensed heteroaryl group (however, when γ is 2 or more, they may be the same or different from each other).

1 c 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

1 10 1 10 1 10 represents a phenyl group, a phenyl group, a biphenyl group, a naphthyl group, a chenyl group, a pyrrolyl group, a furyl group, or a condensed heteroaryl group (however, when Z is 2 or more, they are the same or different from each other) Anyway, please)

n represents an integer of 2 or more. ]

An energy storage device electrode composition comprising a polyaminoquinoxaline compound represented by the formula (2) and a carbon material.

[Chemical 2]

1 10

A pyridyl group, a biphenyl group optionally substituted with γ, a naphthyl group optionally substituted with γ, a chenyl group optionally substituted with Y, a pyrrolinole group optionally substituted with Y , A furyl group optionally substituted with Y, or a condensed heteroaryl group optionally substituted with Y (R ¹ and R ² are the phenyl group, pyridyl group, biphenyl group, naphthyl group, In the case of an phenyl group, a pyrrolyl group, a furyl group or a condensed heteroaryl group, these groups may be bonded by a single bond), or R ¹ and R ² together represent CH CH CH-

2 2 2

, -CH CH〇1, -OCH CH -CH OCH OCH O CH CH S

2 2 2 2 2 2 2 2 2 -SCH CH -CH SCH CH CH N (R) N (R) CH CH

2 2 2 2 2 2 2 2 CH N (R) CH CH CH CH CH CH CH CH 0, OCH CH

2 2 2 2 2 2 2 2 2 2 2

CH, -CH CH OCH, -CH OCH CH, -CH OCH 0, -OCH C

2 2 2 2 2 2 2 2 2 2

H〇1, -SCH CH S—, -OCH CH S—, one SCH CH O—, one CH CH = CH

2 2 2 2 2 2 2 2 1, -CH = CHCH, 1 OCH = CH-, 1 CH = CH 0, 1 SCH = CH-,-

2

CH = CHS-, _N (R) CH = CH-, _CH = CHN (R)-, _〇CH = N-, _N = CHO-, one SCH = N-, _N = CHS-, one N (R) CH = N—, _N = CHN (R) One, one N (R) N = CH—, One CH = N (R) N—, One CH = CHCH = CH—, -OCH

2

CH = CH—, -CH = CHCH Yes, _N = CHCH = CH—, -CH = CHCH = N

2

-, _N = CHCH = N-, _N = CHN = CH_, or CH = NCH = N- may be formed.At this time, the hydrogen atom bonded to the carbon atom of these groups is replaced with Y. R is a hydrogen atom, C-C alkyl group, C-C haloalkyl group, C-C

1 10 1 10 1 10 Cyanoalkyl group, phenyl group optionally substituted with Z, pyridyl group optionally substituted with Z, biphenyl group optionally substituted with Z, substituted with Z Good naphth A til group, a benzyl group optionally substituted with Z, a pyrrolyl group optionally substituted with Z, a ring substituted with Z, a ring, a furyl group or a ring substituted with Z Represents a condensed heteroaryl group.

R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a cyan group, a nitro group, an amino group, a C to C alkyl group, a C to C alkoxy group, or a phenyl group optionally substituted with Y.

1 10 1 10

Group, pyridyl group optionally substituted with Y, biphenyl group optionally substituted with Y, naphthyl group optionally substituted with Y, chenyl group optionally substituted with Y, substituted with Y A pyrrolyl group which may be substituted, a furyl group which may be substituted with Y, or a ring which may be substituted with Y, or a condensed heteroaryl group (R ³ and R ⁴ are the phenyl group, pyridinole Group, a biphenyl group, a naphthyl group, a chenyl group, a pyrrolyl group, a furyl group or a condensed heteroaryl group, these groups may be bonded by a single bond.), Or R ³ and R ⁴ and becomes one cord, _CH CH CH-, -CH CH 〇_, _〇_CH CH-, -CH OCH

2 2 2 2 2 2 2 2 2 1, -OCH 0-1, -CH CH S-,-SCH CH 1, CH SCH 1, CH CH

2 2 2 2 2 2 2 2 2

N (R) —, -N (R) CH CH one, -CH N (R) CH one, CH CH CH CH one, C

2 2 2 2 2 2 2 2

H CH CH 0, -OCH CH CH 1, CH CH OCH 1, CH OCH CH

2 2 2 2 2 2 2 2 2 2 2 2

, 1 CH OCH O—, -OCH CH 0, 1 SCH CH S, 1 OCH CH S, 1 S

2 2 2 2 2 2 2 2

CH CH O, 1 CH CH = CH, 1 CH = CHCH-, 10 CH = CH, 1 CH

2 2 2 2

= CHO, 1 SCH = CH, 1 CH = CHS, 1 N (R) CH = CH, 1 CH = C HN (R) —, 1 OCH = N, 1 N = CHO, 1 SCH = N, 1 N = CHS, N (R) CH = N-, N = CHN (R)-, N (R) N = CH-, CH = N (R ') N-, CH = CHCH = CH-, -OCH CH = CH—, 1 CH = CHCH 2 O, 1 N = CHC

twenty two

H = CH, 1 CH = CHCH = N—, _N = CHCH = N—, _N = CHN = CH—, or 1 CH = NCH = N— The hydrogen atom bonded to may be substituted with Y. R ′ is a hydrogen atom, a C to C alkyl group,

1 10

a c to c haloalkyl group, a C to C cyanoalkyl group, a phenyl optionally substituted with Z

1 10 1 10

Nyl group, pyridyl group optionally substituted with z, biphenyl group optionally substituted with z, naphthyl group optionally substituted with z, chenyl group optionally substituted with z, substituted with z Substituted with les, mayore, pyrrolyl, z, substituted with les, mayole, furyl, or z And represents a condensed heteroaryl group.

Y is a halogen atom, cyano group, nitro group, amino group, epoxy group, vinyl group, c to

1 c 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

1 10 1 10 1 10 group, phenyl group optionally substituted with Z, pyridyl group optionally substituted with Z, biphenyl group optionally substituted with Z, substituted with Z A naphthyl group which may be substituted with Z, a pyrrolyl group which may be substituted with Z, a pyrrolyl group which may be substituted with Z, a thiol, a furyl group or a thiol substituted with Z However, it represents a condensed heteroaryl group (however, when Y is 2 or more, they may be the same or different from each other).

Z is a halogen atom, cyan group, nitro group, amino group, epoxy group, bur group, C to C

1 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

n represents an integer of 2 or more. ]

The composition for an energy storage device electrode according to claim 1 or 2, wherein R ¹ and R ² are each independently represented by the formula (3).

[Chemical 3]

1 10 1 4 1

10 1 4

Substituted with, ret, ret, naphthyl group or Z, rep, pos, or cheyl group, z represents a halogen atom, cyan group, nitro group, amino group, epoxy group, Bulle group, c ~

1 c 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl Represents a thio group, a phenyl group, a biphenyl group, a naphthyl group, a chenyl group, a pyrrolyl group, a furyl group, or a condensed heteroaryl group. )

The energy storage device electrode composition according to claim 1 or 2, wherein R ¹ and R ² are each independently represented by the formula (4).

[Chemical 4]

(Wherein R ^{12 to} R ¹⁸ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bur group, C-C substituted at any position on the ring) Archi

1 10

, Mayoele, naphthyl group or substituted with Z represents les, mayole, cheryl group,

1 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

1 10 1 10 1 10 represents a phenyl group, a phenyl group, a biphenyl group, a naphthyl group, a chenyl group, a pyrrolyl group, a furyl group or a condensed heteroaryl group. )

The energy storage device electrode composition according to claim 1 or 2, wherein R ¹ and R ² are each independently represented by the formula (5).

[Chemical 5]

( ⁵ )

(In the formula, ^ ~! ^ ¹ is independently hydrogen atom, halogen atom, cyano group, nitro group, amino group, epoxy group, bier group, C ~ C Archi

1 10

Z is a halogen atom, cyan group, nitro group, amino group, epoxy group, vinyl group, C to C Alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

1 10 1 10 1 10 represents a phenyl group, a phenyl group, a biphenyl group, a naphthyl group, a chenyl group, a pyrrolyl group, a furyl group or a condensed heteroaryl group, and A ¹ represents NH, ○ or S. )

6. The composition for an energy storage device electrode according to claim 5, wherein the polyaminoquinoxaline compound is represented by the following formula (21).

[Chemical 6]

1 10 1 10

Phenyl group, pyridyl group which may be substituted with γ, biphenyl group which may be substituted with Y, naphthyl group which may be substituted with Y, chenyl group which may be substituted with Y, Y A pyrrolyl group which may be substituted, a furyl group which may be substituted with Y, or a condensed heteroaryl group which may be substituted with Y (R ⁷⁵ and R ⁷⁶ are the above phenyl group, pyridyl group; , A biphenyl group, a naphthyl group, a chenyl group, a pyrrolyl group, a furyl group or a condensed heteroaryl group, these groups may be bonded by a single bond.

In the formula, R ^{77 to} R ⁸² are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bur group, a C to C alkyl group, a C to C alkoxy group, or Z.

1 10 1 10

Substituted les, mayore, phenyl groups, substituted with Z, les, mayole, naphthyl groups, or substituted with Z, represent ele, mayore, phenyl groups,

1 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

1 10 1 10 1 10 group, phenyl group, biphenyl group, naphthyl group, chenyl group, pyrrolyl group, furyl group or Represents a condensed heteroaryl group (however, when Z is 2 or more, they may be the same or different from each other).

n represents an integer of 2 or more. ]

The energy storage device electrode composition according to claim 1 or 2, wherein R ¹ and R ² are each independently represented by the formula (6).

[Chemical 7]

(In the formula, a halogen atom or a cyano group is represented, and R ″ to R are independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bier group,

0 1 10

Being substituted with a naphthyl group or Z represents a ret, tomo les, or a cheryl group,

Z is a halogen atom, cyan group, nitro group, amino group, epoxy group, vinyl group, c to c

1 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

The composition for an energy storage device electrode according to claim 1, wherein R ⁵ is represented by formula (7).

[Chemical 8]

1 10

, Mayoele, naphthyl group or substituted with Z represents les, mayole, cheryl group, z is a halogen atom, cyano group, nitro group, amino group, epoxy group, vinyl group, c to c

1 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

The composition for an energy storage device electrode according to claim 1, wherein R ⁵ is represented by formula (8).

[Chemical 9]

(In the formula, ~! ^ Is independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bur group, or a C to C alkyl group substituted at any position on the ring.

1 10

1 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

1 10 1 10 1 10 represents a phenyl group, a phenyl group, a biphenyl group, a naphthyl group, a chenyl group, a pyrrolyl group, a furyl group or a condensed heteroaryl group, and W ¹ represents NH, O or S. )

The composition for an energy storage device electrode according to claim 1, wherein R ⁵ is represented by formula (9).

[Chemical 10]

(Wherein ^1-4 are each independently any of hydrogen atoms substituted at a position on the ring, a halogen atom, Shiano group, a nitro group, an amino group, an epoxy group, Biel group, C～C alkyl

1 10 group, C-C alkoxy group, phenyl group optionally substituted by Z, substituted by Z , Mayoele, naphthyl group or substituted with Z represents les, mayole, cheryl group,

1 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

1 10 1 10 1 10 represents a phenyl group, a phenyl group, a biphenyl group, a naphthyl group, a chenyl group, a pyrrolyl group, a furyl group or a condensed heteroaryl group, and Q ¹ represents NH, O or S. )

The composition for an energy storage device electrode according to claim 1, wherein R ⁵ is represented by formula (10).

[Chemical 11]

1 10

1 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

The composition for an energy storage device electrode according to claim 1, wherein R ⁶ is represented by formula (11).

[Chemical 12]

1 10 group, C-C alkoxy group, phenyl group optionally substituted by Z, substituted by Z Re, mayore, naphthyl group or substituted with Z represents les, mayole, or cheyl group, and Z is a halogen atom, cyano group, nitro group, amino group, epoxy group, vinyl group, C ~ C

10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c cyanoalkyl

1 10 1 10 c ~

1 10

Represents a ruthenium group, a phenyl group, a biphenyl group, a naphthyl group, a chenyl group, a pyrrolyl group, a furyl group, or a condensed heteroaryl group. )

[13] The composition for an energy storage device electrode according to [1], wherein R ⁶ is represented by the formula (12).

[Chemical 13]

, 45 ^ 46

(Wherein R ^{4a to} R ^w are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bier group, C-C substituted at an arbitrary position on the ring) Archi

1 10

Les, mayoele, naphthyl groups or substituted with z represent les, mayole, cheryl groups,

z is a halogen atom, cyano group, nitro group, amino group, epoxy group, vinyl group, c to c

1 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

1 10 1 10 1 10

R 2, phenyl, biphenyl, naphthyl, chenyl, pyrrolyl, furyl or condensed heteroaryl, W ² represents NH, O or S. )

14. The composition for an energy storage device electrode according to claim 1, wherein R ⁶ is represented by formula (13).

[Chemical 14]

(Wherein R ⁴ ′ to ⁸ each independently represents a hydrogen atom substituted at an arbitrary position on the ring, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bur group, C to C Archi

1 10 Group, C-C alkoxy group, phenyl group optionally substituted with Z, substituted with Z

1 10

1 c 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

1 10 1 10 1 10 represents a phenyl group, a phenyl group, a biphenyl group, a naphthyl group, a chenyl group, a pyrrolyl group, a furyl group, or a condensed heteroaryl group, and Q ² represents NH, O, or S. )

The composition for an energy storage device electrode according to claim 1, wherein R ⁶ is represented by formula (14).

[Chemical 15]

1 10

1 10 alkyl group, c ~

1 c haloalkyl group,

10 c ~

1 c alkoxy group,

10 c ~

1 c Shiano Archi 10

Represents a thio group, a phenyl group, a biphenyl group, a naphthyl group, a chenyl group, a pyrrolyl group, a furyl group, or a condensed heteroaryl group. )

The composition for an energy storage device electrode according to claim 1 or 2, wherein R ¹ and R ² form a ring and represented by formula (15).

[Chemical 16]

(Wherein A ² represents C or N, IT ^{5 to} R ⁵⁷ and R ^{∞ to} R ⁶² , and when A ² is C, R ^{55 to} R ⁶² are Each independently substituted with a hydrogen atom, halogen atom, cyano group, nitro group, amino group, epoxy group, bier group, C-C alkyl group, C-C alkoxy group, or Z.

1 10 1 10

Re, phenyl group, substituted with Z, ret, may ret, naphthyl group or substituted with Z, ret, may represent chelenyl group,

1 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

1 10 1 10 1 10 represents a phenyl group, a phenyl group, a biphenyl group, a naphthyl group, a chenyl group, a pyrrolyl group, a furyl group or a condensed heteroaryl group. However, when A ² is N, R ⁵⁸ and R ⁵⁹ do not exist. The composition for an energy storage device electrode according to claim 1 or 2, wherein the group formed by combining R ¹ and R ² is represented by formula (16).

[Chemical 17]

Ten

Substituted with a til group or z represents a thio group,

z is a halogen atom, cyano group, nitro group, amino group, epoxy group, bur group, c to

1 c 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

The composition for an energy storage device electrode according to claim 1 or 2, represented by a basic formula (17) formed by combining R ³ and R ⁴ together.

[Chemical 18]

(Wherein A ⁴ represents O or S, and R ^{67 to} R ⁷ ° each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, an epoxy group, a bur group, c to c An alkyl group,

10 c ~

1 1 c alkoxy group, phenyl group optionally substituted with z, naphth optionally substituted with Z

Ten

Substituted with a til group or Z represents a thio group,

1 c 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

The composition for an energy storage device electrode according to claim 1 or 2, represented by a basic formula (18) formed by combining R ³ and R ⁴ together.

[Chemical 19]

1 10 1 10

Substituted with R, maye, phenyl, Z, substituted with R, mayo, naphthyl, or substituted with Z, may represent, chain,

1 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

The carbon material is activated carbon, carbon black, or graphite. 2. A composition for an energy storage device electrode according to item 1.

[21] The composition for an energy storage device electrode according to any one of [20] to [19], wherein the carbon material is a fibrous carbon material.

22. The composition for an energy storage device electrode according to claim 21, wherein the fibrous carbon material is carbon felt.

23. The composition for an energy storage device electrode according to claim 21 or 22, wherein the fibrous carbon material has a fiber diameter of 10 to 50 μm.

24. The composition for an energy storage device electrode according to claim 23, wherein the fibrous carbon material has a fiber diameter of 10 to 20 μm.

[25] The composition for an energy storage device electrode according to [1], wherein a polyaminoquinoxaline compound represented by the formula (1) is attached to the surface of the carbon material.

26. The composition for an energy storage device electrode according to claim 2, wherein a polyaminoquinoxaline compound represented by the formula (2) is attached to the surface of the carbon material.

27. The composition for an energy storage device electrode according to claim 21, wherein the fiber surface constituting the fibrous carbon material is coated with a polyaminoquinoxaline compound represented by the formula (1).

28. The composition for an energy storage device electrode according to claim 21, wherein the surface of the fiber constituting the fibrous carbon material is coated with a polyaminoquinoxaline compound represented by the formula (2).

[29] An energy storage device electrode comprising the composition for an energy storage device electrode according to any one of claims 1 to 28.

[30] An energy storage device comprising at least a pair of positive and negative electrodes, a separator interposed between these electrodes, and an electrolyte,

30. An energy storage device, wherein at least one of the positive and negative electrodes is an electrode for an energy storage device according to claim 29.

[31] The energy storage device, wherein the positive and negative electrodes are both electrodes for an energy storage device according to claim 29.

32. The electrolyte is a non-aqueous electrolyte solution containing an electrolyte salt and a non-aqueous organic solvent. The energy storage device according to 0 or 31.

[33] The method for producing a composition for an energy storage device electrode according to [1], wherein the polyaminoquinoxaline compound represented by the formula (1) is applied to a surface of a carbon material.

[34] The method for producing a composition for an energy storage device electrode according to [2], wherein the polyaminoquinoxaline compound represented by the formula (2) is applied to a surface of a carbon material.

[35] The method for producing the composition for an energy storage device electrode according to [1], wherein the aminoquinoxaline compound represented by the formula (19) is electropolymerized on the surface of the carbon material.

[Chemical 20]

~ C alkoxy group, phenyl group optionally substituted with Y, pyridinole group optionally substituted with Y, biphenyl group optionally substituted with γ, and optionally substituted with γ Phthyl group, Cenyl group that may be substituted with Y, Pyrrolylene group that may be substituted with Y, Furyl group that may be substituted with Y, or A condensed heteroaryl group that may be substituted with Y (When R ¹ and R ² are the phenyl group, pyridyl group, biphenyl group, naphthyl group, phenyl group, pyrrolyl group, furyl group or condensed heteroaryl group, these groups are bonded by a single bond. Moyole,.) Or R ¹ and R ² together, _CH CH CH-

, -CH CH0, -OCH CH, -CH OCH, -OCH O, 1 CH CH S, -SCH CH, -CH SCH, -CH CH N (R)-, 1 N (R ) CH CH 1, CH N (R) CH CH CH CH CH CH CH CH 0, OCH CH

CH, CH CH OCH, CH OCH CH, CH OCH 0, OCH C

H〇,-SCH CH S—, -OCH CH S SCH CH O CH CH = CH, -CH = CHCH, OCH = CH, one CH = CH, SCH = CH—, one CH = CHS-, — N (R ') CH = CH—, — CH = CHN (R') —, —〇 CH = N—, — N = CHO, 1 SCH = N, 1 N = CHS, 1 N (R) CH = N, 1 N = CHN (R) 1, 1 N (R) N = CH, 1 CH = N (R) N, 1 CH = CHCH = CH, 1 OCH

2

CH = CH—, -CH = CHCH Yes, _N = CHCH = CH—, -CH = CHCH = N

2

1 10 1 10

Group, pyridyl group optionally substituted with Y, biphenyl group optionally substituted with Y, naphthyl group optionally substituted with Y, chenyl group optionally substituted with Y, substituted with Y A pyrrolyl group which may be substituted, a furyl group which may be substituted with Y, or a condensed heteroaryl group which may be substituted with Y (R ³ and R ⁴ are the phenyl group, pyridinole group, biphenyl group). R ^{3 group} , R ⁴ group, R ⁴ group, R ⁴ group, R ⁴ group, R ⁴ group, R ⁴ group, R ⁴ group, R ⁴ group, R ⁴ group, R ⁴ group, or R ⁴ group. In the beginning, CH CH CH 1, -CH CH 01, OCH CH 1, CH OCH

2 2 2 2 2 2 2 2 2 1, -OCH 0, -CH CH S-, -SCH CH 1, -CH SCH 1, 1 CH CH

2 2 2 2 2 2 2 2 2

N (R) —, —N (R) CH CH, _CHN (R) CH—, —CH CH CH CH, _C

2 2 2 2 2 2 2 2

H CH CH〇一、 -OCH CH CH 一、 -CH CH OCH 一、 -CH OCH CH-

2 2 2 2 2 2 2 2 2 2 2 2

, -CH OCH O—, -OCH CH〇1, -SCH CH S, one OCH CH S, one S

2 2 2 2 2 2 2 2

CH CH O—, -CH CH = CH—, -CH = CHCH one, ten CH = CH—, -CH

2 2 2 2

= CHO_, _SCH = CH-, _CH = CHS-, _N (R ') CH = CH-, _CH = C HN (R')-, one OCH = N-, _N = CHO, one SCH = N-, _N = CHS, one N (R ') CH = N-N = CHN (R')-N (R ') N = CH-CH = N (R') N-CH = CHCH = CH— -OCH CH = CH CH = CHCH O— N = CHC

twenty two

H = CH— CH = CHCH = N— N = CHCH = N— N = CHN = CH or one CH = NCH = N— may be formed, at which time the hydrogen bonded to the carbon atom of these groups Atom may be substituted with Y R 'is hydrogen atom, CC alkyl group,

1 10

c c haloalkyl group, C C cyanoalkyl group, phenyl optionally substituted with Z

1 10 1 10

X ² represents _NH_R ⁷³ _NH or one NH—R ⁷⁴ ,

2

R ⁷³ is a C to C alkylene group, substituted with one C (O) CH—, one CH C (O) —, Y

1 10 2 2

Divalent benzene ring, optionally substituted with Y, divalent pyridine ring, optionally substituted with Y, divalent biphenyl group, optionally substituted with Y 2 Divalent naphthalene ring, may be substituted with Y, may be divalent thiophene ring, may be substituted with Y, may be divalent pyrrole ring, may be substituted with Y, may be, 2 Substituted with a valent furan ring or Y, represents a ring, a ring, a condensed heterocyclic ring,

R ⁷⁴ represents a C to C alkyl group, a acetyl group, a phenyl group optionally substituted with Y, Y

1 10

Pyridyl group optionally substituted with Y, biphenyl group optionally substituted with Y, naphthyl group optionally substituted with Y, chenyl group optionally substituted with Y, substituted with Y Represents a substituted heteroaryl group which may be substituted with R, maye, pyrrolyl, Y substituted with R, maye, furyl or Y;

γ is a halogen atom, cyan group, nitro group, amino group, epoxy group, bur group, C to C

1 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

1 10 1 10 1 10 group, phenyl group optionally substituted with Z, pyridyl group optionally substituted with Z, biphenyl group optionally substituted with Z, substituted with Z A naphthyl group which may be substituted with Z, a pyrrolyl group which may be substituted with Z, a pyrrolyl group which may be substituted with Z, a thiol, a furyl group or a thiol substituted with Z It may represent a condensed heteroaryl group. However, when Y is 2 or more, they may be the same or different from each other. ),

Ζ is a halogen atom, cyano group, nitro group, amino group, epoxy group, vinyl group, C ~ C

1 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

1 10 1 10 1 10 represents a phenyl group, a phenyl group, a biphenyl group, a naphthyl group, a chenyl group, a pyrrolyl group, a furyl group or a condensed heteroaryl group. (However, if Z is 2 or more, they may be the same or different.)

3. The method for producing an energy storage device electrode composition according to claim 2, wherein the aminoquinoxaline compound represented by the formula (20) is electropolymerized on the surface of the carbon material.

[Chemical 21]

1 10

2 2 2

, -CH CH 0, -OCH CH 1, -CH OCH 1, 1 OCH 0, 1 CH CH S

2 2 2 2 2 2 2 2 2 One,-SCH CH one, -CH SCH one, one CH CH N (R) —, one N (R) CH CH one,

2 2 2 2 2 2 2 2

-CH N (R) CH 1, -CH CH CH CH 1, CH 1 CH CH CH 1, OCH CH

2 2 2 2 2 2 2 2 2 2 2

CH, CH CH OCH, CH OCH CH, CH OCH 0, OCH C

2 2 2 2 2 2 2 2 2 2

H〇1, -SCH CH S—, -OCH CH S, one SCH CH O, one CH CH = CH

2 2 2 2 2 2 2 2 1, -CH = CHCH, 1 OCH = CH, 1 CH = CH 0, 1 SCH = CH-, 1

2

CH = CHS, 1 N (R) CH = CH, 1 CH = CHN (R) —, 10 CH = N, 1 N = CHO-SCH = N-N = CHS-N (R ') CH = N-N = CHN (R') N (R) N = CH CH = N (R) N CH = CHCH = CH OCH

2

CH = CH—, -CH = CHCH Yes, N = CHCH = CH CH = CHCH = N

2

R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a cyan group, a nitro group, an amino group, a CC alkyl group, a CC alkoxy group, or a phenyl group optionally substituted with Y.

1 10 1 10

Group, pyridyl group optionally substituted with Y, biphenyl group optionally substituted with Y, naphthyl group optionally substituted with Y, chenyl group optionally substituted with Y, substituted with Y A pyrrolyl group which may be substituted, a furyl group which may be substituted with Y, or a condensed heteroaryl group which may be substituted with Y (R ³ and R ⁴ are the phenyl group, pyridinole group, biphenyl group). group, a naphthyl group, a thienyl group, a pyrrolyl group, when Teroari Le group into a furyl group or a condensed, these groups may be bonded by a single bond.) represents, or R ³ and R ⁴ are cord CH CH CH -CH CH 0, OCH CH CH OCH

2 2 2 2 2 2 2 2 2 -OCH 0, -CH CH S-, -SCH CH CH SCH CH CH

2 2 2 2 2 2 2 2 2

N (R) -N (R) CH CH, _CHN (R) CH—, -CH CH CH CH, _C

2 2 2 2 2 2 2 2

H CH CH〇一、 -OCH CH CH 一、 -CH CH OCH 一、 -CH OCH CH-

2 2 2 2 2 2 2 2 2 2 2 2

, -CH OCH O—, -OCH CH〇1, -SCH CH S, one OCH CH S, one S

2 2 2 2 2 2 2 2

CH CH O—, -CH CH = CH—, -CH = CHCH one, ten CH = CH—, -CH

2 2 2 2

= CHO_, _SCH = CH―, _CH = CHS―, _N (R ') CH = CH―, _CH = C HN (R')-, one OCH = N-, _N = CHO-, one SCH = N-, _N = CHS-, 1 N (R ') CH = N―, _N = CHN (R') ―, _N (R ') N = CH―, _CH = N (R') N―,- CH = CHCH = CH OCH CH = CH CH = CHCH ON = CHC

twenty two

H = CH CH = CHCH = NN = CHCH = NN = CHN = CH or CH = NCH = N— may be formed. At this time, the hydrogen atom bonded to the carbon atom of these groups is replaced with Y. R 'can be a hydrogen atom, a CC alkyl group,

1 10

1 10 1 10

1 10 alkyl group, c-c haloalkyl group, c-c alkoxy group, c-c cyanoalkyl

1 10 1 10 1 10 group, phenyl group, biphenyl group, naphthyl group, chenyl group, pyrrolyl group, furyl group or condensed heteroaryl group (however, if Z is 2 or more, they are the same or Can be different))]