JPH01311161A - High polymer composition - Google Patents

Abstract

PURPOSE:To obtain a composition, excellent in processability and capable of exhibiting extremely good electric conductivity characteristics by doping an electron acceptor by blending a specific copolymer with a compound selected from polypyrrole-based and polythiophene-based compounds. CONSTITUTION:A composition obtained by mixing a copolymer expressed by formula I (R<1> is H or 1-20C hydrocarbon; R<2> is H, furyl group, pyridyl group, etc.; n and x are integers of >=2) with a compound selected from polypyrrole- based compounds expressed by formula II (R<3>, R<4> and R<5> are H or 1-20C hydrocarbon residue; p is an integer of >=2), polythiophene-based compounds expressed by formula III (R<6> and R<7> are H or 1-10C hydrocarbon residue; q is an integer of >=2) and polyaniline-based compounds expressed by formula IV (R<8>, R<9>, R<10> and R<11> are H or 1-10C hydrocarbon residue; r is an integer of >=2).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel polymer composition. More particularly, the present invention relates to a novel polymer composition that is particularly easy to process and exhibits excellent conductive properties when doped with an electron acceptor.

<Prior Art and Problems to be Solved by the Invention> Polyacetylene, polyparaphenylene, polythiophene, polypyrrole, and the like are known as polymers used to form conductive polymers. These polymers can be used as conductive polymers by doping them with certain compounds, but they have the drawbacks of deterioration in air and changes in electrical properties. In addition, these conductive polymers have poor meltability and solubility, and therefore have problems such as extremely difficult processability, which is a major obstacle in practical use.

For example, as an application field for conductive polymers, it has been proposed to apply them to electrodes for secondary batteries that take full advantage of the reversible redox properties of conductive polymers, but in most cases, the electrolyte solution of secondary batteries is Among them, they are physically or chemically unstable, and therefore stable repeatability of photodischarge (cyclability), which is the basic performance required of secondary batteries, cannot be expected. In addition, the polymer skeleton of the electrolytic polymer is composed of a rigid π-electron conjugated system, so it is insoluble and infusible, which is a major obstacle to its practical application. As a method for solving these problems, US Pat. No. 4,452,725 describes
An electroactive polymer obtained by doping a polymer having a carbazolediyl structure as a repeating unit with an electron acceptor has been proposed.

However, the above-mentioned carbazole-based polymers are oligomers with a low degree of polymerization, and lack the mechanical strength and moldability that a polymer compound should have. If so, please charge it repeatedly.
The til bath components are released and the cyclability is improved.
The problem is that it cannot be expected. In addition, in order to provide the above carbazole polymer with good electrochemical properties as well as mechanical strength and moldability, it is necessary to obtain a polymer with a higher degree of polymerization (high polymer). It is difficult to obtain high molecular weight polymers by methods such as Grignard coupling, oxidative coupling, Friedel-Krach reaction, and electrolytic oxidative polymerization, which are commonly used as synthesis methods for polyaromatic compounds and polyheteroaromatics. Even if the reaction conditions are made more severe, dissimilar bonds and cross-linking reactions will be induced, making it impossible to increase the molecular weight.In addition, the processability, which is one of the advantages of polymer compounds, will be lost, resulting in insoluble and infusible properties, and furthermore, electrical The problem is that the polymer becomes inert.

A polymer having C13,6-N-methylcarbazolylmethylene structure as a repeating unit is soluble in an organic solvent, and by doping this polymer with an electron acceptor, a DC conductivity of 101 to 10-1S can be achieved. It has been reported that the conductivity is on the order of /cm (5ynthetic M
etals, 10, p. 281-292 (1985)
).

However, the above-mentioned carbazolyl methylene polymers do not have reversible doping, that is, reversible redox reactions, because doping causes the elimination of methylene hydrogen in the polymer main chain. There were drawbacks.

In order to overcome all the drawbacks of these conventional techniques, the present inventors have already developed a VC[i, Moreover, by doping with an electron-accepting compound, the electroactivity is improved and the redox reaction can be performed with good repeatability, and the general formula (1 ) (where l<I is B or carbon number 1-20
a hydrocarbon residue, R2 is H or a hydrocarbon residue having 1 to 20 carbon atoms, or a nolyl group, a pyridyl group, or a methoxyphenyl group, and 9 and 2 are integers of 2 or more). A patent application has already been filed (%Application No. 153427/1982).

However, the above-mentioned copolymers have problems such as not being able to obtain sufficient conductivity for use as various electronic functional materials even if the copolymers are fully doped with an electron-accepting compound. In particular, when the above-mentioned copolymer is applied to battery electrodes, 1) due to low conductivity, the resistance of the electrode itself is large (large current cannot be taken (charging/discharging current is small));

2) Internal resistance becomes large and voltage flatness becomes poor.

3) The charge/discharge capacity is small (I think about the efficiency of use of the active material).

There were problems such as.

A widely known method for improving the conductivity of battery electrodes is to mix carbon black or graphite into the electrodes, but in order to obtain high conductivity, this method requires mixing a large amount of carbon black, etc. As a result, the amount of electrode active material is reduced, creating a new problem that significantly reduces battery capacity.

<Means for Solving the Problems> As a result of further intensive research in order to improve all of these drawbacks, the present inventors have found that the soft copolymer (1) above contains a polypyrrole compound and a polythiophene compound. From VC, using a polymer composition consisting of a mixture of at least one glaze compound selected from polyaniline compounds,
The inventors have discovered that the drawbacks of conventional contact can be solved and have arrived at the present invention.

That is, the present invention is based on the general formula (1) (wherein R' is a hydrogen atom or a hydrocarbon residue having 1 to 2 carbon atoms, R2 is hydrogen or a hydrocarbon residue having 1 to 20 carbon atoms, or a furyl group, It represents a pyridyl group, a nitrophenyl group, a chlorophenyl group, a methoxyphenyl group, and 9 and 2 represent an integer of 2 or more. Into one union,
-Softball (II)! (a (wherein R3, R4 and RS each represent a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, and p represents an integer of 2 or more), - Soft formula (It) (In the formula, R6 and R7 each represent a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, and q represents an integer of 2 or more.)
A polythiophene compound represented by, and -soft formula (IV') (wherein R'', R'', 7?10 and 7?11 are each a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, and r is 2 The present invention relates to a polymer composition obtained by mixing a compound selected from polyaniline compounds represented by the above integer.

The present invention also relates to an electrocardiographic polymer composition obtained by doping the above polymer composition with an electron acceptor.

The present invention will be explained in detail below.

(1) - Copolymer represented by the general formula (11) The copolymer represented by the general formula (1) of the present invention is a polymer having a 3,6-carbazolediyl structure as a repeating unit represented by the -soft formula (V). It can be obtained by polycondensing the polymer and an aldehyde represented by -soft formula (Vl) or a polymer thereof in the presence of an acid or alkali catalyst.

A polymer having a 3,6-carbazolediyl structure represented by Rt CHO(Vl) -soft formula (V) as a repeating unit is synthesized by a known method. For example, methods for synthesizing carbazole dipolymers using various oxidizing agent/solvent systems reported in Journal of Organic Synthetic Chemistry, No. 23 @ No. 5, p. 447 (1965), P.
, Haday 8-ford at al, /, Ch
am, Soe, Perki%, 1. p276(1
974), the oxidative coupling method or Grignard coupling method used in %Kokai No. 1161-141725 or JP-A No. 56-88422. There are other methods. General formula (V) represents hydrogen or a hydrocarbon residue having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, and examples of the hydrocarbon residue include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. , butyl group, i
Examples include alkyl groups or allyl groups such as -butyl group and 3-hexyl group, aryl groups such as phenyl group, tolyl group and ethylphenyl group, aralkyl group and seven b conductors. n is 2 or more, usually 2 to 50, preferably 2 to 30.

As the aldehyde represented by the general formula (Vl), R2 in the formula is hydrogen, a hydrocarbon residue having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, or a furyl group, a pyridyl group, a nitrophenyl group, a chlorophenyl group, a methoxy A phenyl group compound is used, and the hydrocarbon residue is an alkyl group such as a methyl group, ethyl group, n-propyl group, i-propyl group, 3-butyl group, i-butyl group, or -hexyl group, or An allyl group, various aryl groups such as a phenyl group, tolyl group, and ethylphenyl group, an aralkyl group, and derivatives thereof can be used. Representative examples of these aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, acrylaldehyde, cinnamaldehyde, anisaldehyde, nicotinaldehyde,
Examples include nitrobenzaldehyde, chlorobenzaldehyde, and furfural.

In addition, aldehyde polymers are produced by self-condensing aldehydes represented by the general formula (Vl) in a concentrated solution at °C,
Represents a polymer obtained by condensation in the presence of an acid catalyst,
Polymer) 1 represents a polymer that is easily hydrolyzed to produce an aldehyde monomer under the reaction conditions used to synthesize the copolymer of the present invention. Typical examples include paraformaldehyde, which is a polymer of formaldehyde, and paraaldehyde, which is a trimer of acetaldehyde.

Polycondensation of a carbazole polymer and an aldehyde can be carried out in an organic solvent in which both are soluble at a temperature of θ°C to 200°C using an acid or alkali catalyst. Examples of acid catalysts include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, perchloric acid, formic acid,
Examples include organic acid gold such as acetic acid, propionic acid, methanesulfonic acid, and p-toluenesulfonic acid. Examples of preferable organic solvents include ethers such as ethyl ether, tetrahydrofuran, and dioxane; nitric acid hydrocarbons such as chloroform, dichloromethane, and chlorobenzene; nitro compounds such as nitrobenzene; acetonitrile, propylene carbonate, dimethylformamide, and -Methylpyrrolidone and the like. The reaction time is 1 minute to 500 hours, preferably 5 minutes to 200 hours.
You can choose as appropriate within the time range.

Through the above reaction, a substantially linear copolymer of the present invention having a high degree of polymerization is obtained. The copolymer of the present invention is soluble in solvents such as N-methylpyrrolidone, nitrobenzene, chloroform, and sulfuric acid, but is insoluble in alcohols, aliphatic hydrocarbons, and acetonitrile and propylene carbonate used in organic electrolyte batteries. It is a thermoplastic resin that can be melted by heating.

As mentioned above, the polymer composition of the present invention includes a polypyrrole compound, a polythionene compound, or
) and polyaniline compounds (hereinafter referred to as blended compounds). These coordination compounds may be used alone or in combination of two or more.

(2) Compound compound The pyrrole compound in the present invention is a compound represented by general formula (II), and two or more of these compounds may be used in combination. In the general formula (n), Hs, B4 and R'' each represent a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and examples of the hydrocarbon residue include a methyl group, an ethyl group, a 9-carbon Alkyl groups such as probyl group, e-propyl group, duck-butyl group, 1-butyl group, 1-c-butyl group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, exo-butoxy group, etc. Alkoxy group, phenyl group, tolyl group, aryl group such as naphthyl group, phenoxy group, methylphenoxy group,
Examples include allyloxy groups such as naphthoxy groups, thioether groups such as methylthioether groups and ethylthioether groups, and derivatives thereof.

p is 2 or more, but usually 2 to 10,000. Both ends of the molecule are usually nuclear substituted hydrogens.

Specific examples of these include polypyrrole, poly(N-methylpyrrole), poly(N-ethylpyrrole), poly(
N-s-7'robilvirole), BoIJ (3-methylpyrrole), poly(3-ethylpyrrole), poly(3-methyl-N-methylpyrrole), poly(3-ethyl-N-
methylpyrrole), poly(3-methoxypyrrole), poly(3-ethoxypyrrole), poly(3-methoxy-N
-methylpyrrole), poly(3-ethoxy-N-ethylpyrrole), poly! J(3-phenylhyrol), 1(3
-phenyl-N-methylpyrrole), poly(3-phenoxypyrrole), BoIJ (3-4 phthoxypyrrole),
Examples include poly(3-methylthiopyrrole), poly(3-ethylthiopyrrole), poly(3,4-dimethylpyrrole), poly(3,4-diethyl-N-methylpyrrole), and the like.

The polythiophenyl compound in the present invention has the general formula (
Ill), and two or more of these compounds may be used in combination. In general formula (III),
R6 and Bq are each a hydrogen atom or a carbon number of 1 to 2
0, preferably 1 to 1O, and examples of the hydrocarbon residue include methyl group, ethyl M, n-10 pyl group, i-7'' lobil group, s-butyl group, i-butyl group, 1
Alkyl groups such as -c-butyl group, methoxy group, ethoxy group, -propoxy group, (-propoxy group, alkoxy group such as 3-butoxy group, phenyl group, tolyl group,
Examples thereof include an atomyl group such as a naphthyl group, an allyloxy group such as a phenoxy group, a methylphenoxy group, a naphthoxy group, and derivatives thereof.

q is 2 or more, but ranges from 2 to 10,000. Both ends of the molecule are usually nuclear substituted hydrogens.

Specific examples of these include polythiophene, poly(3-
methylthiophene), poly(3-ethylthiophene),
Poly(3-s-propylthiophene), poly(3-4-
propylthiophene), poly(3-s-butylthiophene), poly(3-1-butylthiophene), poly(3-
g*a butylthiophene), poly(3-methoxythiophene), poly(3-ethoxythiene), poly(3-
%-propoxythiophene), poly(3-4-propoxythiophene), poly(3-%-butoxythiophene)
, poly(3-phenylthiophene)% poly(3-)ruylthiophene), poly(3-naphthylthiophene), poly(3-phenoxythiophene), BoIJ(3-methylphenoxythiophene), poly(3-naphthoxythiophene) ), poly(3,4-dimethylthiophene), poly(
3,4-diethylthiophene) and the like.

In addition, as a polyaniline compound, -soft type (IV)
It is a compound that is encapsulated by a combination of two or more of these compounds. -Soft (IV) K: Mite, R6,
R9, R” and Rlm are hydrogen atoms or have 1 to 2 carbon atoms
0, preferably 1 to 10 hydrocarbon residues, and examples of the hydrocarbon residues include methyl group, ethyl group, n-propyl group,
i-propyl group, 5-butyl group, i-butyl group, 8$6
- Alkyl groups such as butyl groups, alkoxy groups such as methoxy groups, ethoxy groups, propoxy groups, i-propoxy groups, and bean-butoxy groups, aryl groups such as phenyl groups, tolyl groups, naphthyl groups, phenoxy groups, methyl Examples include allyloxy groups such as phenoxy groups and naphthoxy groups, and derivatives thereof.

De is 2 or more, but usually 2 to 10,000. Both ends of the molecule are usually nuclear hydrogen atoms.

Specifically, polyaniline, poly(3-methylaniline), poly(3,5-dimethylaniline), poly(3-ethylanili/), poly(3-n-propylaniline),
Poly(3-methoxyaniline), poly(3,5-dimethoxyaniline), poly(3-ethylaniline), poly(
3,5-jethoxyaniline), poly(3-2enylaniline), poly(3,5-diphenylaniline), poly(3-naphthylaniline), poly(3-tolylaniline), poly(2゜5- dimethylaniline), poly(3-
phenoxyaniline), poly(3-naphthoxyaniline), poly(N-methylaniline), poly(N-ethylaniline), poly(3-methyl-A-methylaniline),
Poly(3,5-dimethyl-N-ditylaniline), poly(3-ethyl-N-methylaniline), poly(3-methoxy-N-methylaniline), poly(3,5-methoxy-y-methylaniline) Examples include octopoly(3-phenoxy-N-methylaniline).

(3) Mixing of copolymer and blended compound The molecular composition of the present invention can be obtained by uniformly dispersing and mixing the blended compound in the copolymer represented by the general formula (1). At that time, the compounded compound may be completely mixed alone in the copolymer represented by the soft formula (1), or two or more compounded compounds may be used in combination, or ordinary conductive additives such as carbon black and graphite may be added. Even if mixed ('J etc.) there is no problem.

- The mixing ratio of the copolymer represented by the soft formula (1) and the blended compound is - 1 to 400 parts by weight of the blended compound to 100 parts by weight of the copolymer represented by the soft formula (I), and the preferred trench position is 5 parts by weight.
~100 parts by weight.

The mixing method is not particularly limited, and known methods can be used. For example, by utilizing the feature that the co-1 polymer represented by the -soft formula (1) is soluble in solvents such as N-methylpyrrolidone, nitrobenzene, chloroform, and sulfuric acid, first, the co-1 polymer is dissolved in a sulfur medium. There is a method of obtaining a polymer composition by adding the compounded compound, dispersing it uniformly, mixing the two, and then drying it. Thereafter, the compounded compound is added, uniformly dispersed and mixed, and then cooled to obtain a polymer composition, or - the copolymer represented by the soft formula (1) and the compounded compound are directly mixed in a completely solid phase by pole milling etc. Examples include methods.

Of course, in addition to the above-mentioned mixing method, for example, in the presence of the copolymer represented by the soft formula (1), the compounded compound may be mixed in the form of a polymer (such as a virol compound, a thiophene compound, or an aniline compound). In addition to monomers, solid phase, liquid phase, gas phase, preferably one strong acid residue, halogen, metal salt having cyanide, peroxide or nitrogen in the dissolved liquid phase of the co-i9 combination represented by general formula (1). There is no problem in producing a commercial molecular composition by polymerizing in the presence of a compound.

(4) Doping The polymer composition of the present invention exhibits high electroactivity by doping with an electron acceptor as a dopant, and can of course perform redox reactions with good repeatability.
Because it has high conductivity, it can be used in various electronic devices, for example, when used as an electrode material for secondary batteries, it can be charged and discharged reversibly.
In particular, even if the number of repetitions (cycles) of charging and discharging is significantly increased, extremely stable characteristics can be obtained without causing deterioration in cyclability due to bath breakage as seen in the case of carbazole polymers. Not only can you do this, but you can also
A large charging/discharging current can be obtained, good '1E pressure flatness during charging and discharging, and since the compounded compound plays a role as a conductive aid and itself performs a reversible redox reaction, the amount of per electrode active material is low. It exhibits excellent effects such as not reducing the total capacity.

Electron-accepting dopants include iodine, bromine, halogen compounds such as hydrogen iodide, arsenic pentafluoride, phosphorus pentachloride, phosphorus pentafluoride, antimono pentafluoride, silicon tetrafluoride, aluminum chloride, and aluminum bromide. , aluminum fluoride, metal chlorides such as ferric chloride, protic acids such as sulfuric acid, nitric acid, chlorosulfonic acid, oxidizing agents such as sulfur trioxide, difluorosulfonyl peroxide, tetracyanoquinodimethane. Examples include organic substances such as.

In addition, dopants that can be electrochemically doped include:
PF, -, SbF6. /% of elements of VakA, such as AmF, -, ma such as BF, -
I-(1,-), a halogenide anion of an element of the genus
B-day, norogen anions such as Ct-, ClO2
Examples include anions such as perchlorate anions such as -.

These dopings are performed by known methods. Typically, when the electron-accepting dopant is a gas or has a vapor pressure, a vapor phase doping method in which the polymer composition is exposed to the vapor atmosphere, and a vapor-phase doping method in which the electron-accepting dopant is placed in an inert solvent. A wet doping method involves immersing a polymer composition in a dissolved solution, or a dry doping method in which an electron-accepting compound is dissolved in an inert solvent and the polymer composition is dissolved in an FC bath liquid. By forming a film,
Examples include a method in which the polymer composition is doped at the same time as it is formed into a film or coating, and a method in which the polymer composition is immersed in a solution containing a dopant and then electrochemically doped by applying an electric field.

Doping in the present invention may be carried out on the polymer composition finally obtained, or may be carried out separately before mixing the compound represented by -dry formula (1) and the blended compound.

Furthermore, when the polymer composition of the present invention is fully doped with anions, the nitrogen atoms in the copolymer represented by the general formula (1), which is one component constituting the composition, are positively charged and stable. Because of its properties, it is stable against repeated oxidation-reduction processes, has high conductivity, and also has excellent processability as mentioned above. Used to construct sexual electrodes.

That is, after dissolving the copolymer represented by the general formula (I) of the present invention in a solvent and adding the compounded compound, it is molded, or
IcIL& can be formed by heating and melting the polymer composition of the present invention, or by pressure molding the polymer composition as a main component, or by molding it into an arbitrary shape using a binder. can.

Examples of the binder include polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, polyethylene, etc., but are not necessarily limited to these.

Further, since the polymer composition of the present invention has a carbazole unit that is promising as a photoconductive material, it can also be used as a photoconductive material.

<Effects of the Invention> Since the polymer composition of the present invention contains a linear copolymer as an essential component, it has excellent processability and can be easily formed into various molded products. Furthermore, by doping the polymer composition of the present invention with a t-electron acceptor, it is possible to exhibit extremely high conductivity, and moreover, the doping is reversible and it has extremely high cyclability. , is extremely excellent as a conductive polymer.

<Examples> Hereinafter, the present invention will be specifically explained using all Examples, but the present invention is not limited thereto.

Example (Synthesis of N-ethylcarbazole dimer) N-ethylcarbazole 8. (1,70% perchloric acid aqueous solution 307! and glacial acetic acid 307 were added to make a homogeneous solution, and 2°3-dichloro-5,6-dicyano-p-benzoquinone 9 was dissolved in 200 tIltK bath of glacial acetic acid while stirring at room temperature. .Of was added dropwise over 1 hour.
After stirring for a minute, the reaction precipitate was filtered and washed with diethyl ether.

The obtained black powder was dissolved in 600% acetone and reduced by dropping a saturated aqueous sodium hydrogen sulfide solution under stirring, and the precipitate was filtered and dried to obtain yellow crude N-ethylcarbazole dimer 7. :lFi obtained. This was further dissolved in chloroform and passed through an alumina column to obtain 6.8v of a pale yellow-white purified N-ethylcarpazole dimer.

As a result of infrared absorption spectroscopy and IR-NMR analysis, the obtained N-ethylcarbazole monomer was 9.9'- having a structure connected at the 3-position of N-ethylcarbazole.
It was found to be diethyl-3,3'-bacarbazolyl.

(Polycondensation of N-ethylcarbazole dimer and formaldehyde) 0.3'li of the above N-ethylcarbazole dimer was placed in a 50-3-L flask and dissolved in 15-1,4-dioxane. A few drops of concentrated sulfuric acid vinegar was added thereto, 82 liters of a 37% formaldehyde solution was added dropwise, and the mixture was heated and stirred at 85° C. for 3 hours to react. After the reaction, the reaction precipitate was filtered, washed with ζ methanol, and dried to obtain 0.36 f of a blue-green polymer.
'i got it. The obtained copolymer was soluble in N-methylpyrrolidone and nitrobenzene, and insoluble in acetonitrile, propylene carbonate, and aliphatic hydrocarbons.

(Synthesis of pyrrole polymer) 300-Mitsuro 7 Lasco with anhydrous FaC1,50,O? After adding 100 g of ethanol to dissolve the mixture, the mixture was cooled to 0°C. Add all pyrrole 2- to this and O
The reaction was allowed to proceed for 1 hour while stirring at 'C. After the reaction, a black-blue precipitate was allowed to stand for a whole day, washed with ethanol and ion-exchanged water, and then dried to obtain a pyrrole polymer in the form of fine particles of 1.52. This pyrrole polymer was press-molded into a disk shape using a tablet molding machine, and its electrical conductivity was measured using a four-probe method and found to be 54 S/cIIL at room temperature.

(Preparation of molecular composition by mixing copolymer and pyrrole polymer) Copolymer obtained by polycondensation of N-ethylcarbazole dimer and formaldehyde 0.50r'1lOtl
After dissolving Lt in chloroform, pyrrole polymer 0.
2 (l) was added and stirred to prepare a co-1 polymer solution in which pyrrole-1 polymer was uniformly dispersed. By casting the co-1 polymer bath solution containing this pyrrole polymer on a Teflon plate and drying it, A uniform film with a thickness of 20 μm was obtained.

The obtained film had fair conductivity and a conductivity of 0.5 S/cTni as measured by the four-probe method.

In addition, this film was used as a positive electrode, a platinum sheet was used as a counter electrode, and A g /A g A' 0 was used as a reference electrode, and 0.7
A charge/discharge test was conducted on a half cell using an acetonitrile solution of M-E t and NPFt as a laminated solution. When we investigated the charge/discharge cycle characteristics at a charge amount of 100 C/l and a charge/discharge current of 5 tmA/cIIL, the coulombic efficiency was 95.
% or more, stable cyclability of 100 times or more was obtained.

Figure 1 shows the discharge curve. In the figure, the horizontal axis shows radiation 'R1, charge amount, and the vertical axis shows A, /AgN0. The discharge is shown in its entirety based on . It has been found that gold exhibits extremely good potential stability even at high current densities of 5mA 7cm''.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing an example of the discharge curve of the present invention's polymer composition.

Claims (1)

[Claims] 1. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R^1 is a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, R^ 2 represents a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, or a furyl group, a pyridyl group, a nitrophenyl group, a chlorophenyl group, or a methoxyphenyl group;
(n and x are integers of 2 or more) are general formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R^3, R^4 and R ^5 is a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, respectively, and p is an integer of 2 or more) General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼( III) A polythiophene compound represented by (wherein R^6 and R^7 are each a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, and q is an integer of 2 or more), and IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, R^8, R^9, R^1^0 and R^1^1
is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, and r is an integer of 2 or more. 2. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 is a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, and R^2 is hydrogen or a carbon number 1 to 20 hydrocarbon residues or a furyl group, a pyridyl group, a nitrophenyl group, a chlorophenyl group, or a methoxyphenyl group, n and x are integers of 2 or more. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^3, R^4 and R^5 are each a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, and p is 2 or more. General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R^6 and R^7 are each a hydrogen atom or a carbon number of 1 to 10) (wherein R^8, R^9, R^1^0 and R^1^1
is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, and r is an integer of 2 or more. A conductive polymer composition obtained by