JPS61220271A - Solid electrolyte battery - Google Patents

Abstract

PURPOSE:To lengthen the life of a battery as a built-in power supply for an electronic appliance of low power consumption, by using a salt-type electroconductive high-molecular substance as a depositive electrode active material. CONSTITUTION:A hydrochloric salt of polycarbazole, which is a salt-type electronconductive high-molecular substance, is used as a positive electrode active material. An outer frame is tightened on the hydrochloric salt pinched between a lithium leaf as a negative electrode active material and a carbon paper as a collector so that a solid-electrolyte battery is constructed. When the battery is discharged through a fixed external resistance of 100kOMEGA, the battery works at a constant voltage of 2.8V for 90hr, the ratio of the discharge capacity to a theoretical capacity is 94% and the energy density is 352whr per 1kg of polymer. The life of the battery is thus lenghtened.

Description

Detailed Description of the Invention (a) Field of Industrial Application The present invention relates to a solid electrolyte battery that has excellent battery capacity per unit weight, and more specifically to a solid electrolyte battery that has low current consumption and power consumption, such as calculators and electronic watches. The present invention relates to a solid electrolyte battery that significantly increases battery life when used as a built-in power source for electronic equipment.

(b) Prior Art In recent years, several solid electrolyte batteries have been proposed with the aim of developing batteries with excellent leakage resistance. However, the main mechanism of solid electrolyte batteries is to retain iodine or bromine in the positive electrode active material and to react this iodine or bromine with the negative electrode active material, so the resulting battery capacity is
The high molecular weight of iodine or bromine inevitably poses a limitation, and it has been virtually impossible to obtain a battery capacity above a certain value.

(c) Problems to be solved by the present invention The inventors
As mentioned above, in view of the fact that conventional solid electrolyte batteries had their own limitations in battery capacity, we conducted intensive research to develop a solid electrolyte battery with an extremely high battery capacity per unit weight, and as a result, we developed a salt-type battery. By using conductive polymers,
The inventors have discovered that such objects can be achieved and have come up with the present invention.

(d) Means for solving the problems and their construction, that is, according to the present invention, there is provided a solid electrolyte battery that solves the above problems and is composed of a salt-type conductive polymer as a positive electrode active material.

The salt-type conductive polymer used as the positive electrode active material in the solid electrolyte battery according to the present invention is a polymer compound in which a salt-forming substrate is bonded as a side chain to a main chain having conductivity, or a conductive A salt of a polymer compound containing a salt-forming substrate in its main chain (herein, a salt having 6 carbon atoms in its main chain)
As specific examples of such conductive polymers, the following alkyl groups, alkoxy groups having 6 or less carbon atoms, amino groups, halogen groups, and phenyl groups may be substituted with one or more without any problem. is polycarbazole, polyphenothiazine, polyquinoline, polyaniline, polypyridine, polypyrazine, polypyridinium, polyacetylenecarboxylic acid dimethylamine, poly-α-pyrroline,
Examples include hydrochloride, hydrofluoride, chloride ion salt, fluoride ion salt, chloroalkyl salt, and fluoroalkyl salt of poly-α-pyrorenine, polybenzo-α-viroline, and the like. Typical examples of such conductive polymers include polycarbazole hydrochloride, polyphenothiazine fluoride,
Chloromethyl salt of polyquinoline, fluoride of polyaniline, hydrochloride of polypyridine, chloride ion salt of polypyridinium, poly-α-pyrroline hydrochloride, fluoride of poly-α-pyrorenine, hydrochloride of polybenzo-α-pyrroline can be mentioned.

The structure of the solid electrolyte battery according to the present invention is the same as that of conventionally known ones except that the salt-type conductive polymer is used as the positive electrode active material, but an alkali metal (for example, lithium) is used as the negative electrode active material. , sodium) or alkaline earth metals (eg, calcium) or alloys of alkali metals (eg, lithium aluminum alloys) are preferred because of their high cell voltages.

The solid electrolyte battery according to the present invention can be manufactured using the above-mentioned positive electrode active material and negative electrode active material according to a conventional method.

That is, for example, a negative electrode lithium foil is placed in a coin-shaped receiver made of 5US304 that serves as a negative electrode current collector and an exterior, and a salt-type conductive polymer is placed in a predetermined amount.

Carbon paper is used as the positive electrode current collector, and after molding with epoxy resin to ensure separation from the coin-shaped receiver that is the negative electrode current collector, a coin-shaped top cover made of 5US304 is covered and caulked. solid electrolyte batteries can be manufactured.

(e) Examples The present invention will be explained in more detail according to the following Examples and Comparative Examples, but it goes without saying that the scope of the present invention is not limited to the following Examples.

Example 1 Hydrochloride 2O of polycarbazole, a salt-type conductive polymer
n+g (0.1 mmol) was used as positive electrode active material.

The polycarbazole hydrochloride was sandwiched between lithium foil as a negative electrode active material and carbon paper as a current collector by caulking it with an outer frame as a positive electrode active material to form a solid electrolyte battery. This solid electrolyte battery has an external resistance of 100
It operated for 90 hours at a flat battery voltage of 2.8 Ω when discharged at a constant resistance of Ω.

The discharge capacity relative to the theoretical capacity was 94% and the energy density was 352 whr/kg polymer.

Examples 2 to 6 Solid electrolyte batteries were produced in the same manner as in Example 1, except that the salt-type conductive polymer shown in Table 1 was used instead of the polycarbazole hydrochloride used in Example 1. .

The performance of the obtained solid electrolyte battery was as shown in Table 1.

Comparative Example 1 Instead of the polycarbazole hydrochloride used in Example 1, a solid electrolyte battery was manufactured using 20 mg of an iodine complex of polyvinylpyridine (71% iodine content), which is not a salt-type conductive polymer. .

The performance of the obtained solid electrolyte battery was as shown in Table 1.

(The following is a blank space) Example 7 A solid electrolyte battery was produced in the same manner as in Example 1 except that a foil cut from a calcium block was used instead of the lithium strip. When a constant resistance discharge was performed at an external resistance of 100Ω, the battery operated for 95 hours at a flat battery voltage of 2.6V. The discharge capacity relative to the theoretical capacity was 99% and the energy density was 345 iv) + r/kg polymer.

Claims (1)

[Claims] 1) A solid electrolyte battery comprising a salt-type conductive polymer as a positive electrode active material. 2) A solid electrolyte battery comprising a salt-type conductive polymer as a positive electrode active material and an alkali metal, an alkaline earth metal, or an alkali metal alloy as a negative electrode active material.