JPS60186564A - Iodized electrical conductor - Google Patents

Abstract

PURPOSE:An electrically-conductive resin composition containing iodine useful as a positive electrode material of cell having no change in electrical conductivity by change of iodine content, having improved electrical conductivity, obtained by dispersing a carbonaceous material into a complex adduct of a specific polymer with iodine and/or a composition obtained by dispersing iodine into the polymer. CONSTITUTION:A complex adduct of a polymer (e.g., polyacrylonitrile, PAREKUSU resin, etc.) bondable to iodine to form a complex compound and/or a composition obtained by dispersing iodine into the polymer is blended with usually 0.5-60wt% carbonaceous material (e.g., carbon black, graphite, etc.).

Description

[Detailed Description of the Invention] The present invention provides an adduct of iodine and a polymer capable of forming a complex compound with iodine, and/or an adduct of a polymer capable of forming a complex compound with iodine in a form J. This invention relates to a conductive 1gl resin composition made of a polymer in which iodine is dispersed and carbon is mixed therein.

Iodine tends to become an anion, and the positive electrode is
1 Of course, it is one of the suitable ones.

This iodine is known to form charge transfer complexes with various organic compounds. Charge transfer complexes of iodine consist of iodine (acceptor) and various electron-donating compounds (organic donor components); electron-donating compounds include heterocycles such as phenothiazine and carbazole; Poly2-vinylpyridine, polyvinylpyrrolidone, polyacrylonitrile, polyethylene,
Polymers such as polypropylene, polymethyl methacrylate, polystyrene, polyamide, polyurethane, polyvinyl alcohol, polyacrylamide, polyether, polyacetylene, polyparaphenylene, polypyrrole, and polyaniline are known.

Each of these charge transfer complexes has a large increase in conductivity compared to the original simple substance. It has been put into practical use as a positive electrode mixture. On the other hand, in recent years, polyacetylene, polypyrrole, polyaniline, polyparaphenylene, and the like have been actively developed as conductive compounds. It is known that the electrical conductivity of these compounds can be increased by doping them with aluminum. However, it has various problems, such as being easily damaged by oxygen, etc., being unstable, and having poor stability.

In particular, when these charge transfer complexes are used as a cathode mixture for a battery, the cathode mixture gradually loses its conductivity because iodine is released as it is discharged.

For this reason, as discharge progresses, the resistance of the positive electrode mixture increases significantly, resulting in a significant decrease in the electromotive force of the battery.

In addition, when a positive electrode mixture made of this charge transfer complex is used in a secondary battery, most of the iodine is released from the positive electrode mixture upon discharge, so the positive electrode mixture usually becomes an insulator. As a secondary battery, it has a decisive drawback: it cannot be recharged. This is polyamide, polyacrylonitrile, polyvinyl alcohol,
This problem frequently arises when using iodine complexes of polymers that are originally insulators, such as polyether and poly-2-vinylpyridine.

The present inventors have made intensive studies to overcome the drawbacks of the charge transfer complex, and have found that the above drawbacks can be overcome by creating a composition in which carbon is added to the complex positive electrode mixture, and also, For example, they have developed a complex adduct of a polymer capable of forming a complex adduct with ions and/or a composition in which iodine is dispersed in the polymer, which is excellent when used as a positive electrode mixture for a battery. This invention provides an iodine-containing conductive resin composition in which carbon is dispersed.

In the present invention, polymers capable of forming complexes with iodine include polyacrylonitrile, balenox resin, polyvinyl alcohol, polyvinyl acetate, polymethyl methacrylate, nylon-6, nylon-6, 6. Particularly preferred are polyurethane, polytetramethylene ether, polyvinylpyrrolidone, poly-4-vinylpyrrolidone, poly-17-2-vinylpyridine, poly-N-vinylcarbazole, polytetrahydrofuran, etc., but of course it is not limited to these. isn't it.

Furthermore, it goes without saying that two or more of these may be used as a blend or a combination of these may be used.

Next, general preparation of the conductive 1-1 fat composition of the present invention/7
．． : Explain about. First, a predetermined amount of the iodine is added to a polymer with a proboscis-forming egg to form a dispersion of carbon.
Contains this. Methods for adding carbon chains include dissolving the polymer in a solvent, adding carbon to this mixture, and then removing the solvent, or directly cross-dispersing carbon into the polymer. . Iodine is added to the polymer-carbon composite thus obtained.

Examples of the iodine addition method 7 include (1) a method of bringing iodine vapor into contact with a polymer carbon composite such as the one shown in 111 above, and (2)
) a method of soaking a polymer carbon composite in a solution containing iodine;
(3) Alternatively, there is a method in which iodine is melted and underlined into a polyamide carbon composite. [6] Instead of preparing the polymer-carbon composite in advance, a method can also be adopted in which carbon and iodine are added to the polymer of χ1 at the same time and kneaded in a dispersed state to prepare the positive electrode mixture in one step. In this case, the order of addition or mixing 111d of the substances added for kneading is! +!
There is no limit to f.

That is, in short, it is only necessary to make a composite in which carbon is dispersed in a complex additive of a polymer and iodine and/or a dispersion composition of iodine, and the method for making it is not particularly limited. do not have.

Carbons added in the present invention include carbon blank, acetylene black, graphite, Ketjen black (trademark of AK7.O), etc.
Easily dispersible shapes such as flakes and short fibers are preferably used. 19 of carbons! Of course, the use varies depending on the type of carbon, but it is usually 0.5 to 60% (weight + 1%, same below) for the polymer to be added, and for Ketjenblack, it is 0.5% to 50%. For crushed graphite products, it is 0.05 to 40%. Below this value, the efficiency of fed batch is low, and the conductivity decreases rapidly at low iodine content, and even if it is used above the above value, the effect will not improve any further and moldability will deteriorate. . /,"oh,
For example, in the case of a Ketjen blank, 5 to 40% is more preferable, and 10 to 60% is particularly preferable.

The iodine-containing 1-conductive resin composition of the present invention does not lose its conductivity even if 141L of iodine is removed. II. When used as a positive electrode mixture for a battery, the electromotive force of the battery can be maintained constant even as discharge progresses.

The iodine-containing resin composition of the present invention has excellent electrical conductivity and conductivity due to iodine-containing ants.
It hardly changes, and since it is mainly made of plastic, it has excellent processability, so it can be used as a positive electrode mixture for batteries, electrolytic capacitors, conductive films, etc. ″1111,4′：
It is possible to suitably apply it to various fields such as L plastic plates.

The present invention (・i1″1(/This is inexpensive, large-scale production, processing ↑
When applied to iodine charge transfer complexes of polymers such as polyacryloni, 1-11, polyether, polyvinyl alcohol, polyamide, polyurethane, etc. Its practical effects are clearly demonstrated.

For example, to use this composition as a positive electrode mixture for batteries, it can be molded into an appropriate shape as the positive electrode, and metals such as lithium, aluminum, magnesium, zinc, cadmium, etc. can be used as the negative electrode. All you have to do is insert an ion conductor between them and bring them into contact.

In addition, the composition can be used as a wet water solution, suitable for batteries.
In this case, a positive electrode made of the composition and a metal negative electrode may be brought into contact with each other via a liquid electrolyte. At this time, in addition to the electrolyte generated by the discharge, ammonium chloride, arsenic salt, zinc chloride, sodium bromide, IJ bromide, lithium iodide, and iodide May be used.

Furthermore, it is convenient to sandwich a porous separator between both active materials to prevent self-discharge.

In addition, if it is applied to a wet type non-aqueous battery, for example, when lithium or sodium is used as the negative electrode, it is possible to use a less reactive heating medium such as propylene carbonate or 1-butyl lactone. - It is preferable to Further, it is convenient to use the metal iodide molten in these melts by impregnating it into a porous material having a large liquid-holding capacity, such as a short glass fiber mat, which serves as a support. A battery can be assembled by sandwiching such a porous electrode impregnated with an electrolyte between a positive electrode and a negative electrode made of the above-described composition of the present invention.

Furthermore, since this is applied to a single cell battery, the positive electrode mixture and the negative electrode metal may be brought into contact via a solid electrolyte thin film, if any.

Hereinafter, the implementation of the present invention will be explained according to Example 9jl! I will explain the law in more detail, but these are just examples.
The technical scope of the present invention stipulated in Article 70 of the Patent Law is ill! It must not be construed as limited.

Example 1 Polyacrylonitrile (average molecular weight 152,000) 8
(weight i1'1-1 and below the same) was dissolved in dimethylformamide, and Ketjen-Pluck old 3-180 (AK2
0 Company Trademark) was added, the mixture was well dispersed, and the dimethylformamide was removed by ξ evaporation method to obtain a black composition.

After pulverizing 10 parts of this composition, the iodine-containing conductive composition A of the present invention was obtained by cross-dispersing iodine and changing the iodine-containing attractiveness.

σ Electrical conductivity of this composition at room temperature (25°C): 1 (, Scm) is shown in FIG.

For comparison, the results of similar measurements were also shown in Figure 1 for the composition UK, which was prepared in the same manner except for Ketjenblack's application.

Example 2 7.2 parts of polyvinyl alcohol (Cran Co., Ltd. J4J) (width, same hereinafter) and 08 parts of polymelamine resin Cymel 30 filter (trademark of Mitsui Toatsu Co., Ltd.) were dissolved in water [dissolved] and added to 2 parts of this aqueous solution. Ketjen Blank KB2 IQO was added and dispersed well. The water was removed by evaporation and the black composition was
I was. After crushing this composition, add 100 ml of 72 parts of iodine from 8 parts of A to three 1] V flasks, seal tightly under reduced pressure, and dissolve hXH at 140"C under pressure.
1 state, cross-disperse iodine and change the iodine content.The iodine-containing core composition A of the present invention is then
)1. two.

Figure 2 shows the conductivity σ ・(Sc+i') of this composition 9 at the IA temperature (25°C).
The results for Composition BK, which was prepared in the same manner as Shima except that Ketjenblack was not added, are also shown in FIG.

Example 6 Nylon-6 (manufactured by Toshiku Co., Ltd.) 8 parts (middle box, same below)
Dissolve in formic acid and add Ketjen Black K1l-180.
(A KZO Co., Ltd.) 2 parts were added, and the liquor was removed by a well-dispersed evaporation method to obtain a black composition. After grinding this composition, 8 to 72 parts of iodine were added to 100 parts of iodine.
Put it in a melting flask and seal it under reduced pressure.
The iodine-containing conductive composition A of the present invention was obtained by bringing it into a molten state at 115"C below 1' and varying the iodine content by dispersing iodine.

6C') Mi5. ni'4'llJ''pa'''' (25-
C) K? +64N, *・(Scm) is shown in Figure 6.

For comparison, the results for Composition 13Vc, which was prepared in the same manner except that Ketjen black was not added, are also shown in FIG.

Example 4 Polymethyl methacrylate (average molecular weight 152 aoa
) Dissolve part a (-weight, same hereinafter) in taX-resistant chill, Ketjen Black I (+1-E(j (AKZ
2 parts of O Company trademark) were added, and ethyl acetate was removed by a well-dispersed evaporation method to obtain a black composition. After crushing this composition, add 72 parts of iodine from 8 parts to 100 ml of each.
Pour 5 liters into a flask, seal tightly under reduced pressure, and stir while stirring.
Iodine was dispersed in a melted state at 5"C, and the iodine content was varied to obtain the iodine-containing conductive composite acid of the present invention.

Electrical conductivity of this composition at room temperature (25°C)* (S
Ca11') is shown in FIG.

For comparison, 11 except without adding Ketjenblack.
The results for the composition BK created using the old SF are shown in the 41st page.
Shown in conjunction with section 1.

Example 5 8 parts (amount taken, same below) of polyvinylpyrrolidone (average molecular weight 163000) was dissolved in tetrahydrofuran,
Ketjen Black+<, nL-igc (AKZO
Two parts of Row 1 (Nara Slip) were added, the mixture was well dispersed, and the tetrahydrofuran was removed by evaporation to obtain a black composition.

After pulverizing the composition, 8 parts to 72 parts of iodine were respectively placed in 100 m65 flasks under reduced pressure and airtight, and stirred at 115"C to make it ready for dissolution. The iodine was dispersed. An iodine-containing conductive composition A of the present invention was obtained in which the iodine-containing needle was changed.

The electrical conductivity of this composition at room temperature (25"C) elk
(S c+++ ”) wof, 5 Figure IFI shows.

For comparison, the results are shown in Figure 5 (C
Also shown.

Practical IN Example 116 Poly 2-vinylpyridine (average molecular weight 8.0000)
8 parts (weight, same below) of tetrahydrofuran VcM
Kashi, Ketchen Black K 13-1 (0 (AKZ
After adding 2 parts of Tetrahydrofuran (Trademark of Company O) and thoroughly dispersing the mixture, tetrahydrofuran was removed by evaporation method to obtain a black composition. After pulverizing this composition, 8 to 72 parts of iodine (3 100 mg) were placed in each flask, sealed tightly under reduced pressure, and melted at 115°C with stirring to disperse the iodine. This is the iodine-containing conductive composition A of the invention.

This composition was tested at room temperature (25'IC).
CIll) is shown in FIG.

For comparison, the result of Composition B) (Z-1), which was prepared in the same manner except that Ketjenblack was not added, is also shown in FIG.

Example 7 Polytetramethylene ether (reduced viscosity in 0.1% benzene solution 1.12; T, 01su, cl
ad.

Makranol +' Ohem, 171 150
(1964) )' 8 parts were dissolved in ethyl cellosolve acetate and 0. (A
Ethyl cellosolve acetate was removed by evaporation method to obtain a black composition. After crushing this composition, 7 parts from 8 parts each.
The iodine-containing conductive material of the present invention was prepared by placing 2 parts of iodine into a flask, sealing it under reduced pressure, and melting it at 115''C under stirring to remove the iodine. Take 1 serving of sexual composition A.

The electrical conductivity F at room temperature (25”C) for this set 1j2
5can 1) is shown in FIG. For comparison, Figure 7 also shows the results for Composition B, which was prepared in the same manner except that Ketjenblack was not added.

Example 8 3-J-1: A polyurethane prepared by combining 4.2 parts of tolylene diisocyanate (1-(T old-8'0/20) manufactured by IE Ru Urethane Co., Ltd. and 38 parts of tripropylene glycol) was prepared. Dissolved in phenol, added 2 parts of Ketjen Plack KB-"O (trademark of AKZO Company) and dispersed well. Phenol was removed by evaporation method, resulting in a black composition: ↓). After pulverizing this composition, , put 72 parts of iodine into 13 100 m flasks from 8 units 1s,
The mixture was sealed under reduced pressure and melted at 150''C to obtain an iodine-containing conductive composition A of the present invention in which iodine was dispersed and the iodine content was changed.

The electrical conductivity of this person at room temperature (25℃)! -(S
' cm 5 is shown in FIG. 8. For 1-0 comparison, the results for Composition B, which was prepared in the same manner except that Ketjenblack was not added, are also shown in FIG.

As is clear from the above examples, the iodine-containing conductive resin composition of the present invention has the outstanding feature that its conductivity hardly changes depending on the iodine content and exhibits high conductivity.

This effect is particularly greatest when the composition has a low iodine content, and can be said to be a very desirable 4-'1 when applied to battery positive electrode mixtures and electrolytic capacitors.

However, resin compositions that do not contain carbon have low conductivity even when the iodine content is high, and the conductivity decreases rapidly as the iodine content decreases, making them suitable for positive electrodes in batteries and storage batteries. It is very difficult to apply it to a mixture or an electric 1'l'r condenser! It can be seen that it is lG.

Example 9 Polyacrylonitrile (average molecular g: 152000
) 24.9 was dissolved in dimethylformamide Km, and 6 g of Ketjen Blank KB-IJO (trademark of AKZO) was added and well dispersed. Dimethylformamide was removed by evaporation to obtain a black composition. After crushing this composition soy, 100n+/? with 3oy of iodine. Put it in a third flask, seal it under reduced pressure, and add 1.j, el-f'-F.
The mixture was brought to a mixed state at 14 U'C and mixed with iodine to obtain a 1-fat composition of the present invention.

This composition 60 Q yng was applied to a disk-shaped carbon fiber assembly (IU-715 manufactured by Kureha Kasho (Makashi)) with a diameter of 4.5 cm, and this was used as Ll [pole].

The negative electrode was a 0.3 nna thick Jlj lead plate (manufactured by Mitsui Kinzoku Co., Ltd.).

tun, uJt (=(nightkl: NIi, Od) 1 mol/
7J
ml, and a Selemion OMV membrane manufactured by Asahi Glass Co., Ltd. was sandwiched therebetween as a fake separator.

This material was placed between the two electrodes to form a battery.

The experiment was conducted at 25° C. under a nitrogen stream, and the initial short circuit current (Isc) during discharge was measured to be 767 ηA/crit. Further, the open circuit voltage at this time was 135V. When this battery was exposed to an im4 constant current, it could be discharged for 50 hours until the voltage dropped to 0.9V.

Also, use this battery as 2771. A constant current from 135V to 0
．． A charge/discharge test was conducted with a cycle of discharging to 9V for 15 hours and charging from 0.9V to 1.5V for 15 hours, and at least 300 cycles were possible.

This shows that this battery can be used not only as a primary battery but also as a secondary battery.

For comparison, a battery was made using Ketjen Black and a positive electrode mixture to which B-E C was not added, in exactly the same manner as described in Section 2, and evaluated under the same conditions. The initial short circuit current (Isc) during discharge of this battery was measured at 8 full A/
It was i. Also, is it open at this time? The pressure of 1 is 1.35
It was V. Furthermore, when I conducted a charging/discharging test, I was able to charge the battery after discharging, but the voltage rose so sharply that I was unable to charge it.

[Brief explanation of drawings]

1 to 8 are graphs showing the characteristics of the electrically conductive alcohol composition of the present invention. Particularly, ;i "Applicant Mitsui Toatsu Kagaku Co., Ltd. 1 - - → Yo 7 - Jg trial [14] Iodine smell - 1 Yu - m - - Su Yoi self-resistance - JR, Ko's Yo , Awl Chiku - Replacement Kidney 9゛℃ ←----Denko, + Gokino←---- Dimensions □+ 艷←---- Heavy Iton ~ Ding 〒 〒 〒 〒 Space Distortion ℃ Gu-m--ya call

Claims (1)

[Claims] (An iodine-containing conductive material obtained by dispersing carbon in a composition in which carbon is dispersed in a composition in which iodine and iodine are dispersed in a composition in which iodine is dispersed in a composition in which iodine is mixed with a polymer having an R potential to form a complex addition percentage.) 1☆l fat composition.