JPH02638A - Polyaniline - Google Patents

Abstract

PURPOSE:To obtain an electronic material having excellent corrosion resistance, high conductivity, etc., and suitable for a battery electrode, etc., by controlling the amount of the portion in a state of a benzoimide-ammonium salt in a polyaniline and the amount of the portion in a state of a quinoid-diimine. CONSTITUTION:The amount of the portion of formula I (benzoimide-ammonium salt state) in a polyaniline and the amount of the portion of formula II (quinoid- diimine state) are controlled so that they may be 7mol% or below and 25mol% or below, respectively. For instance, this control is performed by oxidatively coupling aniline in, for example, an acidic atmosphere, immersing the obtained polymer in an aqueous acid solution of, e.g., hydrazine hydrochloride and treating it with hydrazine. In addition to the above states, a polyaniline has a state of formula III (dope-semiquinone radical state), etc., and the composition of these states can be determined by X-ray photoelectron spectroscopy, an electrochemical process or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION Industrial Problems The present invention relates to polyaniline, which is suitably used as an electrode material, a conductive material, a material for nine-circuit elements, and the like.

In recent years, polyaniline has attracted attention as an organic conductive material, and its application to various fields such as batteries, sensors, and electromic displays has been proposed.

Polyaniline is usually obtained by oxidative polymerization of aniline, but when it is used as an electronic material, polyaniline is preferably thinned and polymerized by electrolysis or catalyst using an acidic aqueous solution of aniline. In this case, methods for oxidative polymerization of aniline include electrolytic oxidation of aniline from an acidic aqueous solution of hydrochloric acid, hydrofluoroboric acid, sulfuric acid, perchloric acid, etc. to obtain polyaniline; A method of obtaining polyaniline using an oxidizing agent such as potassium diiron dichromate or potassium permanganate is known.

However, when applying polyaniline to electronic materials, high conductivity is particularly important, and polyaniline produced by the above method has higher conductivity than polyaniline polymerized in a neutral or alkaline solution. However, it is also true that they have lower conductivity than inorganic materials such as metals, and further improvement in conductivity is desired.

Furthermore, when applying polyaniline to electronic materials, it is important not to cause chemical changes such as corrosion to other materials, but polyaniline produced by the above method contains the acid used in the polymerization process. Causes corrosion when used with other metal materials. Therefore, it has been proposed to neutralize such polyaniline by treating it with an alkali such as ammonia or sodium hydroxide, but this method has the drawback of causing a decrease in electrical conductivity.

Furthermore, when applying polyaniline to electronic materials,
There is a need to further improve the properties of electronic materials such as durability, and in particular, when used as battery electrode materials, further improvements in durability and discharge capacity are desired.

The present invention has been made in view of the above circumstances, and has high corrosion resistance and high conductivity as an electronic material, and particularly when used as a battery electrode material, has improved self-discharge, service life, and discharge capacity, and can be used as a sensor or The purpose is to provide polyaniline that has a long life when applied to circuit elements.

In order to achieve the above object, the present inventors have determined that the proportion of the benzonoid in the ammonium salt state is 7 mol % or less, and the portion is in the quinoid = diimine state. It has been found that polyaniline having a content of 25 mole % or less is effective.

That is, according to the research of the present inventors, polyaniline has the following formulas (A) to (D) (formulas (B) and (C) are examples in which the negative ion species is BF4), as shown in Benzonoid = amine state (Formula A).

Benzonoid ammonium salt state (formula B), dope =
It consists of a mixed state of a semiquinone radical state (Formula C) and a quinoid=diimine state (Formula D). In this case, the conventional theory is that polyaniline exhibits battery behavior between the benzonoid=amine state (formula A) or the benzonoid niummonium salt state (2B) and the quinoid=diimine state (formula D) ( For example, A, G, Mac Di
armid et al.: 5ynthetic
Metals, 13.

291-297 (1986)), but according to the research of the present inventors, charging and discharging is possible in the benzonoid = amine state (formula A) or the benzonoid niummonium salt state (2 B) and the dope = It was found that the battery behavior was shown between the semiquinone radical state (Formula C) and that the discharge capacity was higher when the quinoid=diimine state (Formula D) was less.

Furthermore, regarding the conductive mechanism, it was found that the semiquinone radical cation of 2C is responsible for the conductivity of polyaniline, rather than doping with bond alternation as in the formula.

In other words, in polyaniline, the lone pair of electrons on the N atom plays an essentially important role in electrical conductivity, and when polyaniline undergoes valorization, it becomes an unpaired electron and delocalizes with the π-electron system of the phenyl group. This is essentially important for the conductive mechanism of polyaniline, and in order to obtain polyaniline with high conductivity, the doped state of polyaniline should not be generated in the quinoid = diimine state, but should be controlled to the doped = semiquinone radical state. It turns out that this is preferable.

Furthermore, in the conventional theory, the benzonoid=amine state (formula A
) and benzonoid niummonium salt state (2B), polyaniline in the benzonoid niummonium salt state has higher conductivity and is said to be suitable as a battery electrode material (for example, N, ○yama: J,
Electroanal, Chem, 161,399-
4-05 (1984)). However, according to the findings of the present inventors, the conductivities of the benzonoid=amine state and the benzonoid niummonium salt state are comparable, and it has been found that there is no superiority or inferiority between the two. Rather, when polyaniline is used as a battery material, especially when used as a positive electrode of a non-aqueous electrolyte lithium secondary battery, the lower the content of benzonoid ammonium salt, the better the self-discharge and float characteristics. When polyaniline is used as a sensor or circuit element material, especially in a non-aqueous system (for example, E, W, Paul, A, J,
Ricco, M.S., Wright: J.
, Phys., Chew.

89.1441 (1985)), the lower the content of benzonoid ammonium salt, the less malfunction occurs.
Therefore, in terms of performance, a lower content of benzonoid ammonium salt was preferable for such uses. Moreover, it was also found that the benzonoid in the ammonium salt state is highly corrosive.

Based on the above knowledge, the present inventors conducted further intensive research on the composition of polyaniline in order to obtain polyaniline with excellent properties as an electronic material. It has been discovered that polyaniline having a nitrogen imine state moiety of 25 mol % or less can achieve the above object, and has led to the present invention.

The present invention will be explained in more detail below.

As mentioned above, the polyaniline of the present invention has a benzonoid niummonium salt state moiety of 7 mol% or less and a quinoid nidiimine state moiety of 25 mol% or less. The mol% of the salt state moiety and the mol% of the quinoid diimine state moiety are shown. The preferable range of these ratios is 0 to 3 mol% for the benzonoid niummonium salt state part and 0 to 1 mol% for the quinoid nidiimine state part.
It is 8 mol%. Further, it is preferable that the benzonoid=amine state part is 18 to 100 mol%, particularly 34 to 100 mol%, and the dope=semiquinone radical state part is 0 to 50 mol%, particularly 0 to 45 mol%.

In the polyaniline of the present invention, the portion in the benzonoid niummonium salt state is as small as 7 mol% or less, and the portion in the quinoid diimine state is also as small as 25 mol% or less, so the corrosion resistance is improved and the conductivity is improved. Especially when this polyaniline is used as a battery electrode material, it has low self-discharge, life span, discharge capacity, etc., and is excellent in durability as a circuit element material.

On the other hand, in conventional polyaniline, the portion in the benzonoid niummonium salt state is 0 to 25 mol%, and the portion in the quinoid/diimine state is 0 to 55 mol%; No material with a quinoid diimine state of less than 25 mol% has been obtained, and its properties as an electronic material are poor.

That is, the method of Koyama et al. (J, Electroanal,
Chem.

161.399 (1984)), the benzonoid ammonium salt state was approximately 0 mol%.
However, the quinoid diimine state is about 55 mol%, and the method of MacDiamide et al.
In Example 1 of No. 169), the benzonoid in the ammonium salt state is about 25 mol %, and in Example 3, the ammonium salt state is 30 to 40 mol %. These include MacDiamide et al. which amines the behavior of polyaniline →
This is due to a factual misunderstanding that it is due to a change between imine, benzonoid←quinoid, and the double bond between imine and quinone as described in claims 4.5 and 9.11 of the above publication is Does not contribute to battery charging and discharging. This is proven by the fact that a sample having a peak only around 1470an-1 and no peak around 1320cXn-1 cannot be discharged by Raman spectroscopy.

As a method for specifying the polyaniline of the present invention, a method using a combination of X-ray photoelectron spectroscopy and an electrochemical method is suitably employed.

To explain this method in more detail, in X-ray photoelectron spectroscopy, the C1s orbit is 284. It is calibrated to OeV, and the peak of the N I 5 orbital of the sample polyaniline is divided using a Gaussian distribution. In this case, it is usually divided into three peaks, but
Among these, the area of the peak centered at 398.2 to 398.8 eV represents the sum of the benzonoid=amine state and the quinoid diimine state, and the area of the peak centered at 398.9 to 400.5 eV represents doped; semiquinone Represents a radical state, 401. The area of the peak centered at ○eV or higher represents the benzonoid ammonium salt state.

If either state does not exist, the peak will not appear. Here, the quinoid=diimine state appears in the same peak as the benzonoid=amine state, but in order to calculate the amount of the quinoid=diimine state, use the sample polyaniline as the working electrode, lithium as the counter electrode, and 1 mol/Q LiBF. An electrochemical cell was constructed using a propylene carbonate solution containing the electrolyte as an electrolyte, and the voltage was fixed at +2V compared to lithium for 100 hours, then at +3.6V for 24 hours, and again at +2V for 24 hours, and the discharge capacity at this time was Measure. If this discharge capacity is x A h / kg per polyaniline, then
The amount expressed by the formula is the amount of quinoid=diimine state. Therefore, the amount of benzonoid in the ammonium salt state was determined from NIS analysis by X-ray photoelectron spectroscopy, the amount of quinoid = diimine state was determined from the above-mentioned second discharge capacity, and the amount of benzonoid = amine state, dope =
The amount of semiquinone radical state is also determined from this.

In this case, Raman spectroscopy can be employed as an auxiliary means to the above method.The resonance Raman effect caused by excitation at 514.5 nm in a discharge state of +2V and a charge state of +3.6V relative to lithium for the polyaniline sample This is a method to measure and verify that there is substantially no quinoid=diimine state.

That is, in a discharge state (a state in which polyaniline is not doped with negative ions, +2 V or less compared to lithium), polyaniline is excited with a laser beam of 514.5 nm,
By measuring the Raman scattered light, polyaniline in the benzonoid=amine state was found to be 1590■-1 to 164
Polyaniline in the quinoid = diimine state has a scattering peak between 0 and -1 and has a scattering peak of 1450QTI-' to 1520c.
This can be determined from the property that it has a scattering peak between m-''.

On the other hand, polyaniline in a doped semiquinone radical state exhibits 514.5 nm excitation laser Raman failure in a charged state (polyaniline is doped with negative ions, +2.5 V or more, especially +3.6 V compared to lithium potential). It can be confirmed by analysis that it has a scattering peak between 1300an-'' and 1350an-1.

Here, how does the change from the dope = semiquinone radical state to the quinoid = diimine state occur in the charged state? The following formula (E) (Note that this is an example where the negative ion species is BF4) As shown in , positive charges are released from the main chain of polyaniline along with hydrogen ions,
The change in semiquinone radical to quinone can be determined by exciting polyaniline with a 514.5 nm laser beam and measuring the Raman scattered light at 1300 cm-
”The scattering peak between ~1350 cm-1 decreases with the decrease of the doped=semiquinone radical state, all quinone=
This can be confirmed by the disappearance of this peak when the state changes to the diimine state. Therefore, we analyzed the Raman scattered light of polyaniline in the charged state, and found that when excited at 514.5 nm, 13
If scattered light is observed between 00cm-'' and 1350an-1, the dope=semiquinone radical state can be confirmed, and if charging is attempted in the quinoid=diimine state, 13oOaIf-' to 1350an-1. No Raman scattering occurs in between.

Note that the amount of the benzonoid in the ammonium salt state can be determined from NIS analysis using the above-mentioned X-ray photoelectron spectroscopy, or can also be determined from elemental analysis.

Therefore, as polyaniline, 514
．． 1 in Raman scattering analysis using 5 nm excitation laser light.
The main component is polyaniline in the benzonoid=amine state with a scattering peak between 590■-1 and 1640■-1, and the polyaniline in the quinoid=diimine state with a scattering peak between 1450cff+-" and 1520■-1 as the main component. or not included in 514. in the charging state.
13 by Raman scattering analysis using 5 nm excitation laser light.
By using dope = semiquinone radical state material with a scattering peak between COan-1 and 1350 cm-' as an electrode material for a secondary battery, it was confirmed that polyaniline in the quinoid = diimine state is not substantially contained. Therefore, a secondary battery with a very large discharge capacity can be obtained.

Furthermore, as mentioned above, the dope=semiquinone radical state contributes greatly to the conductivity of polyaniline, and the benzonoid niummonium salt state and the quinoid=diimine state are unfavorable in terms of corrosion and conductivity. The fact that polyaniline does not form a quinoid-diimine state in the doped state and is in the doped semiquinone radical state means that the intensity of the peak appearing at 7 to 9 eV is 15 in the valence band analysis by X-ray photoelectron spectroscopy. ~20
This can be confirmed by the peak intensity being larger than the peak intensity between eV (note that the electron density peak of valence band analysis using Polyaniline in the radical state is between 7 and 9 eV, and polyaniline in the benzonoid=amine state and benzonoid ammonium salt state occurs in the energy range of 15 to 20 eV. Contact time 1 m S E C, relaxation time ○, 140 ppm ~ 145
This can be confirmed by having a peak between ppm and having no peak with an intensity of 85% or more of the above peak below 14Qppm.

Therefore, in analysis by X-ray photoelectron spectroscopy, 15~20e
The maximum electron density between 7 and 9 eV is larger than the maximum electron density between V and the main component is polyaniline in a doped semiquinone radical state, or C□3 solid-state high-resolution NMR According to the analysis, when the contact time is 1m5EC and the relaxation time is 0, it has a peak between 140 ppm and 145 ppm, and does not have a peak with an intensity of 85% or more of the above peak below 140 ppm.Substantially doped = A material containing polyaniline in a semiquinone radical state as a main component is particularly suitable as a conductive material.

Furthermore, when polyaniline is used as a sensor, circuit element material, etc., the benzonoid ammonium salt state is not preferable because it tends to cause malfunctions during switching, as described above. In addition, such devices usually perform switching by utilizing the fact that conductivity improves when polyaniline is doped with anions, but when the quinoid=diimine state is included, the resistance is higher than the benzonoid=amine state. Therefore, the switching characteristics are inferior. Therefore, the main component is benzonoid = amine state,
Polyaniline, which can perform switching by changing it into a doped semiquinone radical state, is preferable as a material for sensors and circuit elements. The fact that the main component of polyaniline is polyaniline in a benzonoid=amine state means that C
In the analysis using the R method, the contact time was set to 1m5.
EC, when relaxation time is Q, 115
~120ppm and 1l35-140ppm, and a peak between 140 and 180ppm with an intensity of 10% or more of the larger peak between 115 and 120ppm or 135 and 140ppm, respectively. You can confirm this by not having it. Also,
NI by a combination of the analytical methods mentioned above, especially by X-ray photoelectron spectroscopy
In S analysis, the main peak is 398.2 eV to 398.8 eV, and in 514.5 nm excitation laser Raman scattering analysis, it has a peak at 1590 to 1640 an-'.

By not having a peak at 1500 to 1200an-1, or when no electrolyte is detected in single element analysis, and 5
1500 ~ by 14.5 nm excitation laser Raman scattering analysis
This can also be confirmed by the fact that there is no peak at 1200an-1.

Therefore, in the analysis using the solid-state high-resolution NMR method,
When the contact time is 1m5EC and the relaxation time is ○, it is between 115 and 120 ppm and 135
~140 ppm, and 14
0 to 180 ppm, which does not have a peak with an intensity of 10% or more relative to the larger peak between 116 to 120 ppm or 135 to 140 PPm, which is mainly composed of polyaniline in a benzonoid=amine state; Furthermore, materials that do not substantially contain polyaniline in the quinoid-diimine state or benzonoid-niammonium state are preferably used as materials for sensors and circuit elements.

The benzonoid ammonium salt state of the present invention is 7 mol%
Although there is no restriction on the method for producing polyaniline having a quinoid=diimine state of 25 mol% or less, a method of oxidatively polymerizing aniline in an acidic atmosphere and then removing the benzonoid ammonium salt state is preferably used.

That is, first, aniline was converted into HBF4. HF, HCQ, HCf
Oxidative polymerization is carried out using electrolysis and/or a catalyst in an acidic aqueous solution such as lO4. In the polymerization solution immediately after polymerization, the polyaniline polymerized at this time has the following states: benzonoid=amine state 20-60 mol% benzonoid ammonium state 12-25 mol% tope=
Semiquinone radical state is 30 to 55 mol%,
If the pH is more acidic than 1, the quinoid-diimine state will hardly form. Therefore, the benzonoid ammonium salt state may be removed from this state.

In this case, one possible means is to change the benzonoid niummonium salt state to the benzonoid=amine state by alkali treatment or the like as shown in the following formula (1).

However, according to this method, as shown in the following formula (2), the dope=semiquinone radical state in polyaniline releases protons from the main chain of polyaniline and changes to the quinoid=diimine state, resulting in a decrease in capacity.

According to the research conducted by the present inventors, the change from the dope = semiquinone radical state to the quinoid = diimine state occurs at pH 4.
Since the process progresses rapidly on the alkaline side compared to .

Further, even if the polyaniline is returned to the acidic solution, the polyaniline which has become the -degree quinoid=diimine state will not completely return to the dope=semiquinone radical state.

More specifically, benzonoids polymerized in acidic solution =
It is a mixed state of amine state, benzonoid niummonium salt state, and dope=semiquinone radical state, and when this polyaniline is washed with water, the benzonoid niummonium salt changes to benzonoid=amine, and the dope= state occurs at a slightly slower rate than that change. The semiquinone radical state changes to the quinoid=diimine state, and such a state has a small content of the doped=semiquinone radical state. Actually, X
When the valence band is analyzed by line photoelectron spectroscopy, a peak between 7 and 9 eV is observed due to the doped = semiquinone radical state, and a peak between 15 and 20 eV due to the benzonoid = amine state and benzonoid niummonium salt state.
The peak intensity of is strong (for example, P, S
ert et al.: Synthe, Met.
.

18 (1987) 335-340). Furthermore, when analyzed by solid-state high-resolution NMR method, it was found that 140 ppm to 145 ppm due to the dope = semiquinone radical state.
A peak between
rg, et al., J., Po1. Sci, Pol.

Let, 23 (1985) 503-508).

In addition, even with alkali treatment or acid treatment, the amount of dope = semiquinone radical state cannot be significantly increased, and when measuring the valence region of the ydJ photoelectron spectrum, it is found that in alkali treatment, dope = The 7-9 eV peak based on the semiquinone radical state was not observed, and even with acid treatment, the 15-20 eV peak was 7-9 eV.
greater than the peak of V (e.g., W, R, S al
aneck et al, :5ynthe, Met,
, 18 (1987) 291-296), and when analyzed by solid-state high-resolution NMR method, it was found that in alkali treatment, there was not only a peak at 140 to 145 ppm based on the dope = semiquinone radical state. 120-13
A peak was observed at 0 ppm, and in acid treatment it was 130 ppm.
A peak is observed only in the vicinity.

Therefore, the quinoid diimine state is not generated from the polyaniline after polymerization, the benzonoid niamonium salt state is removed, and the benzonoid niamonium salt state is 7 mol % or less, and the quinoid ni diimine state is 25 mol %. As a method for obtaining the following polyaniline, any one of the following first to third methods or a combination thereof is preferred.

The first method is preferably immersed in an acidic aqueous solution of a hydrazine compound such as hydrazine hydrochloride or hydrazine borofluoride, and then treated with hydrazine. There are no particular restrictions on the conditions for this treatment, but as acidic treatment, 50
It is effective to treat 100 mg of polyaniline with an acidic aqueous solution containing hydrazine of mmol/Q to 2 mol/Q in an amount of 50 cc or more. In addition, when using hydrazine fluoroboric acid, an aqueous solution of fluoroboric acid and an aqueous hydrazine solution can be appropriately mixed and used. There is no need to be particular about the molar ratio; good results can be obtained as long as the pH is more acidic than 3, so for example 10
0 mmol/Q to 4 mol/Q of fluoroboric acid and 50
An aqueous solution containing hydrazine at mmol/Q to 2 mol/Q is preferably used. Standard processing solutions include 286.5 cc of 42% fluoroboric acid and 4 ml of hydrazine monohydrate.
8.5, distilled water 665. N2H mixed in the ratio of ○■
A 1M aqueous solution (pH 1) of 4.2HBF4 is preferably used. Note that the immersion time is preferably 3 to 24 hours. Further, as a method for hydrazine treatment, a method of exposing a thin film sample to hydrazine vapor, and a method of immersing a thick film sample in an aqueous hydrazine solution are suitable. In this case, the exposure time to hydrazine vapor is preferably from 5 minutes to 72 hours, particularly preferably from 5 minutes to 3 hours. In addition, in the hydrazine aqueous solution immersion treatment, the concentration of hydrazine was 1
0 to 50% by weight/volume, and the treatment time (soaking time) is 1
It is preferable to set it as 2 to 48 hours. Here, direct treatment with hydrazine without hydrazine treatment in an acidic atmosphere is inappropriate because hydrazine is alkaline and polyaniline suddenly treated with hydrazine will generate a quinoid diimine state. be. In addition,
It is relatively easy to distinguish between the benzonoid=amine state and the quinoid diimine state, and polyaniline in the benzonoid=amine state is colorless (thin film is transparent, thick film is white).
On the other hand, polyaniline that has formed a quinoid diimine state becomes blue, and polyaniline that has further deteriorated has a gray color.

In both of the above immersion methods, the treatment temperature is -5℃ to 30℃.
It can be done. In addition, in the above method, it is important to remove hydrazine after treatment, but it is important not to expose it to an oxidizing atmosphere, and polyaniline in the benzonoid = amine state cannot be oxidized even by oxygen in the air over a long period of time. methanol that has been vacuum degassed or inert gas vented.

It is preferable to wash with a solvent such as ethanol, acetonitrile, or water. There are no restrictions on the drying method, but it is preferable to dry without raising the temperature above 100°C, especially at 60°C.
It is preferable to dry under vacuum at a temperature below ℃. Even in preservation,
It is preferable to store it in a cool, dark place under vacuum or inert gas, but it can also be stored indoors as long as it is protected from direct sunlight.

In addition, by this method, analysis by solid-state high-resolution NMR shows 1l15-120pp when the contact time is 1m5EC and the relaxation time is 0.
and between 135 and 140 ppm, and between 140 and 180 ppm, the above 115-1
It is possible to obtain polyaniline whose main component is polyaniline in a benzonoid=amine state that does not have a peak with an intensity of 10% or more with respect to the larger peak of 20 ppm or 135 to 140 ppm.

That is, doping of polyaniline = semiquinone radical state, benzonoid niummonium salt state, benzonoid =
Marker bands determined by solid-state high-resolution NMR in the amine state and quinoid=diimine state are as follows:
When the carbonyl of glycine is calibrated to 176.5 ppm, the dope=semiquinone radical state is approximately 1
gives a single peak at 30 ppm (e.g. F, De
vreux, et al.

J, Physique 4 G (1985)), the benzonoid ammonium salt state similarly gives a single peak around 130 ppm. The benzonoid=amine state gives one peak each between 115-120 ppm and 135-140 ppm, and the quinone diimine state gives 115-12 peaks like the benzonoid=amine state.
1 between 0 ppm and 135-140 ppm, respectively.
140-180 ppm in addition to giving two peaks.
During analysis using solid-state high-resolution NMR, the contact time was set to 1m5EC and the relaxation time was set to O.
between 115 and 120 ppm and between 135 and 14
Each has a peak between 0 ppm and 140 to 1
By controlling the amount so as not to have a peak between 80 ppm, it is possible to obtain polyaniline that is substantially in a benzonoid=amine state. In this case, as mentioned above, it is preferable that there be no peak between 140 and 180 ppm, but between 115 and 120 ppm and between 135 and 140 ppm.
If the peak has an intensity of less than 10% of the larger peak between pm and pm, there is almost no problem with the decrease in conductivity due to polyaniline in the quinoid=diimine state.

The second method is to dope the benzonoid in the ammonium salt state as shown in the following formula (3) by applying a potential of about +3.9 V to polyaniline compared to lithium in a non-aqueous electrolyte that does not contain an ether solvent. = This is a method of changing to semiquinone radical state.

In this case, there is no limit to the method of changing the benzonoid niummonium salt state to the doped semiquinone radical state by electrolysis, but lithium borofluoride.

Lithium perchlorate, LiAsF6. LiSbF6.
LiPF.

Using an organic solvent containing 0.5 to 3 mol/Q of lithium salt, typically a known electrolyte for lithium batteries described below,
Apply a voltage of 3 to 4 V with lithium as the counter electrode for 1 to 50 hours,
More preferably, a method in which the voltage is applied for 1 to 12 hours can be adopted, and as an example, lithium fluoroborate is applied for 0.5 to 12 hours.
A method is preferably used in which a sufficiently dehydrated propylene carbonate solution containing 5 to 2 mol/Q is used as the electrolytic solution, and a voltage of 3.9 V is applied for 3 to 6 hours using lithium as a counter electrode. Note that the time period for applying the voltage of 3.9 V is preferably within 50 hours, since there is a risk that deterioration of the polyaniline and polyaniline may occur.

The polyaniline created in this way is stored in thoroughly dehydrated hexane and acetonitrile.

It is preferable to store it in an electrolytic solution for lithium batteries, or in a vacuum or inert gas, and preferably to avoid an alkaline environment that releases water or hydroxyl groups. This is to prevent the polyaniline in the doped = semiquinone radical state from undergoing a neutralization reaction similar to the above formula (2) and changing into the quinoid = diimine state.

In addition, analysis by X-ray photoelectron spectroscopy shows that the
The maximum value of electron density between 7 and 9 eV is larger than the maximum value of electron density between So, the contact time is 1m5EC, and the relaxation time is 0.
polyaniline containing as a main component polyaniline in a substantially doped semiquinone radical state, which has a peak between 140 and 145 ppm when After refining polyaniline, an electrochemical cell is created in an electrolytic solution without proton acceptors (e.g., non-aqueous electrolyte), and the doped state (a state in which polyaniline is doped with negative ions. Lithium potential Contrast, +2.
5 V or more) does not change from the doped = semiquinone radical state to the quinoid diimine state. In other words, by creating an electrochemical cell using polyaniline under various conditions, Raman collapse of polyaniline in the doped state is controlled. 1320 at the time of 514.5 nm excitation when analyzing the light
am-", or as a strong electron density peak is observed at 7 to 9 eV by X-ray photoelectron spectroscopy, or by solid-state high-resolution NMR analysis.
An electrochemical cell may be created and doping conditions may be adjusted so that the peak between 40 and 145 ppm does not decrease. In this case, electrochemical cell electrolyte composition, polyaniline purification status.

Outside air temperature, doping voltage, temperature rise during doping, etc. are important control factors. That is, a known electrolyte for lithium batteries such as propylene carbonate or ethylene carbonate is suitably used as the electrolyte, but when an ether such as dimethoxyethane is added to this to reduce the viscosity, the dope voltage is set to 0.1V. It is preferable to reduce the degree. Since an increase in outside air temperature or a temperature increase during doping also promotes the transformation of semiquinone radicals into quinone, it is preferable to lower the doping voltage. Doping voltage has a large effect on the process by which semiquinone radicals change into quinones, and lowering the doping voltage stops the conversion to quinones. The purification state of polyaniline is also important; if it is doped from a benzonoid = amine state, it will change once to a doped = semiquinone radical state, but it will be +4.3 compared to lithium.
A voltage of about V changes it to a quinoid diimine state. To prevent this, if the temperature is around 20° C., the doping voltage may be lowered to around 3.7V. Also,
As for subsequent treatment, it is preferable to wash with a solvent with low proton acceptability such as acetonitrile and vacuum dry.

The third method is a reaction similar to the above equation (1) in which the benzonoid niummonium salt state changes to the benzonoid=amine state, but a reaction similar to the above equation (2) in which the dope = semiquinone radical changes to the quinoid diimine state. This is a method that takes advantage of the fact that the reaction proceeds faster when the pH is between 3 and 8 compared to similar reactions, and allows a cleaning solution with a pH of 3 to 8 to pass through polyaniline at high speed, in large quantities, and in a short period of time to quickly dry it. . There are no specific restrictions on the specific method, but examples include distilled water with a pH of 6 to 8, ion exchange water with a pH of 3 to 8, and cleaning solutions with a pH of 6 to 8.
8 various buffer solutions, or aqueous solutions of acids such as fluoroboric acid, hydrochloric acid, and perchloric acid having a concentration of 50 mmol/flood or less and having a pH of 3 to 6 are preferably used. In addition, when diluting fluoroboric acid with distilled water, 0.
An aqueous solution of 1 to 5 mmol/Q is suitable.

As a method of passing these washing liquids through polyaniline, for example, 5 c/min of polyaniline under reduced pressure can be used.
An effective method is to pass a cleaning solution of c/cxK or higher. Washing time is within 1 hour at pH 6-8, pH 3-8
5, preferably within 3 hours, more preferably within 25 minutes at pH 6 to 8, and preferably within 50 minutes at pH 3 to 5. For storage after washing, it is preferable to store in vacuum or in an inert gas, but it is also possible to store it indoors for about a week, avoiding direct sunlight.

In addition, the polyaniline obtained by the first to third methods above was given a potential of 2 to 3.9 V relative to lithium in a non-aqueous electrolyte to convert the benzonoid=amine state portion into a doped=semiquinone radical state. Polyaniline whose conductivity has been adjusted by changing the part is also preferable.

Specifically, a potential of about 2 to 3.9 V relative to lithium is applied to polyaniline in a nonaqueous electrolyte that does not contain an ether solvent, and in this case, lithium fluoroborate, lithium perchlorate, LiAsF, etc. are used.

0.5 to 3 lithium salts such as Li5bF, LiPF, etc.
Using an organic solvent containing mol/Q, typically a known electrolyte for lithium batteries described below, and using 2 to 3 mol/Q of lithium as a counter electrode,
．． 9v voltage for 10 minutes to 72 hours, more preferably 2 to 72 hours.
A method of applying a voltage of 3.6 ■ for 1 to 24 hours can be adopted; for example, lithium borofluoride is
．． A method is preferably used in which a sufficiently dehydrated propylene carbonate solution containing 5 to 2 mol/Q is used as the electrolytic solution, and a voltage of 2 to 3.6 V is applied for 1 to 24 hours using lithium as a counter electrode.

The polyaniline of the present invention is suitably used as a positive electrode material for batteries, and it is possible to obtain batteries with excellent charge/discharge characteristics and 1-meter durability. In this case, various negative electrode active materials can be used, but it is particularly preferable to use a material that can reversibly transfer cations into and out of the electrolyte. That is, the negative electrode active material preferably incorporates cations into the active material in a charged state (reduced state) and releases cations in a discharged state (oxidized M).

Examples of negative electrode active materials include substances with a high degree of conjugated bond in the molecule, specifically polynuclear aromatic compounds such as centracene, naphthalene, and tetracene, organic conductive polymer substances, and graphite materials. Can be mentioned. Furthermore, metals that can be monovalent or divalent cations, specifically lithium, sodium, potassium, magnesium, calcium, barium, zinc, etc., and alloys containing them can also be suitably used.

Among these, lithium and lithium alloys are preferably used as negative electrode active materials because of their ability to obtain high battery voltage, good cycle performance, and resistance to self-discharge. By combining these, it is possible to construct a non-aqueous lithium secondary battery with high battery voltage and excellent battery performance such as capacity density, cycle life, and self-discharge. In addition, as a lithium alloy, Li-AQ, Li-AQ-In, Li AQ-B
i etc. are preferably used, but there is no particular restriction as long as it is an alloy with a metal that can form an alloy with lithium.
l, Mg, In, Pb, Sn, Bi, Sb
, Ta, Zn.

An alloy with one or more types of Cd etc. is used.

The electrolyte constituting the battery is a compound consisting of a combination of an anion and a cation, and examples of anions include halide anions of VA group elements such as PFG"', 5bF1.AsF, -8bCQ6-, B F4 -,
Halide anions of group IIIA elements such as AQCQ4-, halogen anions such as I-(I3-), B r-CQ-, perchlorate anions such as Cρ04-, HF
2-, CF, SC2-; 5CN-'', SO knee, H8
04-, etc., but the anion is not necessarily limited to these anions. In addition, examples of cations include alkali metal ions such as Li", Na", and alkaline earth metal ions such as Ma", Ca", and Ba2+, as well as AQ3+, and R4N"(
Examples include quaternary ammonium ions such as (R represents hydrogen or a hydrocarbon residue), but the cations are not necessarily limited to these cations.

Specific examples of electrolytes having such anions and cations include LiPF, Li5bFG, and LiAsF.
G, Li (404, Lid, LiBr, LiCf
1. NaPF, Na5bF, NaAsF,
NCfO4, NaI, KPF6. KSbF,,
KAsFG, KCQO4, LiBF4. LiAUC
Q4. LiHF2. Li5CN, KSCN, L
iSO3CF, (n-C,H7)4NAsFG.

(n-C4H7)4NPF, (n-C4H7), NC
f1O4゜(n -C4H7)4 N B F 4 t
(C2H5)4 N CQO41(n-C4H,)4
Examples include NI. Among these, especially LiCΩ
○, LiBF4 is suitable.

Note that these electrolytes are usually used in a state dissolved in a solvent, and in this case, a relatively polar non-aqueous solvent is preferably used as the solvent. Specifically, propylene carbonate, ethylene carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, γ-butyrolactone, triethyl phosphate, triethyl phosphate 1~, dimethyl sulfate, dimethylformamide, dimethylacetamide,
Examples include one or a mixture of two or more of dimethyl sulfoxide, dioxane, dimethoxyethane, polyethylene glycol, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, and the like.

In addition, organic solid electrolytes in which the above electrolytes are impregnated with polymers such as polyethylene oxide, polypropylene oxide, isocyanate crosslinked products of polyethylene oxide, phosphazene polymers having ethylene oxide oligomers in their side chains, and inorganic ions such as Li, N, and LiBCQ4 are also available. A conductor, an inorganic solid electrolyte such as lithium glass such as Li4SiO, -Li3B○1, etc. can also be used.

Batteries are usually constructed by interposing an electrolyte between the positive and negative electrodes, but in this case, if necessary, a diaphragm (such as a porous membrane made of synthetic resin such as polyethylene or polypropylene, natural fibers, etc.) may be used between the positive and negative electrodes. separator).

The environment from polymerizing polyaniline to assembling the battery can be achieved by filling the surrounding atmosphere with an inert gas such as argon gas or nitrogen gas, by creating a non-oxidizing atmosphere such as hydrazine vapor, or by filling the surrounding atmosphere with an inert gas such as argon gas or nitrogen gas; A method of controlling the time until battery assembly, a method of controlling the cleaning solution for polyaniline to be in the range of weak acidity to acidity, etc. are preferably adopted. What is the composition of the battery electrolyte? As the A adjustment, a method of controlling the water concentration, a method of controlling the concentration of proton acceptors such as hydroxyl groups, etc. are suitably employed.

The polyaniline of the present invention can be further used in conventionally known applications, and in this case, the polyaniline can be used in conventional manners and methods.

As explained above, in the polyaniline of the present invention, the portion in the benzonoid niummonium salt state is 7% or less, and the portion in the quinoid nidiimine state is 25% or less. Due to these characteristics, it has good properties as an electronic material, high corrosion resistance, and high conductivity, and when used as a battery electrode material, it has excellent high-temperature self-discharge properties, float properties, discharge capacity, Demonstrates durability,
Furthermore, it has a long life when used as a sensor or circuit element material, and is therefore suitably used as an electrode material for batteries, sensor electrochromic displays, photovoltaic cells, etc., conductive materials, and single circuit element materials.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples; however, the present invention is not limited to the following Examples.

[Example 1] Using an electrolytic solution consisting of 5 cc of aniline, 15 cc of 42% fluoroboric acid, and 30 cc of ion-exchanged water, electricity was applied at a constant current of 10 mA for 2.8 hours using platinum as the polymerization electrode and platinum as the counter electrode. , polyaniline was obtained.

This polyaniline was immersed in a 1 mol/Q aqueous solution of hydrazine hydrochloride (pH approximately 1) for 24 hours at room temperature, further immersed in an aqueous hydrazine solution containing 30% by weight/volume of hydrazine for 24 hours at room temperature, washed with methanol, and dried in vacuum. did.

Next, the above polyaniline was used as a positive electrode, lithium was used as a negative electrode,
A battery was constructed using LiBF/propylene carbonate 1 mol/Q as an electrolyte. Using this battery, the polyaniline electrode was 0.0V until the voltage of the polyaniline electrode reached 3.6V vs. lithium.
The battery was charged at a constant current of 1 mA, and then discharged at a constant current of 0.1 mA until reaching 1.7 cm compared to lithium.

The composition of this polyaniline was investigated by Raman scattering analysis using 514.5 nm excitation, and the composition was found to be 1590 Sen-1 to 16.
The main component is polyaniline in a benzonoid=amine state with a scattering peak between 40an-' and 1450c.
It did not contain a quinoid diimine state having a scattering peak between g-1 and 1520an-1 (Fig. 1).

In addition, the results of examining the NIS spectrum by X-ray photoelectron spectroscopy show that there is no dope=semiquinone radical state or benzonoid niummonium salt state, and benzonoid=
The amine status was essentially 100% (Figure 2). In addition, in Figure 2, the values on the horizontal axis and the numbers written in the figure do not match because the values written in Figure 1 are after calibration, and the values in the figure after this calibration. is the correct value (the same applies to Figures 3 and 4).

Then, 0.1mA until reaching 3.6■ compared to lithium.
Charge with a constant current of 2. compared to lithium. 0.1m to OV
When discharged at a constant current of A, the discharge capacity density was 110A.
h/kg.

Similarly, the battery was charged until the voltage reached 3.6V compared to lithium, and the capacity retention rate after being left at 60°C for 10 days was 91%.

[Example 2] Aniline 5 cc, 42% borohydrogen fluoride 915 cc,
Using an electrolytic solution consisting of 30 cc of ion-exchanged water, using platinum as the polymerization electrode and platinum as the counter electrode, a constant current of 10 mA was used.
Electricity was applied for a certain period of time to obtain polyaniline.

This polyaniline was washed with distilled water and then vacuum dried.

Next, the above polyaniline was used as a positive electrode, lithium was used as a negative electrode, and 50cc of LiBF/propylene carbonate 1
Construct an electrochemical cell using a mol/Q solution as an electrolyte, and
．． After applying a constant voltage of 9v for 3 hours, the constant voltage of 3.8v was fixed for 3 hours. This was washed with deoxygenated acetonitrile and dried under vacuum.

The spectrum of this polyaniline obtained by X-ray photoelectron spectroscopy is shown in FIG.

Next, the above polyaniline was used as a positive electrode, lithium was used as a negative electrode, and L
A battery was constructed using iBF,/propylene carbonate 1 mol/Q as the electrolyte, discharged at 2V for 100 hours, charged at 3.6V for 24 hours, and then charged at 2V for 24 hours.
The discharge capacity was measured at a fixed time and the discharge capacity was 110 Ah/h. Therefore, from the above, the composition of the polyaniline is benzonoid = amine state, 54 mol% doped =
It was found that the semiquinone radical state was 466 mol%, and the quinoid diimine state was 0 mol%.

Similarly, the battery was charged until the voltage reached 3.6V compared to lithium, and the capacity retention rate after being left at 60° C. for 10 days was 91%.

[Example 3] Using an electrolytic solution consisting of 5 parts of aniline, 15 cc of 42% fluoroboric acid, and 30 cc of ion-exchanged water, one polymerization electrode was charged with SU.
A constant current of 10 mA was applied for 2.8 hours using an SUS 316 wire mesh and an SUS 316 wire mesh as the counter electrode, to obtain polyaniline.

Next, this polyaniline was washed with 80 cc of distilled water for 5 minutes under a reduced pressure of 40 anHg.

The spectrum of this polyaniline obtained by X-ray photoelectron spectroscopy is shown in FIG.

Next, the above polyaniline was used as a positive electrode, lithium was used as a negative electrode, and L
x B F 4 /propylene carbonate 1 mol/
Construct a battery using Q as the electrolyte, discharge it by fixing it at 2V for 100 hours, and charging it by fixing it at 3.6V for 24 hours.
The battery was discharged for 24 hours at a fixed voltage of V, and the discharge capacity at that time was measured, and the result was 105 Ah/kg.

Therefore, from the above, the composition of the polyaniline is: benzonoid = amine state 75.7 mol% benzonoid niummonium salt state 3.4 mol% dope = semiquinone radical state 16.4 mol% quinoid = diimine state 4.5 It was found to be mol%.

Similarly, the battery was charged until the voltage reached 3.6V compared to lithium, and the capacity retention rate after being left at 60'C for 10 days was 88%.

[Comparative Example 1] Using an electrolytic solution consisting of 5 cc of aniline, 15 cc of 42% borofluoric acid, and 30 cc of ion-exchanged water, electricity was applied at a constant current of 10 mA for 2.8 hours to obtain polyaniline.

Next, add 5 cc of water to 1 cc of this polyaniline.
It was exchanged several times, washed with water for a total of 120 hours, and then dried in vacuum.

According to elemental analysis of the elements nitrogen and fluorine, this polyaniline had a total amount of 10 mol % in the benzonoid niummonium salt state and the doped semiquinone radical state.

In addition, when the battery was constructed and the amount of dope=semiquinone radical state was determined from the initial discharge capacity, it was 8 mol%, so the benzonoid ammonium salt state was 2 mol%.
It was concluded that.

Furthermore, when it was charged to 3.6V and the discharge capacity was measured, it was 76Ah/kg, and the quinoid diimine state was 31
It was concluded that the benzonoid=amine status was 59 mole %.

Next, a battery was constructed using the polyaniline described above in the same manner as in Example 1, and a similar battery test was conducted.The discharge capacity was 70Ah/kg, and the capacity was maintained after being left at 6°C for 10 days. The rate was 90%.

[Comparative Example 2] Aniline 5 cc, 42% Hofu R&I 5 cc,
Using an electrolytic solution consisting of 30 cc of ion-exchanged water, 10 mA
A constant current of 2.8 hours was applied to obtain polyaniline.

Next, 1 inch of this polyaniline was washed with 10 cc of water for 30 minutes, and then dried under vacuum.

This polyaniline was analyzed in the same manner as in Comparative Example 1, and the results showed that 42 mol% was in the benzonoid=amine state, 30 mol% was in the dope=semiquinone radical state, 17 mol% was in the benzonoid niummonium salt state, and 17 mol% was in the benzonoid niummonium salt state. The imine state was 11 mol%.

Next, a battery was constructed using the polyaniline described above in the same manner as in Example 1, and a similar battery test was conducted.The discharge capacity was 105Ah/kg, and the capacity retention rate after being left at 60'C for 10 days. was 55%.

[Example 4] Aniline 5 cc, 42% fluoroboric acid 15 cc
.

Using an electrolytic solution consisting of 30 cc of ion-exchanged water, 10 mA
A constant current of 2.8 hours was applied to obtain polyaniline.

Next, this polyaniline was immersed in a 1 mol/Q aqueous solution of hydrazine hydrochloride (pH approximately 1) for 24 hours, further immersed in an aqueous solution containing 30% by weight/volume of hydrazine for 24 hours, washed with methanol, and vacuum dried.

Next, the above polyaniline was used as a positive electrode, lithium was used as a negative electrode,
An electrochemical cell was constructed using L x B F 4 /propylene carbonate 1 mol/Q as an electrolyte.

Using this electrochemical cell, the polyaniline electrode was doped with a constant current of 0.1 mA until the voltage reached 3.8 V relative to lithium, washed with acetonitrile, and then dried in vacuum.

When this polyaniline was analyzed by X-ray photoelectron spectroscopy, there was a strong peak between 7 and 9 eV, and doping =
The content of semiquinone radical state was extremely high (Figure 5). When its electrical conductivity was measured, it was 50 S/mouth.

When this polyaniline was analyzed by C13 solid state high resolution NMR, it was found that it had a peak between 140 and 145 ppm, and 85% of this peak was below 140 ppm.
It was confirmed that the content of the dope=semiquinone radical state was extremely high from this point as well (Figure 6).

[Comparative Example 3] Using an electrolytic solution consisting of aniline 5a, 15 cc of 42% fluoroboric acid, and 30 cc of ion-exchanged water, electricity was applied at a constant current of 10 mA for 2.8 hours to obtain polyaniline.

This polyaniline was then dissolved in 1M sodium hydroxide for 24 hours.
It was soaked for an hour, washed with methanol, and dried in vacuum.

When this polyaniline was analyzed by X-ray photoelectron spectroscopy, it showed two low peaks in the energy region of 5 eV or less.
The content of the quinoid diimine state was high (
Figure 7). When its conductivity was measured, it was found to be 10-'S/
■It was below.

Next, the above polyaniline was used as a positive electrode, lithium was used as a negative electrode,
A battery was constructed using LiBF4/propylene carbonate 1 mol/Q as an electrolyte. Using this battery, the polyaniline electrode was 0.0V until the voltage of the polyaniline electrode reached 3.6V vs. lithium.
Charge with a constant current of 1mA.

Next, the battery was discharged at a constant current of 0.1 mA until reaching 1.7 V relative to lithium. This polyaniline.

When its composition was investigated by Raman scattering analysis using excitation at 514.5 nm, it was found to contain polyaniline in a quinoid diimine state with a scattering peak between 145o mark -1 and 1520o mark (Fig. 8). In addition, polyaniline in a charged state, which was charged at a constant current of 0.1 mA until reaching 3.6 compared to lithium, was 13 by Raman scattering analysis with excitation at 514.5 nm.
Since it did not have a scattering peak between 00<-1> and 1350 rho1, but rather had a scattering peak near 1470 (m""), it was confirmed from this point that it was a quinone diimine structure.

Then 0.1mA until reaching 3.6v vs. lithium
Charge with a constant current of 2. compared to lithium. Q to Ov, 1m
When discharged at a constant current of A, the discharge capacity density was approximately OA
h/kg.

[Comparative Example 4] 5 cc of aniline, 5915 cc of 42% hydrogen borofluoride,
Using an electrolytic solution consisting of 30 cc of ion-exchanged water, 10 mA
A constant current of 2.8 hours was applied to obtain polyaniline.

Next, this polyaniline was washed with water and then vacuum dried.

When this polyaniline was analyzed by X-ray photoelectron spectroscopy, it showed a peak between 8 and 9 eV, but
The peak between 20 eV is larger and P, Sn
auwaert at al,: 5ynthe, M
etc.

18 (1987) 338, similar results were obtained. When its conductivity was measured, it was 2S/■ [Example 5] 5 cc of aniline, 15 cc of 42% fluoroboric acid,
Using an electrolytic solution consisting of 30 cc of ion-exchanged water, 10 mA
A constant current of 2.8 hours was applied to obtain polyaniline.

Next, this polyaniline was immersed in a 1 mol/Q aqueous solution of hydrazine hydrochloride (pH approximately 1) for 24 hours, further immersed in an aqueous solution containing 30% by weight/volume of hydrazine for 24 hours, washed with methanol, and vacuum dried.

This polyaniline has C□, between 115 and 120 ppm and between 135 and 120 ppm, as analyzed by solid state high resolution NMR.
One peak was obtained between 140 ppm (Figure 9). Next, when the conductivity was measured, it was found that 1O-5S/
It was an.

[Comparative Example 5] Using an electrolytic solution consisting of 5 cc of aniline, 15 cc of 42% fluoroboric acid, and 30 cc of ion-exchanged water, electricity was applied at a constant current of 10 mA for 2.8 hours to obtain polyaniline.

Next, this polyaniline was immersed in 1M sodium hydroxide for 24 hours, washed with methanol, and dried in vacuum.

This polyaniline has concentrations between 115 and 120 ppm and between 135 and 140 ppm by C□3 solid state high resolution NMR analysis.
peaks were given between 140 and 180 ppm, and the content of quinone diimine state was high (10
figure). Next, when the conductivity was measured, it was found to be 10-'S/a
It was below ++.

[Comparative Example 6] Using an electrolytic solution consisting of 5 cc of aniline, 15 cc of 42% fluoroboric acid, and 30 cc of ion-exchanged water, electricity was applied at a constant current of 10 mA for 2.8 hours to obtain polyaniline.

Next, this polyaniline was washed with water and then vacuum dried.

This polyaniline gave a single peak around 130 ppm (11th
figure). When I measured the conductivity, it was 2S/■, but when I stored it in a galvanized iron can, it was 1S/■.
The can had rusted within a week.

[Brief explanation of the drawing]

FIG. 1 shows 514.5% of polyaniline in a discharge state according to an embodiment of the present invention. Raman scattering spectrum using Snm excitation laser light, Figure 2 shows C15-284 by X-ray photoelectron spectroscopy of the polyaniline, N calibrated to OeV.
IS spectrum, FIG. 3 is cls=284 obtained by X-ray photoelectron spectroscopy of polyaniline according to another example of the present invention.
, OeV NIS spectrum, FIG. 4 shows the cis" 284, ○eV NIS spectrum of polyaniline according to yet another embodiment of the present invention by X-ray photoelectron spectroscopy, and FIG. 5 shows the X Line photoelectron spectroscopy spectrum, Figure 6 shows the C13 solid-state high-resolution NMR spectrum of the same polyaniline, Figure 7 shows the X-ray high electron spectrum of the polyaniline of Comparative Example 3, and Figure 8 shows the 514.Snm excitation laser in the discharge state of the same polyaniline. A Raman scattering spectrum using light, FIG. 9 is a C-processed, solid-state high-resolution NM of polyaniline according to yet another embodiment of the present invention.
R spectrum, FIG. 10 is the solid-state high-resolution NMR spectrum of polyaniline according to Comparative Example 5, and FIG. 11 is the solid-state high-resolution NMR spectrum of polyaniline according to Comparative Example 6.
This is the R spectrum.

Claims (1)

[Claims] 1. Polyaniline in which the portion in the benzonoid niummonium salt state is 7 mol% or less, and the portion in the quinoid=diimine state is 25 mol% or less.