JPS6210861A - Nonaqueous secondary battery - Google Patents

Abstract

PURPOSE:To increase energy density and charge-discharge reversibility of a battery by using an alkali-treated aniline (aniline derivative) polymer in a positive electrode. CONSTITUTION:An aniline (aniline derivative) polymer is used in a positive electrode. Alkali metal (alloy), conductive polymer, or a complex of alkali metal alloy and conductive metal is used in a negative electrode. The aniline (aniline derivative) polymer is prepared by electrochemical polymerization or chemical polymerization and treated with alkali before use. Thereby, energy density and reversibility of battery are increased.

Description

[Detailed Description of the Invention] The present invention provides a high-performance nonwoven fabric with high energy density, good reversibility of charging and discharging, extremely low self-discharge rate, and excellent thermal stability. Regarding water-based secondary batteries.

The speed of light is about to increase.

Currently, commonly used secondary batteries include lead-acid batteries, -1-
There are N1/Cd batteries, etc. These secondary batteries have a single cell battery voltage of about 2.0 square meters at most, and are generally aqueous batteries. BACKGROUND ART In recent years, research has been actively conducted on the development of secondary batteries that use Li as a negative electrode as a secondary battery that can provide a high battery voltage.

When Li is used for the negative electrode, it is necessary to use a non-aqueous electrolyte because of the high reactivity between water and li.

However, when performing a secondary battery reaction using Li as a negative electrode active material, dendrites are generated when L1+ is reduced during charging, resulting in problems such as a decrease in charge/discharge efficiency and a short circuit between the positive and negative electrodes. Therefore, many technological developments have been reported to prevent dendrites and improve the charge/discharge efficiency and cycle life of negative electrodes. M. Abraham et al. Palitium Batchries'', edited by G.P. Calvano 1.

Academic Press, London (1983): H. braham et at, in
“Lithium Batteries”.

J, P, Gabano, editor, Aca
demic press, London (198
3) ), a method of preventing L+ dendrites by blending additives into the electrolyte system, or alloying the electrode itself with AI:L [JP-A-59-108281], etc. has been proposed. .

In addition to alkali metals and alkali metal alloys such as l-i/8, it is also known to use conductive polymers having a conjugated double bond in the main chain as negative electrode active materials [G.H. Curfman, Ji-Kou-Double Cowfer
, Nie J. Heger, Earl Kerner, Nie.
G. McDiarmid, Physics Review, 82
Volume 6, page 2327 (1982); J, H, K
aufman, J., W., Kavfer.

A1. Heeger, R, nianer, ^, G, Ha
cDiarmid, phys.

Rev., 826 2327 (1982)) Well-known conductive polymers used in this method include polyacetylene, polythiophene, polyparaphenylene, polypyrrole, and the like.

On the other hand, it is known that conductive polymers are used as positive electrode active materials in the same way as negative electrode active materials, and materials that form interlayer compounds with alkali metals such as T+82, chalcogenide compounds, and inorganic oxides are also used as positive electrode active materials. It is also known to use objects etc.

Conductive polymers used as positive electrode active materials include polyacetylene, similar to those used in negative electrodes,
Examples include polythiophene, polythiophene derivatives, polyparaphenylene, polyparaphenylene derivatives, polypyrrole, polypyrrole derivatives, and other well-known polymers of aniline and aniline derivatives. Further, specific examples of chalcogenide compounds and inorganic oxides used as positive electrode active materials include TtS2, Nb 3 Sn
, MO3Sn, Co82, FO82.

V205, Cr2O5, MnO2, Si02.

Co 02, Sn 02, etc. are known.

Among these positive electrode active materials, both the oxidation state and the reduction state are relatively stable in the air, and when used in batteries, they have good discharge flatness, can operate with high charge/discharge sodium bicarbonate, and have low self-discharge. Active materials with high energy density include aniline or polymers of aniline derivatives.

Electrochemical polymerization methods and chemical polymerization methods are known as methods for producing polymers of aniline or aniline derivatives. An example of a known document on the electrochemical polymerization method is Journal of the Chemical Society of Japan, No. 11.1801 (1984), and an example of a known document on the chemical polymerization method is A.G. Green and A. E. Woodhead, Journal of the Chemical Society, p. 2388.

1910 (A, G, Green and^, EJ
Iodhead, J., Chem.

30C, 2388 (1910)) is known, but
Generally, polymerization of aniline or aniline derivatives is carried out by anodic oxidation, with an electric field voltage of about 0.01 to 50 mA/cJR2, usually 1 to 3
Within the range of 00V, a constant current method, a constant voltage method, and any other method can be used. Polymerization takes place in aqueous solution;
The reaction is carried out in a non-aqueous solvent such as an alcohol, a nitrile, or a mixed solvent thereof, but it is preferably carried out in an aqueous solution. The non-aqueous solvent may or may not dissolve the produced polymer (oxidized polymer).

There is no particular restriction on the pH of the electrolytic solution, but it is preferable that the pH of the electrolyte be
H is 3 or less, particularly preferably pH is 2 or less. pH
Specific examples of acids used to adjust
, CF3C0OH, H25o71 and l-IN
03, etc., but is not particularly limited to these.

In the case of chemical polymerization methods, for example, aniline or aniline derivatives can be oxidatively polymerized in aqueous solution with oxidizing strong acids or with a combination of strong acids and peroxides such as potassium persulfate. The polymer (oxidized polymer) obtained by this method can be obtained in powder form, and can be used after being separated and dried.

In addition, in both electrochemical polymerization and chemical polymerization, it is also possible to add other additives to the polymerization electrolyte, such as carbon black, Teflon powder, polyethylene glycol, polyethylene oxide, etc. It is.

That is, a polymer of aniline or an aniline derivative is produced by the above method or a method similar to the above method, but since either method is polymerized in an acidic solution, the resulting polymer of aniline and aniline derivative is It is obtained in an acidic atmosphere and doped with a dopant in an amount of several mol % to several tens of mol % per repeating unit. Moreover, the polymers of aniline and aniline derivatives are obtained in a form containing electrolytes, oxidizing agents, additives in the sputum polymerization solution, impurities in the superposition solution, or side reaction products and oligomers during polymerization. often.

When using a polymer of aniline or an aniline derivative obtained by such a method as a battery active material, the obtained polymer is already doped at the time of polymerization, so it can be dried under reduced pressure and used in the battery as it is. Generally, the polymer is washed with water to remove impurities and the like and then dried under reduced pressure, or the polymer is washed with a solvent used in batteries before use, or a combination of these is used.

However, a polymer of aniline or aniline derivative produced and treated by the above method is used as the positive electrode, and an alkali metal, an alkali metal alloy, a conductive polymer, or a composite of an alkali metal alloy and a conductive polymer is used as the negative electrode. The non-aqueous secondary battery used has a low self-discharge rate, a high energy density, and is not necessarily capable of exhibiting good battery performance.
It cannot be said that it is an epoch-making product that greatly exceeds the performance of batteries and lead-acid batteries, and is not completely satisfactory.

The reason for this and No. 1 is that impurities and dopants, electrolytes, or oligomers that cannot be effectively activated after the above-mentioned post-treatment remain in the positive electrode active material, that is, the polymer of aniline or aniline derivative. In addition, the maximum capacity that can be accommodated per positive electrode weight is small, or the structure of the positive electrode active material itself, that is, the difference in morphology, specific surface area, or molecular weight = 7 -, makes it difficult to fill up the capacity per unit active material of the positive electrode. The capacitance decreases, either because the amount of electricity that can be discharged is suppressed, or because of differences in the mechanism of the positive electrode active material itself, such as the distribution of the quinoid structure in the polymer or the coordination state of the nitrogen atoms in the main chain. It is possible that it is not sufficient.

As a result of intensive studies to solve the drawbacks of the above-mentioned conventional techniques, the inventors of the present invention have developed an alkali solution for polymers of aniline or aniline derivatives obtained by electrochemical polymerization or chemical polymerization. By using it as a positive electrode after cleaning,
The present inventors have discovered that a high-performance non-aqueous secondary battery with extremely low self-discharge rate, high electric capacity, high energy density, and excellent thermal stability can be obtained, leading to the completion of the present invention.

That is, the present invention uses a polymer of aniline or an aniline derivative for the positive electrode, and uses an alkali metal, an alkali metal alloy, a conductive polymer, or a composite of an alkali metal alloy and an eleventh polymer for the negative electrode. -〇^^ The present invention relates to a non-aqueous secondary battery characterized in that, in the aqueous secondary battery, the polymer of aniline or aniline derivative is treated with an alkali.

The polymer of aniline or aniline derivative used in the positive electrode of the battery in the present invention means an oxidized polymer of aniline or aniline derivative represented by the following general formula.

[In the formula, R1-R4 may be different or the same and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an allyl group, or an aryl group having 6 to 10 carbon atoms. ] Representative examples of aniline or aniline derivatives represented by the above general formula include aniline, 2-methoxyaniline,
3-methoxy-aniline, 2,3-dimethoxy-aniline, 2,5-dimethoxy-aniline, 2,6-simethoxyaniline, 3゜5-dimethoxy-aniline, 2-ethoxy-3-methoxy-aniline, 2 .5-diphenylaniline, 2-phenyl-3-methyl-aniline, 2゜3.5-trimethoxy-aniline, 2,3-dimethyl-
Examples include aniline, 2,3,5,6-titramethyl-aniline, etc., and among these, aniline is most preferred.

The polymer of aniline or aniline derivative used in the present invention can be produced by either the electrochemical polymerization method or the chemical polymerization method, as described above.

Next, a method for alkali treatment of a polymer of aniline or an aniline derivative in the present invention will be explained.

As mentioned above, the polymer of aniline or aniline derivative obtained by polymerization by electrochemical polymerization method or chemical polymerization method is in an acidic atmosphere, and in addition, the electrolyte, oxidizing agent, additives, and polymers in the polymerization solution are It is often obtained in a form containing impurities in the lightning solution, side reaction products during polymerization, oligomers, etc.

In the present invention, the method of treating the polymer of aniline or aniline derivative obtained by polymerization with an alkali includes a method of washing the polymer once with water, or directly washing it several times with an aqueous alkaline solution, or a method of washing the polymer with an alkali. , washing with water, repeating this several times alternately, and finally washing with water again until the pH of the washing water is finally in the range of 5 to 9, preferably in the range of 6 to 8. can give.

As the alkaline aqueous solution used here, any aqueous solution having l)H of 12 or more can be used, but in order to increase treatment efficiency, one with a roughly high alkalinity is preferable.

As the alkali species, either an inorganic alkali or an organic alkali may be used as long as it is water-soluble, but from the viewpoint of cost, it is preferable to use a general-purpose alkali species. Specific examples of such alkali species include K 01-1, Na OH
Alkali metal hydroxides such as Mg (OH)2, Qa
Examples include aqueous solutions of alkaline earth hydroxides such as (OH)2, ammonia, and amines. Preferred among these alkal species are KOH, NaOH, and ammonia aqueous solutions, which are particularly useful for removing residual alkali or neutralized salts during water washing after neutralization and vacuum drying of the polymer. An alkaline species that is easy to use is ammonia water.

The number of times a polymer is treated with alkali varies depending on the type or shape of the polymer to be treated, the process of manufacturing the polymer, the concentration and amount of the treatment liquid, the size or shape of the treatment container, etc.
Usually, washing is performed once to several times.

When treating polymers with alkali, simply immersing the polymer in an aqueous alkaline solution is sufficiently effective, but for even more rapid and effective cleaning,
A method may be used in which an alkaline aqueous solution is circulated or the polymer is stirred as a whole while being immersed in the alkaline aqueous solution, or external energy such as ultrasonic waves may be applied. Like the number of alkali treatments, the alkali treatment time cannot be unconditionally defined because it varies depending on the amount and shape of the polymer, the temperature of the treatment liquid, and the size and shape of the treatment container.

It goes without saying that the shape of the aniline or aniline derivative polymer to be washed with alkali may be in the form of a film, particles, or powder.

Examples of the alkali metal used as the negative electrode active material in the present invention include Li, Na, and the like, and examples of the alkali metal alloy include Li/An.

Li/Hg, Li/Zn, Li/Cd, Li
Examples include alloys of three or more metals including /Sn 2 , Li /Pb, and alkali metals used in these alloys. Further, examples of the conductive polymer include polypyrrole and polypyrrole derivatives, polythiophene and polythiophene derivatives, polyquinoline, boriacene, polyparaphenylene, polyacetylene, and the like. Furthermore, examples of composites include composites of alkali metal alloys, such as Li/A1 alloys, and various conductive polymers. The composites referred to here are homogeneous aggregates of alkali metal alloys and conductive polymers, laminates, and substrates modified with other components, which are aprotic and have a high dielectric constant. is preferred. For example, ethers, ketones, amides, sulfur compounds, phosphate ester compounds, chlorinated hydrocarbons, esters,
Carbonates, nitro compounds, sulfolanes, etc. can be used, but among these, ethers, ketones, phosphate ester compounds, chlorinated hydrocarbons, carbonates, and sulfolanes are preferred. Representative examples of these solvents include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, monoglyme,
-Methyl-2-pentanone, 1,2-dichloroethane,
γ-butyrolactone, valerolactone, lame 1-xyethane, methylformate, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl sulfoxide, dimethylthioformamide, ethyl phosphate, methyl phosphate, chlorobenzene, sulfolane,
Examples include 3-methylsulfolane. Two or more of these solvents may be used in combination.

A specific example of the supporting electrolyte used in the non-aqueous secondary battery of the present invention is Li PFs.

Li5bFe, LiCJIO4, LiAsFa.

CF3803 Li, Li BF4, Li B (
Bu)4.

L i B (Et)2 (BLJ)2 , Na
PFe.

Na BF4 , Na As Fa , Na B (B
u) 4°KB (BL114, KAsFe, etc.) can be mentioned, but are not necessarily limited to these. These supporting electrolytes may be used alone or in combination of two or more.

The concentration of the supporting electrolyte varies depending on the type of aniline or aniline derivative polymer used in the positive electrode, the type of cathode, charging conditions, operating temperature, type of supporting electrolyte, type of organic solvent, etc., so it is generally non-uniform even in a regular system. It may be a system.

In the non-aqueous secondary battery of the present invention, the amount of dopant doped into the aniline or aniline derivative polymer is 1 repeating unit of the aniline or aniline derivative polymer.
It is 10 to 100 mol%, preferably 20 to 100 mol%, based on the mole.

The amount of doping can be freely controlled by measuring the amount of electricity flowing during electrolysis. The doping can be carried out either under constant current, constant voltage or under varying conditions of current and voltage.

In the present invention, the effect of treating a polymer of aniline or an aniline derivative with an alkali is extremely remarkable. This may be because the removal of impurities, ineffective dopants, excess electrolytes, oligomers, etc. is more effective than in aniline or aniline derivative polymers that are not treated with alkali. It is not clear what contributed greatly, such as whether alkaline treatment could effectively improve the material to make it suitable as a battery positive electrode.

However, when we actually used aniline or aniline derivative polymers treated with alkali or not as electrodes and compared the electrode properties such as electrode capacity, we found that aniline or aniline derivative polymers treated with alkali It showed extremely good electrode properties compared to polymers of aniline or aniline derivatives that do not contain aniline or aniline derivatives.

This can be interpreted as not only the effect of simply removing impurities etc. in the polymer, but also the effect of improving the structure and mechanism of the polymer.

In other words, when a polymerized aniline or aniline derivative that is not treated with alkali is used as an electrode, the dopant is not completely released even if it is discharged to a certain discharge end voltage, similar to the polymer of aniline or aniline derivative treated with alkali. It is presumed that the discharge was terminated by a mechanism that contained a considerable amount of dopant inside the electrode. However, it is thought that the polymer of aniline or aniline derivative treated with alkali has extremely low residual dopant at the end of discharge, and most of the dopant can be released until reaching the same end-of-discharge voltage as the polymer not treated with alkali.

The non-aqueous secondary battery of the present invention has a higher energy density than existing Ni/Cd batteries and lead-acid batteries, good reversibility of charging and discharging, and an extremely low self-discharge rate. Demonstrates high performance battery characteristics.

In addition, non-aqueous secondary batteries that use alkali-treated aniline or aniline derivative polymers as positive electrodes have a lower charge rate than non-aqueous secondary batteries that use aniline or aniline derivative polymers that are not treated with alkali as positive electrodes. It has battery performance with extremely low self-discharge rate, large electric capacity, and high energy density.

EXAMPLE 1 The present invention will be explained in more detail below with reference to Examples and Comparative Examples.

Example 1 [Manufacture of polyaniline] A platinum plate (15#φ, diameter 0.5M
A constant current density of 1.0 Tr is applied on the surface of
Electrolytic polymerization was performed using LA/crtt2. In this case, a platinum plate with the same diameter as above is used as the counter electrode, and ACt/A is used as the reference electrode.
gC! J, poles were used.

When the polymerization was stopped when the electrolytic polymerization electricity amount reached 20 coulombs, a total weight of 9.5 m' was deposited on both sides of the platinum plate.
A film-like polyaniline in which dark green fibrils were entangled was obtained. The average polymerization potential is Ag/A(+
It was 0.74V with respect to the On reference electrode.

[Processing of polyaniline]

The film-like polyaniline obtained by electrolytic polymerization on a platinum plate is immersed in distilled water for about 30 minutes together with the platinum plate to wash away the incorporated acids, and then the film-like polyaniline is placed in ammonia water with a concentration of 28 wt%. The whole board was soaked for about 1 hour. While immersed in ammonia water, ultrasonic waves were applied for about 1 minute. Next, the polyaniline film together with the platinum plate was transferred to distilled water, and the above operation was repeated twice. Finally, the polyaniline film together with the platinum plate was washed with distilled water for about 1 hour, and the pH of the washing water was 7.2.

Next, it was dried under reduced pressure at 80° C. for 4 hours.

The amount of polyaniline after drying was 5.9 mg and had a purple color.

[Experimental cell configuration]

The polyaniline obtained on the platinum plate by the above operation was used as the positive electrode, and the platinum plate itself was used as a current collector, and the negative electrode was placed on a nickel wire mesh with 100 ml of alloy powder with an atomic ratio of Ij and A1 of 50:50. A nickel wire was pressure-molded at 350° C. into a 15 #φ shape, and a nickel wire was pulled out from the negative part of the nickel wire mesh to serve as a negative electrode lead wire.

As an electrolyte, 1 mol 1 m degree of Li BF4 is mixed with PC (propylene carbonate) and DME in a volume ratio of 1:1.
(1,2-dimethoxyethane) dissolved in a mixed solvent was used.

The experimental cell shown in FIG. 1 with the above configuration was used.

[Battery performance test]

First, heat the assembled battery for 5' until the voltage reaches 2.0■.
Although it was discharged with baking soda at a constant rate of rrLA/α2, almost no current flowed. Next, the battery was immediately charged at the same current density until the battery voltage reached 4.3 V, and the above operation was repeated under the same conditions. At the fourth repetition, both the amount of electricity charged and the amount of electricity discharged become almost constant, and the amount of electricity is 3.22 coulombs, which is 51 mol% per monomer unit (91 g) of positive electrode polyaniline. This is a calculation that allows the dopant to be charged and discharged.

After that, after repeating the above charging and discharging,
The charging/discharging efficiency was almost 100%, and even at the 200th cycle, the same amount of electricity could be charged and discharged as at the 4th cycle. Further, after charging for the 201st cycle, the battery system was left in an open circuit for 720 hours, and the electrical efficiency was 6.5%. The electric capacity density per positive electrode weight at the 200th repetition of this battery is 151Ah/Kg, and the energy density is 4
50wh/to'lc0 Comparative Example 1 [Manufacture of polyaniline] Polyaniline was manufactured in the same manner as in Example 1, and the weight of polyaniline obtained by polymerization on a platinum plate was the same as in Example 1. It was exactly the same, 9.5m9.

[Processing of polyaniline]

The polyaniline obtained by electrolytic polymerization on a platinum plate was immersed together with the platinum plate in distilled water for 1 hour, and during the immersion, it was washed with ultrasonic waves for about 1 minute. After that, the distilled water was replaced and the above washing was repeated three times, and the final pH of the washing water was 6.
．． It became 8.

Next, the polyaniline was dried under reduced pressure at 80° C. for 1 hour, and then washed again with distilled water for 1 hour. pH of distilled water after this washing
was 6.8, which was the same as the DH of the washing distilled water before drying.

Next, polyaniline was dried together with the platinum plate under reduced pressure at 80°C for 4 hours, and the weight of polyaniline after drying was 9.
．． It was Omg.

[Battery performance test]

Battery characteristics were investigated under exactly the same conditions as in Example 1 using the same electrolytic epidemiology and experimental cell as in Example 1.

The amount of electricity discharged for the first time was different from Example 1, and was 2.16.
The amount of electricity in coulombs was obtained. Thereafter, charging and discharging were repeated in the same manner as in Example 1, but the amount of electricity for charging and discharging reached a nearly constant value at the fourth cycle, and the value was 2.87.
It was Coulomb.

This amount of electricity is equivalent to the initial discharge amount of 2.15 coulombs.
When calculated considering the net positive electrode polyaniline weight as 7.0 IItg, which is the value obtained by subtracting the i-dopant weight from the polyaniline weight of 9.0η, it corresponds to a doping level of 39 mol %. Thereafter, when the battery was repeatedly charged and discharged under the same conditions, the charging and discharging efficiency remained at almost 100%, but the amount of electricity charged and discharged at the 200th cycle was 2.82 coulombs.

Further, when a self-discharge test was conducted for 720 hours at the 201st cycle, the amount of discharged electricity after being left was reduced to 2.19 coulombs. Self-discharge rate per month is 22%
Met.

In addition, the electric capacity density per positive electrode weight at the 200th repetition is 111Ah/Ng, and the energy density is 3
It was 9 in 32wh/.

Example 2 [Manufacture of polyaniline] Aniline concentration of 0.22 mol/further I N -1-I
While stirring 100 cc of C1 aqueous solution with a magnetic stirrer, 0.25 mol/cross equivalent of (
N+-14>28208 was added to chemically polymerize aniline. The obtained polyaniline was in powder form.

[Processing of polyaniline]

The powdered polyaniline obtained by the above method was transferred to distilled water and washed for about 30 minutes while stirring. Then I N
The polyaniline was transferred to a KOH aqueous solution and washed with stirring for about 2 hours. Next, it was washed with distilled water for 30 minutes while stirring, and the distilled water was replaced with fresh water and washed again for 15 minutes, and the pH of the washing water was 8.5. The washed polyaniline was then dried under reduced pressure at 80° C. for 4 hours.

[Battery performance test]

Li8 at a concentration of 1 mol/1 as in Example 1 was used as the electrolyte.
F4 dissolved in a mixed solvent of PC and DME at a volume ratio of 1:1 was used. In addition, the obtained polyaniline 10R
A mixture of g and acetylene black 1.5 cm was placed on a platinum wire gauze and pressure-molded into a disk shape of 105*φ.
Although the battery was discharged with low sodium bicarbonate (No. 2) until the voltage reached 2.0V, almost no electricity was obtained.

This was then used for the positive electrode, and for the negative electrode by Takashi Yamamoto and Akio Yamamoto, Chemical Letters, 1977, p. 353 ('
/amamoto, T and Yamamoto, A
, chem, Leet.

1977.353), polybara phenylene powder synthesized from dibromobenzene using a Grignard reagent, 15η, and acetylene black i, s* were mixed, and this mixture was placed on a nickel wire mesh to form a 10#φ
The battery characteristics were investigated using the experimental cell shown in Figure 2, with a polypropylene diaphragm impregnated with an electrolyte sandwiched between the positive and negative electrodes. The current density for charging and discharging was set at 1 mA/cm2, and the battery was first discharged in the discharging direction until the battery voltage reached 2.0 square meters, and then charged at the same current density until the battery voltage reached 4.5 square meters. Hereinafter, repeated charging and discharging tests were conducted under the same conditions.

At the fifth cycle, a nearly constant amount of charge/discharge electricity is reached, with a value of 6.15 coulombs, which corresponds to a doping level of 58 mol% for the polyaniline cathode, and for the polyparaphenylene cathode. This corresponds to a doping level of 32 mol %. This battery was able to charge and discharge almost the same amount of electricity as the 5th charge and discharge even after the 50th cycle, and when a 720-hour self-discharge test was conducted at the 51st cycle, the self-discharge rate was approximately 1 month. It was 10%.

Energy density per positive and negative electrode type set (excluding carbon black) after 50 cycles of this battery, 198
vth/Kfl.

Comparative Example 2 [Processing of polyaniline] Polyaniline obtained by polymerization in exactly the same manner as in Example 2 was first washed in distilled water with stirring for 30 minutes, and then
The distilled water was replaced and washing was repeated three more times in the same manner. This was dried under reduced pressure at 80°C for 4 hours, and after further drying,
It was washed for 30 minutes with a mixed solvent of PC and DME in a volume a ratio of 1:1, and then dried under reduced pressure at 80° C. for 2 hours.

[Battery performance test] A cell exactly the same as in Example 2 was used, and the positive electrode was made of polyaniline 15cm treated by the above method and carbon black 1.5cm.
Mix Rg, place this mixture on a platinum wire mesh, and
After compression molding, the cell used in Example 1 was heated to 2.0
When the battery was discharged with a constant voltage stand of 1771Δ/cm2, an amount of electricity of 2.15 coulombs was obtained. After that, when the net weight of polyaniline was measured, it was found to be 13.3m.
It was 9. Next, this was used as a positive electrode in the same manner as in Example 2, and 15 m'J of polyparaphenylene produced in the same manner as in Example 2 and 1.5 m9 of carbon black were mixed and molded, and a molded product was used as a negative electrode. The battery performance characteristics were investigated.

When the battery was subjected to a charging/discharging test under the same conditions as in Example 2, it reached a nearly constant electrical charge at the 6th cycle, and the value was 5.81 coulombs.

This amount of electricity corresponds to a doping level of 41 mol% for the positive electrode polyaniline and 30 mol% for the negative electrode polyparaphenylene.

The energy density per weight (excluding carbon black) of the positive and negative electrodes determined from the discharge curve of this battery at the 50th cycle was 165 wh/Kg.

Further, when a 720-hour self-discharge test was conducted at the 51st cycle, the self-discharge rate was 34% after approximately one month.

Example 3 Polymer fn polymerized and treated in exactly the same manner as Example 1
Using the same cell as in Example 1, using 5.8R9 polyaniline as the positive electrode, lithium metal was used as the counter electrode, and charging was carried out for 30 minutes at a constant voltage of 4.2 .ANG. The amount of electricity that flowed was 3.70 coulombs.

After charging, the polyaniline electrode was immersed in AN (acetonitrile) for 3 hours, washed, and then dried under reduced pressure at 80° C. for 4 hours, and the doping level was confirmed by weight measurement.

In addition, the polyaniline before and after charging was analyzed by elemental analysis and chemical analysis, and the doping level was determined as TMm.

The weight of polyaniline after charging was 9.0 Rg.

This weight increase was equal to the weight increase caused by doping polyaniline with BFi equivalent to 60 mol%, and almost corresponded to the electricity flowing during charging.

In addition, the atomic ratio of H, C, N, and F analyzed was 9.05: 12.01: 2.00 before charging.
: 0.22, and after charging it is 9.30 : 12
．． 05 : 2.00 : 4.85, and the ratio of F was almost the same as the amount of electricity charged when BF''4 was charged. Among the values of H in elemental analysis, Although the influence of moisture during analysis operations may be considered, H, C, N,
The weight ratio of the remaining elements other than F was 0.2% before charging and 5.0% after charging, and it was confirmed that almost no dopants were included before charging. Further, the value of 5.0% of the remaining element after charging, considering this as B in BF4, matched very well with the doping level determined from the amount of charging electricity.

Next, polyaniline with an initial weight of 5.8 cm was charged once at a constant voltage of 4.2 V for 30 minutes in exactly the same manner as above, and then the voltage was increased to 2.2 V with respect to the counter electrode lithium using a 0.1 mA/cm2 heavy stage. When it was discharged until Ov, the amount of charged electricity was 3.70 coulombs, but the amount of discharged electricity 1 was 3.70 coulombs.
It was 59 coulombs.

After washing this polyaniline electrode with AN in the same manner as above, it was dried under reduced pressure at 80° C. for 4 hours, and weight measurement and elemental analysis were performed.

The weight after charging and discharging was 5.9111 g, and P was equal to the weight before charging and discharging.

Also, the ratio of To1, C, N and F obtained by analysis is 9.20
: 6.03 : 1.00 : 0.05, it was confirmed that almost no BF4 remained.

Comparative Example 3 Using the same cell as in Example 3, a polyaniline electrode 9.1 wj obtained by manufacturing and post-processing in exactly the same manner as in Comparative Example 1 was used, and a voltage of 2.0 ■ was obtained with respect to the lithium counter electrode. After discharging with constant baking soda at 0 and 1' MA/crt+2, the polyaniline was washed with AN, and further dried under reduced pressure at 80° C. for 4 hours, and the weight of the polyaniline was measured.

2. The amount of electricity that was discharged to OV was 2.43 coulombs, and the weight of polyaniline after discharge was 6.9 rng.
Met.

In addition, the H, C, N, F
Analysis of the element ratio was conducted in the same manner as in Example 3.

The atomic ratio of H, C, N, and F in polyaniline before discharge is 1
1.50: 12.30; 2:00: 4
．． 02, which means that about 50 mol% of BFi is doped, but the weight of the remaining elements other than H, C, N, and F is 10.0%, and in addition to the dopant 8, A considerable amount of unknowns remained.

Furthermore, the atomic ratio of H, C, N, and F in polyaniline after discharge is 10.80:12.40:2.00:
1.29, and the value of this F is 16 when converted to BF4.
Corresponding to the doping level of mol %, polyaniline without alkaline cleaning treatment cannot completely release the dopant, or the remaining B
It was confirmed that F4 etc. were contained in large amounts.

Example 4 2,5-dimethyl-aniline was dissolved in a 1.5 mol/l concentrated HBF4 aqueous solution, and the concentration of 2,5-dimethyl-aniline was adjusted to 0.22 mol/fL.

Electrolytic polymerization was carried out under the same conditions as in Example 1 to obtain poly(2,5-dimethyl-aniline) on the surface of the platinum plate. The obtained poly(2,5-dimethyl-aniline) was washed with alkali in exactly the same manner as in Example 1, and dried under reduced pressure to obtain poly(2,5-dimethyl-aniline).
-dimethyl-aniline) was measured and found to be 6,
It was 3rng.

This poly(2,5-dimedyluaniline) was used as the positive electrode, Li metal crimped onto a nickel wire mesh was used as the negative electrode, and 1 mol/11 degrees of Li (, fL04 PC
The battery characteristics were investigated using a cell similar to that shown in Figure 1 using the liquid.

The set voltage and current density for charging and discharging were exactly the same as in Example 1.

This battery reached a substantially constant amount of charge and discharge electricity at the fifth cycle, and thereafter the amount of charge and discharge electricity hardly changed, and the amount of charge and discharge electricity at the 50th cycle was 3.12 coulombs. The energy density of this battery was calculated to be 410 wh//(g) per weight of the positive electrode.

Further, when a 720-hour self-discharge test was conducted at the 51st cycle, the self-discharge rate for about one month was 12%.

Comparative Example 4 Poly(2,5-dimethyl-aniline) polymerized under the same conditions as in Example 4 was washed in exactly the same manner as in Comparative Example 1, and dried under reduced pressure. The positive electrode was used, and Li metal was used as the counter electrode. The battery characteristics were investigated under the same conditions as in Example 4 using a cell similar to the cell shown in FIG.

The amount of electricity charged and discharged at the 50th cycle of this battery is 2,70
The energy density was calculated to be 302 Wh/Kg per weight of the positive electrode.

Further, when a 720-hour self-discharge test was conducted at the 51st cycle, the self-discharge rate for about one month was 27%.

[Brief explanation of drawings]

FIG. 1 is a schematic cross-sectional view of a glass cell for battery experiments with a sealed lid, which is a specific example of the present invention, and FIG. It is a cross-sectional schematic diagram. 1...Platinum lead wire 2...Reference electrode 3...Working electrode 4...Counter electrode 5...Electrolyte
6...Glass airtight lid 7...Glass battery cell 8...Negative electrode lead wire 9...Negative electrode current collector
10... Negative electrode 11... Porous polypropylene separator 12... Positive electrode 13...
Positive electrode current collector 14... Positive electrode lead wire 15... Teflon container Fig. 1 Fig. 2

Claims (1)

[Claims] Using aniline or aniline derivative polymer for the positive electrode,
In a nonaqueous secondary battery using an alkali metal, an alkali metal alloy, a conductive polymer, or a composite of an alkali metal alloy and a conductive polymer as a negative electrode, the aniline or aniline derivative polymer is treated with an alkali. A non-aqueous secondary battery characterized by: