JPS58112247A - Battery and storage battery using high molecular compound carrying iodine holding power as electrode - Google Patents

Abstract

PURPOSE:To secure a battery and a storage battery whose internal pressure is not so large, by using an additional body of polymers (2,5-thienylene and 3- methyl 2,5-thienylene) as a main component in a positive black mix. CONSTITUTION:A polymer (2,5-thienylene) (hereinafter referred to as a polymer A) making a radial shown in a separate chemical equation as a repeating unit or a polymer (3-methyl 2,5-thienylene) (hereinafter referred to as a polymer B) or matter coated on a current collection body composed of carbonic fiber-make cloth, platinum, etc., with matter containing these polymers or matter forming these polymers A and B is set to a positive pole, using metal iodide as electrolyte, then equivalent metals are used for a negative pole and a storage battery is thus produced. In charging the battery, DC voltage is applied and when iodine is separated at the positive side and metal at the negattive side is as well separated respectively, the extracted iodine at the positive side makes up an additional body with the polymer A or the polymer B. Afterward, when the DC voltage is disconnected and both poles are connected by a lead wire, discharge is produced and electric power is thus obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION Iodine is a substance that easily becomes an anion and is one of the materials suitable as a positive electrode active material for batteries and storage batteries. However, despite this, there are not many examples of producing batteries using iodine as a positive electrode active material. The present invention uses poly(215-chenylene) (hereinafter abbreviated as polymer A) and poly(
It is easy to form an adduct with 3-methyl 2,5-thennylene) (hereinafter abbreviated as polymer B), and this adduct has a certain degree of electrical conductivity. The content of this study is to fabricate a battery using a substance whose main component is an adduct as a positive electrode mixture, and to apply this battery to a secondary battery (storage battery).

Polymer A and Polymer B have a π-electron conjugated system along the main chain, and since they use sulfur-containing groups as repeating units, they form strong adducts with iodine, resulting in a decrease in the weight of one polymer. #1 The property of strongly absorbing the same superimposed iodine weakens.

Furthermore, the adduct of this polymer and iodine has a certain degree of electrical conductivity.

The present invention takes advantage of this fact in the production of batteries and storage batteries, thereby producing batteries and storage batteries whose internal resistance is not so large. Furthermore, in the storage battery of the present invention, iodine produced at the anode by electrolysis of metal iodide during charging is strongly absorbed by polymer A or polymer B. The negative electrode body of the storage battery uses the same metal as the metal produced at the cathode during electrolysis of the metal iodide. Next, a general method for manufacturing the battery described in the present invention will be described.

First, a predetermined amount of polymer A or polymer B.

Alternatively, iodine is added to materials containing these polymers. As a method for this addition, a method of contacting with iodine vapor, a method of immersing in a solution containing iodine, a method of kneading iodine, etc. are used. Polymer A thus obtained
Or Polymer B.

Alternatively, a battery is produced by iodine with a substance containing these polymers and using a solution of zinc iodide, 1ac1, etc. as an electrolyte solution.

In addition, storage batteries are made of polymer A, polymer B, or a substance containing these polymers coated on six current collectors such as carbon fiber cloth or platinum plates, or polymer A,
When a molded material of Polymer B is used as a positive electrode and a metal iodide is used as an electrolyte, the iodine deposited on the positive electrode side forms an adduct with Polymer A or B. After this, if the DC voltage is turned off and the 9 poles are connected with a conducting wire, a discharge will occur and a stain force will be obtained.

Example 1 16 mg of Polymer B having a molecular weight of 2.400 was dissolved in chloroform 2- and applied to a rectangular platinum plate of lσ×2ffi, and the chloroform was removed by natural evaporation. Next, when this film-like polymer B was exposed to iodine vapor at room temperature for 2 hours, 6 g of iodine was absorbed into the polymer B. Using this adduct of polymer B and iodine, the first
When the battery shown in the figure was assembled, the electromotive force of L3V and 10m
The open circuit current (initial value) of A was obtained. In the case of this example,
In Fig. 1, the current collector is a platinum plate, and the electrolyte solution is 0. A 1.5 (7) x 351 glass filter paper (GA100 type) manufactured by Toyo Roshi Co., Ltd. was impregnated with an aqueous solution of OsW1ol/1 of ZnK2. Also,
A zinc plate of IIMX2m was used as the metal plate.

Example 2 Chloroform-insoluble powdered polymer A326m1F,
When exposed to iodine vapor for two days in a vacuum at room temperature, 161
Absorb Q's iodine. One of the obtained iodine adducts
00Q is taken and solidified at a pressure of 60oky/cd at room temperature using a molding machine manufactured by Shimadzu Corporation (hereinafter referred to as a molding machine).

A steel wire is bonded to one end of the disc-shaped solid body having a diameter of 1.3 cr IH thus created using a conductive resin (mleatroaag +502 sold by Furuuchi Chemical Co., Ltd.).

Next, a battery similar to that shown in FIG. 1 is assembled using this disk-shaped solid material as an anode and a metal plate as a cathode. However, in the case of the 9-piece collection embodiment, the current collector is not used in Figure 1, and the conductor for obtaining power is directly connected.

It is connected to a positive electrode mixture consisting of polymer A and iodine, and an aqueous Mg (NO3) 2 solution (o, o s,
rno'vl) and soaked it into Toyo Roshi Co., Ltd.'s sub-glass J door paper (GA100 type),
1.3v was obtained as an electromotive force, and 2m was obtained by the ammeter.
The electrolyte solution that was confirmed to have a current of
1 aqueous solution (0.32 mOv'l) or KC1 aqueous solution (0.35 mOvl), similar electromotive force and current values were obtained.

Example 3 Nirotsu-6 with a molecular weight of 30.000 was taken in 87j+9 and dissolved in formic acid 1-. This solution and 22 cm of chloroform-insoluble polymer A were mixed in an agate mortar to obtain a paste-like solution. This solution was uniformly applied to a conductive circular carbon fiber cloth with a diameter of 5 crn.

Formic acid is removed by natural evaporation. Next, when the coated surface of the mixture of this polymer and nylon-6 was brought into contact with a benzene solution of iodine (0,y 7 fl/100 mol) for 12 hours, 30 units of iodine were absorbed. When the device shown in Figure 1 was assembled using this polymer and iodine adduct,
An electromotive force of 1.3V and an open current (initial value) of 50V were obtained. In addition, using two of these batteries connected in series, a light emitting diode that emits light with an amount of current of 50
I was able to turn on the light continuously for several minutes. In the case of this example.

In Fig. 1, the current collector is made of carbon fiber cloth, and the electrolyte solution is a ZnI2 aqueous solution of 0.08 mol/l. GAIQO type). A zinc plate with a diameter of 5 cm and a thickness of 0.3 m was used as the metal plate, and the apparatus shown in Fig. 1 was placed under nitrogen gas to avoid the influence of the air battery.

Example 4 Polymer A and polymer B were molded using a molding machine in the same manner as in Example 2, and batteries similar to those in Example 2 were assembled using various electrolyte solutions and metal plates. The results shown in the table below were obtained. The polymer used was about 100cm, and 10-5011I? of iodine was added. Electrolyte concentration is 0.03-m Polymer Negative electrode
Electrolyte solution Electromotive force (V)l Poly?
-AMgKer aqueous solution 1.52 Polymer A Ni, Ni engineering water aqueous solution
0.63 Polymer B O(l
C+(lI2 aqueous solution 084 Polymer B Co 0OI2
0.75 Poly W B Zn
ZnI2 Propylene Carbonate Solution 09 Example 5 Polymer B having a molecular weight of 4400 is taken as 60Q and dissolved in chloroform 10-. This solution is uniformly applied to a conductive circular carbon fiber cloth having a diameter of 5 cIn, and the chloroform is removed by natural evaporation. This material is used on the positive electrode side, and the second
The storage battery shown in the figure was assembled. In the case of this embodiment, the current collector in FIG. 2 is made of carbon fiber cloth. Also, as the metal iodide, an aqueous solution of zinc iodide (0.1 mol/l) was used, and the diameter was measured. +, 5 t'm glass filter paper manufactured by Toyo Roshi Co., Ltd. (GAI00 type) was soaked. A □ zinc plate with a diameter of 5yn and a thickness of 0.3 ml+ was used as the metal plate, and the apparatus shown in Fig. 2 was placed under nitrogen gas to avoid the influence of the air battery. Using a galvanostat model HA-301 manufactured by Hokuto Denko Co., Ltd., I Q OmA was conducted with the poly-r-B side (including the current collector) as the anode and the metal plate side as the cathode
After charging for 2 minutes at a current of 200 volts, the DC power source was removed as shown in FIG. 2, and when the polymer B side (including the current collector) and the metal plate side were connected, an electromotive force of 1.3 V was obtained.

It was possible to apply it to storage batteries).

[Brief explanation of the drawing]

FIG. 1 is a diagram of the battery device. 1 is the current collector, 2 is the polymer A
1 is a positive electrode mixture consisting of an adduct of polymer B and iodine, 3 is an electrolyte solution impregnated into a fibrous material, 4 is a metal plate, and 5 is a voltmeter or an ammeter. FIG. 2 is a diagram of the storage battery (currently being charged). l is the current collector, 2
indicates polymer A or polymer B, 3 indicates metal iodide impregnated into a fibrous material, 4 indicates a metal plate, and 5 indicates a DC power source for charging. Patent applicant Takashi Yamamoto - Figure 1 Figure 2

Claims (1)

[Claims] Poly(2゜5-chenylene) and poly(3-methyl-2,5-chenylene) having the group represented by as a repeating unit
Preparation of a battery characterized in that an adduct of