JPH0582120A - Nonaqueous type battery - Google Patents

Abstract

PURPOSE:To improve an electrode capacity by using mixture of a Li ion introduced inorganic compound and electrically conductive polymer as a positive electrode or a negative electrode of a nonaqueous type battery. CONSTITUTION:A material formed by mixing polyaniline 10 pts.wt. synthesized by means of electrolytic polymerization into MnO2 is used as a positive electrode 1, and Li metal is used as a negative electrode 2, and LiBF4-PC solution is used as electrolyte with which a separator 3 is impregnated. Since an electrode into which electrically conductive polymer such as polypyrrole to dope or de- dope possibly anion or cation is mixed is used as the electrode or as an electrically conductive agent, the electrically conductive polymer can also contribute to a charging/discharging capacity, so that a high capacity nonaqueous type battery capable of being charged/discharged can be provided.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a non-aqueous battery provided with a positive electrode, a negative electrode and a non-aqueous electrolyte.

[0002]

Non-aqueous primary batteries using lithium as a negative electrode active material and a non-aqueous electrolyte have advantages such as high voltage, high energy density, excellent low temperature characteristics, and low self-discharge rate.
It is widely used as a power source for a portable small electric device or a portable small electronic device, or a power source for a memory backup of a computer.

As a positive electrode active material for these non-aqueous primary batteries, conventionally, manganese dioxide or fluorocarbon has been used as a typical one.

On the other hand, this type of non-aqueous battery is repeatedly charged and discharged.
A non-aqueous secondary battery that can be used by
There is. Lithium is used as the negative electrode active material of this non-aqueous secondary battery.
A lithium alloy using a metal that alloys with lithium,
Or carbon material capable of intercalating lithium ions
Fees are known. Further, as the positive electrode active material, Li ₂
MnO₃Containing manganese dioxide, vanadium oxide,
Cobalt oxide, etc. have been proposed.
Some non-aqueous secondary batteries combining
It

By the way, the miniaturization of the above-mentioned small electric devices and small electronic devices has been further advanced, and along with this, the nonaqueous primary batteries for power sources are also required to be miniaturized, that is, have a higher capacity and a higher energy density. It's being done. In addition, many non-aqueous secondary batteries that are currently in practical use still have insufficient characteristics, and there is a demand for higher capacity and higher energy density.

Furthermore, in recent years, a conductive material using a conductive polymer has been proposed. The conductive polymer can be doped with various anions or cations as dopants, and can be undoped, and the doping treatment significantly increases the conductivity. Further, a conductive polymer doped with anions is used as a positive electrode material, a conductive polymer doped with cations is used as a negative electrode material, and a solution containing the above dopant is used as an electrolytic solution. A rechargeable battery is constructed by reversibly performing the rechargeable battery.

[0007]

Conventionally, when an inorganic compound that intercalates lithium ions such as manganese dioxide is used as an electrode active material, a conductive agent such as acetylene black is mixed in order to improve the conductivity of the electrode. Was used. In this case, the conductive agent component leads to a decrease in the capacity of the electrode, and the energy density is insufficient for further miniaturization of this type of battery.

The present invention has been made in view of the above problems, and an object thereof is to improve the electrode capacity and to realize a high capacity and high energy density of a non-aqueous battery.

[0009]

The present invention provides a non-aqueous battery comprising a positive electrode, a negative electrode and a non-aqueous electrolyte, wherein the positive electrode is
Alternatively, a mixture of an inorganic compound that intercalates lithium ions and a conductive polymer is used for either one of the negative electrodes, and particularly, the mixed amount of the conductive polymer is 3 to 30 parts by weight. And

[0010]

According to the present invention, an electrode in which a conductive polymer such as polypyrrole which is reversibly doped or dedoped with an anion or a cation as a conductive agent is mixed is used as the positive or negative electrode. Since the conductive polymer also contributes to the charge / discharge capacity, the electrode characteristics are superior to the case of using a conventional conductive agent, and a high-capacity chargeable / dischargeable non-aqueous battery can be obtained.

[0011]

EXAMPLES The present invention will be specifically described with reference to the following examples. [Example 1] Fig. 1 shows a basic structure of a non-aqueous battery. As a positive electrode 1, a material obtained by mixing 10 parts by weight of polyaniline synthesized by electrolytic polymerization with MnO ₂ was used, and as a negative electrode 2, lithium metal was used. LiBF ₄ -PC solution was used as the electrolytic solution with which the separator 3 was impregnated to prepare the battery A of the invention. As a comparative example, the battery A of the present invention was prepared except that 10 parts by weight of acetylene black was mixed with MnO ₂ for the positive electrode.
Comparative battery B was prepared in the same manner as in. In the battery shown in FIG. 1, 4 is a positive electrode can, 5 is a negative electrode can, 6 is a positive electrode current collector, 7 is a negative electrode current collector, and 8 is an insulating packing.

A charge / discharge test was carried out on these batteries A and B. Charging was performed at a charging current of 1 mA up to 3.6 V, and discharging was performed at a discharge current of 1 mA up to 2.0 V.

FIG. 2 shows the charge / discharge characteristics of these batteries.
The battery A of the present invention can charge and discharge 20 mAh, while the battery B of the comparative example can charge and discharge only 17 mAh.

This is because the comparative battery B uses acetylene black as a conductive agent for the electrodes, so that the capacity is reduced by that amount. However, in the battery A of the present invention, polyaniline as a conductive agent also contributes to charging and discharging, so the capacity is Is believed to have grown. [Example 2] A material obtained by mixing 20 parts by weight of polyaniline synthesized by electrolytic polymerization with MnO ₂ was used as the positive electrode 1, lithium metal was used as the negative electrode 2, and LiBF ₄ -P was used as the electrolytic solution.
The battery C of the present invention shown in FIG. 1 was produced using the C solution. Further, as a comparative example, a comparative battery B was prepared in the same manner as the battery D of the present invention except that 20 parts by weight of acetylene black was mixed with MnO ₂ for the positive electrode.

A charge / discharge test was performed on these batteries C and D. Charging was performed at a charging current of 1 mA up to 3.6 V, and discharging was performed at a discharge current of 1 mA up to 2.0 V.

FIG. 3 shows the charge / discharge characteristics of these batteries.
The battery A of the present invention can charge and discharge 19 mAh, while the battery B of the comparative example can charge and discharge only 16 mAh.

In Comparative Battery D, acetylene black is used as the conductive agent for the electrodes, so the capacity is reduced by that amount. However, in Battery C of the present invention, polyaniline as the conductive agent also contributes to charge and discharge, so the capacity is reduced. Is considered to have become larger. [Example 3] A material obtained by mixing 10 parts by weight of polypyrrole synthesized by electrolytic polymerization in MnO ₂ was used as the positive electrode 1, lithium metal was used as the negative electrode 2, and LiBF ₄ -P was used as the electrolytic solution.
The battery C of the present invention shown in FIG. 1 was produced using the C solution. Further, as a comparative example, a comparative battery F was prepared in the same manner as the battery E of the present invention, except that 10 parts by weight of Ketjen black was mixed with MnO ₂ for the positive electrode.

A charging / discharging test was conducted on these batteries E and F. Charging was performed at a charging current of 1 mA up to 3.6 V, and discharging was performed at a discharge current of 1 mA up to 2.0 V.

FIG. 4 shows the charge / discharge characteristics of these batteries.
Inventive battery E can charge and discharge 20 mAh, whereas comparative battery F can only charge and discharge 17 mAh.

In Comparative Battery F, since Ketjen Black is used as the conductive agent for the electrodes, the capacity is reduced by that amount, but in the Battery C of the present invention, polypyrrole as the conductive agent also contributes to charging / discharging. It is considered that the capacity has increased.

In each of the above-mentioned embodiments, the case where MnO ₂ is used as the electrode material has been described as an example, but in addition to MnO ₂ , TiS ₂ , FeS ₂ , and Nb ₃ which reversibly react with lithium metal. S ₄ , Mo ₃ S ₄ , Mo ₃ Se ₄ ,
CoS ₂ , V ₂ O ₅ , P ₂ O ₅ , CrO ₃ , V ₃ O ₈ , Te
It is possible to use a mixture of an inorganic compound such as O ₂ or GeO ₂ and a conductive polymer such as polyaniline, polypyrrole, or polythiophene, which is reversibly doped or dedoped with an electrolyte anion or a cation.

As the electrolytic solution, aprotic organic solvents such as propylene carbonate, butylene carbonate, 1,2-dimethoxyethane, γ-butyrolactone and sulfolane are used alone or in a mixed solvent of two or more of each, LiClO ₄ and LiBF. ₄ , LiCF ₃ SO ₃ , LiP
Electrolytes such as F ₆ and LiAsF ₆ may be used alone or as a mixture of two or more electrolytes dissolved therein.

Further, as a mixture of an inorganic compound for intercalating lithium ions and a conductive polymer, if the amount of the conductive polymer mixed is too small or too large, good results are not obtained, and it is preferable. 3 parts by weight to 3
0 parts by weight.

[0024]

As described above, according to the present invention, a mixture of an inorganic compound that intercalates lithium ions and a conductive polymer is used for either the positive electrode or the negative electrode. Since the conductive polymer also contributes to the charge / discharge capacity, the electrode characteristics are excellent as compared with the case where the conventional conductive agent is used, the capacity of the nonaqueous battery system electrode can be increased, and its industrial value is very large.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a structural configuration of a battery of the present invention.

FIG. 2 is a charge / discharge characteristic diagram of the battery of the present invention.

FIG. 3 is a charge / discharge characteristic diagram of another example of the battery of the present invention.

FIG. 4 is a charge / discharge characteristic diagram of still another embodiment of the battery of the present invention.

[Explanation of symbols]

 1 Positive electrode 2 Negative electrode 3 Separator

Claims (2)

[Claims] 1. A non-aqueous battery comprising a positive electrode, a negative electrode and a non-aqueous electrolytic solution, wherein a mixture of an inorganic compound intercalating lithium ions and a conductive polymer is added to either the positive electrode or the negative electrode. A non-aqueous battery characterized by being used. 2. The non-aqueous battery according to claim 1, wherein the amount of the conductive polymer mixed is 3 to 30 parts by weight.