JPS63218152A - Organic electrolyte battery - Google Patents

Abstract

PURPOSE:To increase discharge capacity and improve energy density by forming an electrode substrate with primary graphites having many fine pores on the surface and by laminating an electrolytic polymerizate film composed of conductive organopolymer material on the surface of the substrate and the inner surface of pores over a broad area. CONSTITUTION:An active substance is provided by doping electrolytic ions in a conductive organopolymer material. As an electrode substrate 1 coated with this active substance, molded product of primary graphites with many fine pores 2 at least at opening on the surface. Laminating an electrolytic polymerizate film 3 composed of conductive organopolymer material on surface of the substrate 1 and inner surface of pores 2, a positive electrode 4 or both of a positive and a negative electrode of battery are formed. Hence good adhesion of the active substance with the substrate 1 is obtained and the increased thickness of the electrolytic polymerizate film 3 can increase the amount of active substance.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an organic electrolyte battery in which an electrode active material is an electrically conductive organic polymer material doped with electrolyte ions.

(Conventional technology) Polymer materials such as organic semiconductors such as polyacetylene, polypyrrole, polythiophene, and polyaniline are used as electrodes,
LiBF, NaBF, AgBF4゜KBF4 are compounds that can generate ions that can be doped with this.
．． NaAsF, , NaPF, , LiClO4
, AgCl0. An organic electrolyte battery is known in which an electrolyte prepared by dissolving the above in an organic solvent is used as an electrolyte (see, for example, Applied Physics Vol. 52, No. 11 (1983), pp. 971-974).

However, when synthesizing the polymeric material on the surface of the electrode, it is difficult to increase the film thickness of the polymeric material, which is approximately 0.2cm thick at most, and the discharge capacity is limited. There is. In order to increase the discharge capacity, it is necessary to increase the number of polymer films used, but simply stacking the films does not have the effect of increasing the discharge capacity. If a bipolar or stacked type was used to solve this problem, it would require an extra configuration, increase weight, and
The energy density of the battery will decrease.

(Problems to be Solved by the Invention) The present invention provides an electrically conductive organic polymer material in which the positive electrode or both the positive and negative electrodes of an organic electrolyte battery are deposited on a substrate made of a conductive material. To provide an organic electrolyte battery with an electrode having a film thickness as thick as possible,
Increase discharge capacity.

In addition to improving energy density, it also enhances the current collection effect,
The purpose is to lower the internal resistance of the battery and improve the performance of the battery.

(Means for Solving the Problems) The present invention uses, as an electrode substrate on which an active material is to be adhered, one-dimensional graphite molded with a large number of fine pores opened at least on the surface. By using a film formed by electrolytically polymerizing an electrically conductive organic polymer material on the surface of the substrate and the inner surface of the pores as the positive electrode of the battery, or as both the positive electrode and the negative electrode,
The adhesiveness of the active material to the substrate is improved, the thickness of the electrolytically polymerized film is increased, and the amount of the active material is increased, making it suitable for use as a secondary battery.

In the present invention, one-dimensional graphite generally refers to condensation polymers consisting of carbon, hydrogen, and oxygen, specifically polyacene, polyacenacene, polynaphthalene, etc.
A polymer substance in which benzene rings are connected only in one direction is
It is heat treated at a temperature of about 00 to 900°C to develop a layered structure similar to a graphite structure. -dimensional graphite has a structure intermediate between that of polyacetylene and graphite, and has excellent electrical properties.

(Function of the Invention) According to the present invention, the electrode substrate is formed of one-dimensional graphite with a large number of fine pores formed at least on the surface, and the electropolymerized film of the electrode conductive organic polymer material is formed on the surface of the substrate and Since it is layered over a wide area on the inner surface of the pores, doping and undoping of electrolyte ions can be performed efficiently and with low internal resistance.

(Example) FIG. 1 is an enlarged perspective view of a small piece of an electrode of an organic electrolyte battery according to the present invention. FIG. 3 is a diagram showing the applied electropolymerized film removed.

In the figure, reference numeral 1 denotes a plate-shaped substrate made of one-dimensional graphite, and a large number of pores 2 are formed at least on the surface of the substrate 1, and the internal spaces of the pores 2 are formed on the surface of the substrate 1. It is open to For example, the substrate 1 is made by layering fibers of novolac-based phenol formaldehyde resin, which is a polyacene-based polymer material, in the form of a non-woven fabric, immersing this in a 40vt% methanol solution of resol-based resin, and then compressing and drying it to form a plate. 400-9 in a non-oxidizing atmosphere.
Manufactured by heat treatment at approximately 00°C. This substrate 1 has a large specific surface area and has many fine pores formed on its surface. An electrolytic polymer film 3 of polypyrrole is coated on the entire surface of the substrate 1 and the inner surface of the pores 2 to constitute an electrode.

This will be referred to as the positive electrode 4.

The electrolytically polymerized film 3 is deposited on the substrate 1 by an electrolytically polymerized method. That is, LiCl0+ is used as a compound that can generate electrolyte ions, and the substrate 1 is immersed and suspended in an electrolytic solution in which LiCl0+ is mixed in propylene carbonate in which pyrrole is dissolved.The substrate 1 is used as a positive electrode, and an aluminum electrode is used. When electrolysis is performed using the electrode as a negative electrode, the surface of the substrate 1 and the inner surface of the pores 2 formed in the substrate 1 are entirely covered.

An electrode is obtained on which an electrolytically polymerized film 3 of polypyrrole doped with CIO, "" ions is deposited. The deposited electropolymerized film 3 has a part deposited on the surface of the substrate 1 and a part deposited on the inner surface of the pores of the substrate 1, which are continuously formed integrally. The adhered part acts as an anchor and has good adhesion to the substrate 1, and also has a large adhesion area to the substrate 1 made of -dimensional graphite, which reduces the internal resistance of the battery and improves the current collection effect. and improve battery performance.

FIG. 2 is a partially cutaway perspective view of a practical example in which the present invention is implemented in a coin-type secondary battery. In this embodiment, inside a deep plate-shaped positive electrode case 5 made of stainless steel with a circular bottom hole, the substrate 1 is mounted on a disk-shaped substrate 1 having an outer diameter slightly smaller than the inner diameter of the bottom hole. A positive electrode 4 coated with an electrolytic polymer film 3 is placed on the bottom hole, and a separator 6 made of a polypropylene nonwoven fabric is placed thereon. L I C104 is injected into this separator 6 as an electrolyte.
A propylene carbonate solution dissolved at a concentration of +ol/d+m3 was soaked. Next, a negative electrode active material 8 made of AI is brought into close contact with the inner surface of the bottom plate of a stainless steel negative electrode case 7 having a circular bottom plate, and the negative electrode case 7 is held in such a manner that the negative electrode active material 8 comes into contact with the separator 6. is inserted into the positive electrode case 5, and a gasket 9 made of polypropylene, which is attached in advance to the outer peripheral edge of the negative electrode case 7, is inserted into the negative electrode case 7.
and a positive electrode case 5, and the free end of the positive electrode case 5 is caulked inward to seal the space between the two cases. If the peripheral edge of the negative electrode case 7 is formed with a stepped portion as shown in the figure by a conventional method, good sealing performance will be obtained when the positive electrode case 5 is caulked.

The above secondary battery has (1) at the positive electrode during charging.
The reaction shown in the formula (2) occurs at the negative electrode. Note that in formula (1), P represents a positive electrode active material.

During discharge, the opposite reaction occurs and current flows between the positive and negative electrodes. In the present invention, the positive electrode active material P is one-dimensional graphite and an electrically conductive organic polymer material (polypyrrole in the above embodiment), both of which are charged and discharged by the above reaction.

The above coin-type secondary battery, a battery using one-dimensional graphite alone as the positive electrode active material, and a battery using polypyrrole alone were created with the same dimensions, and the battery characteristics were measured by conducting discharge and charging tests. However, as shown in FIG. 3, the example of the present invention had an increased discharge capacity and an increased energy density per volume compared to other batteries.

In addition, as another embodiment of the present invention, the same electrode as the positive electrode 4 can be used as the negative electrode active material 8.

Furthermore, as another example, as a positive electrode and a negative electrode,
An electrolytic polymer film of other electrically conductive organic polymer materials such as polythiophene, polyaniline, polyacetylene, etc. can be used as an active material for the substrate 1 made of -dimensional graphite, and L can be used as a compound that supplies electrolyte ions.
iPF5. Known materials such as LiAsF and tLiBF4 can be used, and the solvents include γ-butyrolactone, acetonitrile, 1,2-dimethoxyethane, detrahydrofuran, and DME.

Known substances such as DMSO can also be used alone or in combination.

(Effects of the Invention) The present invention provides an organic electrolyte battery comprising an electrode active material in which an electrically conductive organic polymer material is doped with electrolyte ions, in which the positive electrode or both the positive and negative electrodes are formed using a large number of fine particles. An electropolymerized film of the electrically conductive organic polymer material is coated on the surface and the inner surface of the pores of a substrate made of one-dimensional graphite with pores opened at least on the surface. In order to improve the adhesion of the part of the electropolymerized film adhered to the inner surface of the pore to the substrate by serving as an anchor and to improve the adhesion of the part of the electropolymerized film adhered to the surface of the substrate integrated with the part to the substrate. The -dimensional graphite becomes a good current collector for the electropolymerized membrane, reducing internal resistance, and the electrolytic polymerization membrane also adheres to the pores of the one-dimensional graphite that makes up the substrate, making it difficult to use other substrates of the same volume. Use□
Compared to the case where the active material is increased, the amount of active material is increased, and the charging capacity is increased, so the discharge capacity is increased, and as a result, there is an effect of improving the energy density per volume. Also, the maximum capacity (for example, I
If you want to configure the battery of Ah), it is necessary to increase the amount of active material, but if only the electrolytic polymer membrane is used as the active material, the maximum thickness is about 0.2 m, and the thickness must be increased further. However, in the present invention, since the one-dimensional graphite that constitutes the substrate also reacts as an active material,
By combining a substrate made of −dimensional graphite and an electrolytically polymerized film made of an electrically conductive organic polymer material,
The thickness can be any desired up to +, and the amount of active material can be increased.

[Brief explanation of the drawing]

FIG. 1 is an enlarged perspective view showing the configuration of the positive electrode in the present invention;
Figure 2 is a partially cutaway perspective view of an example in which the present invention is applied to a coin-type secondary battery, and Figure 3 compares the battery characteristics of the present invention with those of batteries using different positive electrode active materials. FIG. The following symbols in the figure indicate the following parts, respectively. 1... Substrate, 2... Pore. 3... Electropolymerized membrane, 4... Positive electrode, 5... Positive electrode case, 6...
...Separator, 7...Negative electrode case,
8...Negative electrode active material, 9...Gasket with Hl

Claims (2)

[Claims] (1) In an organic electrolyte battery equipped with an electrode active material in which an electrically conductive organic polymer material is doped with electrolyte ions, the positive electrode or both the positive electrode and the negative electrode are provided with numerous fine pores opened at least on the surface. An organic electrolyte battery characterized in that an electrode is formed by depositing an electrolytic polymer film of the electrically conductive organic polymer material on the surface of the substrate made of one-dimensional graphite and the inner surface of the pores. (2) A patent characterized in that the electrode is made by depositing a type of electrically conductive organic polymer material such as polypyrrole, polythiophene, polyaniline, polyacetylene, etc. on the substrate in the form of a film using an electrolytic polymerization method. An organic electrolyte battery according to claim 1.