JPS629978B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a battery using a light metal such as lithium, sodium, or magnesium as a negative electrode active material and a novel organic polyiodine compound as a positive electrode active material. Conventionally, batteries using organic iodine compounds as positive electrode active materials, and those using divalent metals or silver as negative electrodes, have been published in the Journal of the Electrochem.Soc.
Vol. (1967), p. 323, Vol. 115 (1968), p.
359, etc., and solid electrolyte batteries using lithium or the like as the negative electrode are introduced in JP-A-47-8823, JP-A-47-30769, and other publications. The positive electrode active material used in these batteries is
It utilizes an organic iodine charge transfer complex that is generated by using a cyclic compound as an electron donor and transferring electrons from the π electron cloud present in the compound to iodine, which is an electron acceptor. Examples of the cyclic compounds include polycyclic aromatic compounds such as pyrene, perylene, naphthalene, anthracene, and violanthrene, and polycyclic compounds containing heteroatoms such as nitrogen and sulfur such as pyridine, quinoline, acridine, phenazine, and phenothiazine. These include aromatic hydrocarbons. As pointed out in Japanese Patent Application Laid-Open No. 47-30769, the above complex exists in a state where the bonding force between the electron donating substance and the electron accepting substance iodine is extremely weak. is active in However, these complexes are relatively unstable because iodine evaporates rapidly at room temperature and pressure.
Therefore, during the battery assembly process, special consideration must be taken to eliminate the effects of iodine vaporization on the human body. In addition, if the battery is not completely sealed, it will escape as iodine gas to the outside, which will shorten the battery's shelf life.Furthermore, the iodine gas will cause corrosion of the battery case, and even stainless steel battery cases will be damaged. There are various problems such as insufficient service life. The present invention provides a battery that does not have the above-mentioned drawbacks, has an excellent shelf life, and is easy to manufacture. That is, the present invention uses a polyiodine compound of a halide polymer of a quaternary heterocyclic nitrogen compound as a positive electrode active material. The polyiodine compound here is particularly preferably one represented by the following general formula or. (However, in the formula, R represents an alkyl group, a cycloalkyl group, a phenyl group, a phenylalkyl group, or an alkoxycarbonyl group, and R' represents a hydrogen atom,
Alkyl group, phenyl group, phenylalkyl group,
It represents a nitro group or a nitrile group, R ₁ and R ₂ represent a hydrogen atom, an alkyl group, a cycloalkyl group, a phenyl group, a phenylalkyl group, or an alkoxycarbonyl group, and R ₃ represents an alkylene group. Further, n ₁ indicates the degree of polymerization and represents an integer of 1 or more. Y, Y ₁ , Y ₂ represent a halogen atom selected from the group of iodine, bromine, and chlorine, n ₂ represents an integer equal to n ₁ and represents the anion content of the halogen, and x represents the iodine content. Represents a real number greater than or equal to 1. ) Specific examples of the polyiodine compounds represented by the above general formulas () to () are shown in Tables 1 to 3, respectively.

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[Table] The compounds represented by the above general formulas () and () include the following isomers. That is, there are the following three isomers for general formula (). Further, regarding the general formula (), there are the following three isomers. The polyiodine compound of the halide polymer of the quaternary heterocyclic nitrogen compound of the present invention can generally be produced by reacting an organic compound having a quaternary ammonium group with iodine or iodine gas. For example, 1 of the compound represented by the general formula ()
Poly 4-vinyl-N-methylpyridinium polyiodide, which is
First, poly4-vinyl-N-methylpyrivinium iodide is produced by reacting vinylpyridine and methyl iodide in an inert solvent such as ethanol or nitrobenzene. Next, by bringing this compound into contact with iodine or iodine gas, poly-4-vinyl-N-methylpyridinium polyiodide can be easily obtained. Similarly, for compounds represented by the general formula (), RY such as methyl iodide, ethyl iodide, methyl chloride, methyl bromide, etc. are added to polyvinylquinolinine or its derivatives.
Reacting a compound represented by in an inert solvent,
It can be produced by bringing the resulting compound into contact with iodine or iodine gas. An example reaction formula is shown below. Next, regarding the compound represented by the general formula (), for example, polyN-methylene-4,4'-dipyridinium polyiodide is prepared by combining 4-4'-dipyridine and methylene diiodide in an inert solvent. It can be obtained by reacting to produce polyN-methylene-4-4'-dipyridinium diiodide, which is then treated with iodine or iodine gas. In the polyiodine compound used in the present invention, the halogen atoms constituting the monovalent anions represented by Y, Y ₁ , and Y ₂ in the general formula have a high reactivity and a battery active material when producing the polyiodine compound. An iodine atom is most preferable in terms of energy density. Furthermore, it is desirable that x, which represents the iodine content, be as large as possible in terms of energy density. However, if the iodine content is too large, anion
The charge transfer between Y ^- , Y ₁ ^- , Y ₂ ^- and iodine increases, and as a result, the bonding force between iodine becomes weaker, and iodine approaches a state of isolation,
The vaporization into iodine gas at room temperature and pressure is almost the same as that for iodine alone. Therefore, the value of x is preferably up to about 10. Using the above polyiodine compound as a positive electrode active material,
The battery reaction when a light metal M having a valence of m is used for the negative electrode is thought to proceed as follows. Positive electrode I ₂ +2e ^→ 2I -Negative electrode 2/mM→2/mM ^- +2e Total cell reaction I ₂ +2/mM→2/mMI Here, iodine, which is a discharge species at the positive electrode, is supplemented with a polyiodine compound. Taking poly-4-vinyl-N-methylpyridinium polyiodide as an example, as shown in the following equation, the
It is thought that I ₂ is liberated from the polyiodine compound. In the polyiodine compound used in the present invention, unlike conventional organic iodine charge transfer complexes, the iodine atom is more strongly bonded to the quaternary ammonium group, so iodine does not vaporize significantly at room temperature and pressure. few. Furthermore, since a plurality of organic compounds having a quaternary ammonium group are polymerized, it exhibits plasticity, the shape of the electrode can be changed in various ways, and it is extremely active electrochemically. Examples of the present invention will be described below. Figure 1 shows an example of the configuration of a battery. 1 is a negative electrode in which a stainless steel net current collector 2 is press-fitted into a metal lithium plate with a size of 10 x 10 mm and a thickness of 1 mm, and 3 is a negative electrode from which a current collector 2 is inserted. This is a stainless steel lead wire pulled out. 4 is plastic poly-4-vinyl-N-n
- A positive electrode using hexylpyridinium hexaiodide as an active material, 5 is a titanium net current collector embedded in the positive electrode, and 6 is a titanium lead wire. 7
is a solid electrolyte mainly composed of lithium iodide that is produced by bringing a positive electrode and a negative electrode into contact. 8 is a polyethylene battery case, and 9 is a hole with a diameter of 1 mm provided to examine the decrease in battery capacity due to vaporization of the positive electrode active material. Figure 2 shows the results of discharging at 40 μA in a desiccator with an internal volume of 2 for Battery A according to the present invention and Battery B using conventional poly-4-vinylhexylpyridinium hexaiodide as the positive electrode active material. . As is clear from the figure, it can be seen that battery A has a better utilization rate of the positive electrode active material than battery B. In Battery B, iodine was strongly vaporized from the positive electrode active material, and iodine was observed to adhere to the inner wall of the desiccator. The low active material utilization rate of Battery B is due to the dissipation of iodine as described above. On the other hand, in Battery A, almost no iodine vaporization was observed. Further, the battery of the present invention exhibited an open circuit voltage of approximately 2.9 V, and was capable of high rate discharge of approximately 10 mA/cm ² immediately after prototype production. However, as the discharge progresses, an electrolyte layer is generated, which increases the internal impedance of the battery, so it is suitable for use as a battery for low rate discharge, such as a power source for a watch or a power source for a pacemaker. As described above, since the polyiodine compound used in the positive electrode active material of the present invention has almost no iodine vaporization, it is easy to seal the battery, and corrosion of metal materials due to iodine vaporization is also reduced, and furthermore, the battery can be sealed. Shelf life is also improved. Furthermore, since it has plasticity, a battery with spiral electrodes as shown in Figure 3 (in the figure, 10 is a stainless steel container, 11 is a negative electrode, 12 is a positive electrode, 13 is a polyethylene film,
14 and 15 are stainless steel current collectors, 16 is a polyethylene sealing plate, 17 is a positive terminal, 18, 19
2 indicates a lead wire, and 20 indicates a polyethylene insulating plate. ) becomes possible. Furthermore, the structure of the flat battery is easy, and it can be processed into any shape such as a thin film, so it has many features such as increasing the surface area and improving high rate discharge characteristics.

[Brief explanation of the drawing]

FIG. 1 is a schematic vertical cross-sectional view showing one embodiment of the battery of the present invention, FIG. 2 is a diagram comparing discharge characteristics, and FIG. 3 is a partially cutaway perspective view showing another example of the battery configuration.

Claims (1)

[Scope of Claims] 1. A battery comprising a negative electrode having a light metal as an active material and a positive electrode having a polyiodine compound of a halide polymer of a quaternary heterocyclic nitrogen compound as an active material, the battery comprising: As a combined polyiodine compound, the general formula or A battery characterized by using a compound selected from the group consisting of compounds represented by (However, R
is an alkyl group, a cycloalkyl group, a phenyl group,
It represents a phenylalkyl group or an alkoxycarbonyl group, and R' represents a hydrogen atom, an alkyl group, a phenyl group, a phenylalkyl group, a nitro group, or a nitrile group. R ₁ and R ₂ represent a hydrogen atom, an alkyl group, a cycloalkyl group, a phenyl group, a phenylalkyl group, or an alkoxycarbonylalkyl group,
R ₃ represents an alkylene group. n ₁ indicates the degree of polymerization and represents an integer of 1 or more. n ₂ indicates the content of halogen anions and is an integer equal to n ₁ . Y, Y ₁ and Y ₂ represent halogen atoms selected from the group of iodine, bromine and chlorine. X represents the iodine content and is a real number of 1 or more. ).