JPS61190871A - Battery - Google Patents

Abstract

PURPOSE:To prevent decrease in capacity and lengthen life by covering a conductive substrate to which electrically active polymer is bonded as a film with an electrically inactive resin film. CONSTITUTION:Polystyrene or polyethylene is used as a resin used for covering. When the surface of an electrode is covered with the resin by immersing it into a solution, the resin concentration in the solution is increased so that resin molecules are interwined each other in the solution. When it is covered by vapor deposition, the resin is placed in the bottom of a container, and the electrode is hung above the resin, and the container is heated under a reduced pressure. Adhesion of an electrically active polymer to a conductive substrate is increased, and decrease in capacity caused by repeated charge-discharge cycles is prevented and life is lengthened.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to virol, aryn, and thiophene.

The present invention relates to a battery using, as an electrode material, a polymer substance obtained by electrolytically polymerizing organic compounds such as azulene, indole, furan, iminostilbene, toluidine, carbazole, and benzofuran.

[Prior art and its problems]

Organic compounds such as rolls are electrolytically polymerized on a conductive substrate,
It is known that by using this as an electrode, a secondary battery with high energy density can be easily manufactured. However, because the adhesion strength of the polymer to the conductive substrate and the strength of the polymer are insufficient, the polymer may peel off from the substrate or the shape of the film may collapse during repeated charge/discharge cycles. , sufficient cycle life cannot be obtained.

The present invention has been made in view of these points, and has developed a battery that has a longer charge/discharge cycle life by increasing the strength of the electrically active polymer and increasing the adhesion strength to the substrate. It is something.

[Means for solving problems]

A battery using as an electrode an electrically active polymer substance synthesized on a conductive substrate by an electrolytic polymerization method, characterized in that the surface of the electrode is coated with a thin film of electrically inert resin. It's a battery.

The electrically active polymer obtained by electrolytic polymerization in the present invention includes aniline, aniline black, virol, thiophene, and indole.

Aromatic compounds and their derivatives such as azulene, furan, carbazoletoluidine, methylthiophene, methylvirol, or 1-naphthol, 5-
A substance obtained by placing a phenol derivative such as human oxy-1,4-naphthoquinone in a suitable electrolyte solution and performing 7-node oxidation on a conductive substrate set up as an anode. In particular, aniline is preferred as an aromatic compound and its derivatives.

Anrin Black, Birol.

The conductive substrate in the present invention may be any substrate as long as it does not dissolve at the electrolytic polymerization potential of an electrically active organic compound and to which a polymeric precipitate can adhere. Examples of the material of the conductive substrate include metal plates such as nickel, platinum, stainless steel, and copper, or meshes thereof, green graphite, amorphous carbon, activated carbon, and carbon miscellaneous materials.

Examples of methods for electrolytic polymerization on these conductive substrates include anodic oxidation using constant voltage or constant current, or repeated potential scanning.

As a method for coating an electrically active polymer electrodeposited in a film on a conductive substrate, the electrode is immersed in a solution of the resin used as the coating material in an appropriate solvent;
Alternatively, methods include heating a low molecular weight resin and depositing it on the electrode, or applying a resin melt.

Resins used for coating include polystyrene, polyethylene, polypropylene, paraffin, nylon, polyvinyl chloride, polyphenylene, polyphenylene sulfide,
Examples include phenol resins, and particularly preferred are polystyrene and polyvinyl chloride. When coating the electrode surface with these resins, the concentration of the resin must be large enough to cause overlap between resin molecules in the solution when immersing the electrode surface in the solution. In addition, when coating by vapor deposition, the coating material is placed at the bottom of a container that can be evacuated, an electrode is hung above it, and the bottom of the container is heated and evacuated, or the material is placed in a plasma polymerization reactor. Examples of methods include installing an electrode plate and synthesizing benzene, acetonitrile, etc. by plasma polymerization and vapor deposition on the electrode plate.

[Action of the invention]

According to the battery according to the present invention, the conductive substrate on which the electrically active polymer is adhered in the form of a film is coated with a thin film of electrically inactive resin, so that the electrically active By increasing the adhesion of the high molecular weight polymer to the conductive substrate, it is possible to prevent a decrease in capacity even under multiple charge/discharge cycles, and to have a long life.

〔Effect of the invention〕

In the battery according to the present invention, the electrically active polymer composed of an organic compound does not easily peel off from the conductive substrate constituting the electrode even after many charge/discharge cycles, and a decrease in capacity is prevented. , has a long lifespan.

The present invention will be explained in more detail below with reference to Examples.

[Example 1] Aniline at a concentration of 0.1 mol/2 was mixed into an aqueous perchloric acid solution at a concentration of 0.5 mol/2. A platinum plate of 11 x 11 and a nickel mesh plate of 1.5QIX2α were placed opposite each other and immersed in this, and the platinum side was placed positive between the two electrodes.
．． A voltage of 2 volts was applied. After several minutes of corrosion, deep green polyaniline was deposited on the platinum plate. After leaving it for about 10 hours,
This platinum plate was taken out, washed with water, and dried.

The obtained polyaniline was attached to the platinum plate in the form of a film, and the weight attached to one side was about 611 g.

Next, this platinum plate was immersed for 10 minutes in a solution in which polystyrene was dissolved in toluene at a ratio of 10 wt %, and then this was vacuum dried.

Next, this polystyrene-coated platinum plate was placed opposite a lithium plate embedded in nickel expanded metal and placed in an electrolyte solution in which lithium perchlorate was dissolved in propylene carbonate at a concentration of 1 l/2.

The lithium-polyaniline battery constructed as described above exhibited an open circuit voltage of about 3.5V.

Next, when charging and discharging were repeated in the range of 4.0 volts to 2.6 volts at a constant current density of 1 mA/d, approximately 0.1 Ah
A capacity of 10 was obtained, and even after repeating this cycle more than i ooo times, the decrease in volume remained at 10%.

Comparative Example 1 A battery was manufactured in the same manner as in Example 1 except that the polyaniline-coated platinum electrode of Example 1 was used as it was without being coated with polystyrene. When this battery was similarly tested, a clear decrease in capacity was observed after the 100th test, and at the 400th test, the capacity decreased to about 60% of the initial value. When the cycle test was stopped at this point and the pole was taken out, the polyaniline had turned into a powder, and a considerable portion had peeled off from the platinum plate.

[Example 2] The polyaniline-attached electrode obtained in the same manner as in Example 1 was immersed in a 10% by weight benzene solution of polyvinyl chloride for 10 minutes, and a battery was manufactured in the same manner as in Example 1, followed by a cycle test. I did this.

After the 1000 cycle test, the electrode was taken out and observed, and it was found that the polyaniline was well adhered to the platinum plate.

[Example 3] Polyaniline was attached to the electrode in the same manner as in Example 1. Paraffin was placed in the bottom of a glass container, and the electrode was placed at the top of the glass container at 5CIA. After evacuating the inside of the container, the container was heated to 130 ml. It was heated to ℃ and kept in this state for 24 hours.

After this treatment, when the treated electrode was taken out and observed, paraffin was found to have been deposited on the surface. Using this, a battery was produced in the same manner as in Example 1, and a cycle test was performed, resulting in a capacity of 0.08Ah/q, 90% of the initial capacity at the 400th cycle, and 60% at the 1000th cycle.
% capacity.

[Example 4] Virol was mixed at a concentration of 0.1 mol/J2 into a perchloric acid aqueous solution at a concentration of 0.5 mol/°C, and a film was formed on a platinum plate in the same manner as in Example 1. Polypyrrole was synthesized. The polypyrrole layer attached to one side of this platinum plate had a thickness of about 4 mQ.

This electrode was immersed in a polystyrene solution in the same manner as in Example 1. When a battery was manufactured in the same manner as in Example 1 using the polystyrene-coated electrode thus obtained, it showed an open circuit voltage of 3.2 volts, and a voltage of 3.6 volts to 3.6 volts.
When charged and discharged in a potential range of 2.0 volts, 0.0
A capacity of 8Ah/J was obtained. When a cycle test was conducted, the decrease in capacity remained at 10% even after 1000 cycles or more. After the cycle test was completed, the electrode was taken out and observed, and it was found that the polyvirol film was still well adhered to the platinum plate, and there was no change in shape.

Comparative Example 2 A battery was produced in the same manner as in Example 4, except that the polypyrrole-attached IT electrode was not coated with polystyrene and was used as it was, and a cycle test was conducted. A clear decrease in capacity was observed after the 100th cycle, and at the 200th cycle, the capacity decreased to about 60% of the initial value. After the test was completed, the electrode was taken out and observed, and it was found that the polypyrrole had turned into powder, and a considerable portion had flaked off from the platinum plate.

Claims (1)

[Claims] A battery using as an electrode an electrically active polymer substance synthesized on a conductive substrate by an electrolytic polymerization method, characterized in that the surface of the electrode is coated with a thin film of electrically inactive resin. battery.