JPS59149601A - Ion conductive solid composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an ion conducting ηr, 1st solid composition.

In particular, ionic conductivity, which combines the excellent mechanical properties inherently possessed by polymers and high ionic conductivity.

The present invention relates to a solid composition.

Conventionally, ion conductive materials include (a) an electrolyte solution in which an electrolyte is dissolved in water or an atomizing solvent, and (b) beta/alumina β-AI, 0. ．． Lithium iodide/alumina Li
I-A40,1, silver rubidium iodide RbAP4
Solid electrolyte materials such as Ia lithium nitride Li3N and the like are known.

In recent years, there has been a strong demand for high reliability in electronic components as well as high performance, small size and thinness, and this has led to active material development. These materials require not only high performance potential but also excellent mechanical workability, flexibility, and strength, and solid or solid materials are strongly required from the viewpoint of high reliability. .

The electrolytic a solution shown in (a) in Figure 1 is used in various electronic components because of its high ionic conductivity.
Because liquids such as water or organic solvents are used as materials, there is always the problem of liquid leaking to the outside of electronic components, and this leakage may cause performance deterioration of the components or damage to surrounding components. It lacks high reliability as a component. Furthermore, since it is a fluid ion-conductive material, it lacks mechanical strength, resulting in poor mechanical workability, and the parts have drawbacks such as limited shapes.

On the other hand, since the solid electrolyte material (b) is solid, it is suitable for highly reliable and long-life electronic components, and has been actively developed in recent years in response to demands for smaller and thinner components.

However, at present, the ionic conductivity at high temperature is not as high as that of the electrolytic solid solution (a), so the conditions under which the parts can be used are greatly restricted. In addition, solid electrolyte materials had disadvantages such as high cost and poor mechanical workability, such as being difficult to form into any shape or form a film. Not yet reached.

In order to improve the drawbacks of these conventional ion conductive materials, there are ion conductive materials in the form of paste or gel, which can be said to be an intermediate form between (a) and (b). However, even with a paste-like or gel-like phase material, the risk of liquid leakage to the outside of the component cannot be completely eliminated, and a drawback still remains in terms of high reliability. Furthermore, in terms of mechanical workability, it cannot be said that it has improved much because, like liquids, it lacks mechanical strength.

In contrast, the inventors have discovered an ion-conductive solid composition that, under the conditions of use as a solid filler, appears to be in a top-hedral state and becomes an object that is not in a fluid state like a liquid. . This is mainly composed of three components: an organic polymer compound, an organic solvent, and an electrolyte. Moreover, since it is a solid material, it can be said that it is a material that is sufficiently better than paste-like or gel-like materials in terms of reliability.

However, there are a large number of possible combinations of these three components, and there are restrictions on the combinations that meet the conditions for practical use as electronic components. For example, if an ionically conductive circular body composition has sufficient mechanical workability, it may have the disadvantage that its ionic conductivity is much lower than that of an electrolyte solution, making it impractical for practical use. However, when it has high ionic conductivity, it has the disadvantage of poor mechanical workability.

The object of the present invention is to eliminate such conventional drawbacks and to provide an ionically conductive circular body composition that has both higher mechanical workability and higher ionic conductivity.

According to the present invention, the organic polymer compound is polyvinylidene fluoride, and the organic solvent is gamma-butyrolactone.

An ion-precipitable solid composition is obtained in which the power/resistance is comprised of lithium perchlorate.

In general, the ionic conductivity of the ionic conductive circular body composition and 4
The processability and strength of the firewood are determined by the organic solvent and the 111. Depends on solute composition and concentration. From the above points of view, as a result of a detailed study of the silk paraboloids that are essential to the present invention, it has been found that the following composition and range of concentrated IJ1 give excellent results in 11 cases.

That is, the composition of gamma-butyrolactone is 1.0 to 5.
The m> degree of lithium perchlorate relative to gamma-butyrolactone was in the range of J to 8 mol/l.

Hereinafter, the present invention will be explained and explained using 1q examples.

[Example 1] In this example, the composition of gamma-butyrolactone contained in the ionically conductive solid composition will be described.

Add 55'r of polyvinylidene fluoride, an organic polymer compound, to 100 ml of gamma-butyrolactone, an organic solvent,
The mixture was heated to a temperature of 120°0 and sufficiently stirred to dissolve. The electrolyte concentration for gamma-butyrolactone in the obtained ionically conductive circular body composition was 3mo7 of this solution.
/n, a predetermined amount of lithium perchlorate was added, heated to a temperature of 100"O, stirred in the tank, and dissolved to prepare an electrolytic solution. This electrolytic solution was poured into a 1o diameter diameter plate with a horizontal bottom.
After pouring it into a tinted glass petri dish, it was placed in a vacuum heating dryer and heated to a temperature of 140°0. Vacuum degree 300mm)iyo
When drying, gamma-butyrolactone was evaporated by opening fgl to the desired side to form an ion-conductive solid silk composition with a predetermined composition.The above operations removed the remaining gamma-butyrolactone. The electrolyte concentration for
! 3/11. Gamma-butyrolactone composition is 5-60
A uniform thin film sample with a thickness of 0.1 to 1 mm was obtained in the M portion of the film.

Next, punch out this sample into a disk shape with a diameter of 10 mm, sandwich it between platinum black electrodes, measure the electrical resistance value of the sample at a frequency of IKHzΩ AC, and calculate the area between this electrical resistance value and the thickness of the sample as Q of the sample. The conductivity was calculated.

Based on these results, FIG. 1 shows the correlation between the composition ratio of gamma-butyrolactone and the ionic conductivity of the ionically conductive circular body composition according to the present invention.

As shown in Figure 41, the ionic conductivity increases as the composition ratio of gamma-butyrolactone increases.

However, as the composition ratio increases, the mechanical strength of the sample decreases, and the sample changes from a solid state to a paste-like state and loses the characteristics of the present invention. Moreover, if the composition ratio becomes low, high ionic conductivity cannot be obtained and it becomes impossible to put it into practical use. Therefore, the composition ratio of gamma-butyrolactone in the ionically conductive circular body composition has a practical range. In the ion conductive solid silk composition of the present invention, if gamma-butyrolactone is in the range of 10 to 50 parts by weight, it has excellent mechanical strength and processability, and has good ionic conductivity with high ionic conductivity. A sterile material was obtained.

[Example 2] In this example, gamma in an ionically conductive solid silk composition was
The concentration of lithium perchlorate relative to butyrolactone will be described. Polyvinylidene fluoride 5Pr was added to gamma-butyrolactone 100r+J, heated at a temperature of 1.20°0, and sufficiently stirred to dissolve. A predetermined amount of lithium perchlorate was added to 10 ml of this solution so that the concentration of lithium perchlorate in the formed ion conductive circular body composition was 0.5 to 10 mol/l. Thereafter, the mixture was heated to 100°C, stirred, and dissolved to obtain an electrolyte solution. The following manufacturing method is performed according to Example 1. Approximately 30 gamma-butyrolactone remained after the above operation.
Part by weight, concentration of lithium perchlorate is 0.5-101TI
A uniform thin film sample with a film thickness of about 0.15 mm was obtained.

Using this sample, the conductivity was calculated in the same manner as in Example 1, and FIG. 2 shows the correlation between the concentration of lithium perchlorate in the ion conductive circular body composition according to the present invention and the ionic conductivity.

As shown in FIG. 2, the ionic conductivity increases as the concentration of lithium perchlorate increases. However, as the concentration increases, the sample deteriorates (mechanical strength and workability deteriorate,
If it becomes even larger, lithium perchlorate becomes saturated with respect to gamma-butyrolactone and precipitates, resulting in a decrease in ionic conductivity. Moreover, if the concentration becomes low, a high ionic charging rate cannot be obtained and it becomes impossible to put it into practical use. Therefore, there is a practical range for the composition ratio of gamma-butyrolactone and the concentration of lithium perchlorate in the same material. In the ionic lip-electrostatic solid silk composition of the present invention, if the concentration of lithium perchlorate is in the range of 1 to 8 m o 13/e relative to gamma-butyrolactone, the thin film as in this example can be obtained. A plane with a good ion-scented solid body composition that has sufficient mechanical strength and workability, and also has high ionic conductivity.
Gai<(was.

In Examples 1 and 2 of the present Example 5, the preparation of the ion conductive circular body composition and the measurement of the ion conductivity were carried out without argon. The test was carried out in an IG gas atmosphere.

Due to its excellent mechanical workability, the ion-conducting L solid material composition of the present invention can be used to form very thin films of several microns or large area films using film forming techniques such as presses and rolls. I was able to get In addition, these thinner films, larger areas, and high ion conductivity have made it possible to improve ion conductivity and performance in various electronic components such as N&, electrolytic capacitors, sensors, electrochromic devices, as well as timing devices and integral memory devices. Otherwise, it can be put to practical use.

As described above, according to the present invention, it is possible to obtain an ion conductive circular body composition that has excellent mechanical workability, strength, and hollow ion conductivity.

[Brief explanation of drawings]

Figure 1 shows the relationship between the ionic conductivity of the ionically conductive circular body composition according to the present invention and the composition ratio (wt%) of the organic solvent gamma-butyrolactone.
The figure shows the ionic conductivity f1 and the concentration of electrolyte lithium perchlorate relative to gamma-butyrolactone (mol/l
). Agent Patent Attorney Uchihara Kumi, ゛) 1st closing force 7-Guososhitsukton 69 series 8) L stock amount formula M)
x=)2closed0 246Bi.

Claims (3)

[Claims] (1) An ionic barrel, solid silk composition comprising polyvinylidene fluoride, gamma-butyrolactone, and lithium peroxide. (2) The composition of the gamma-butyrolactone is 10 to 50
The ionic hexaelectric solid composition according to claim 1, characterized in that the amount is parts by weight. (3) The ionic conductive solid silk according to claim 81!1, characterized in that the concentration of lithium oxide in the width of the groove for the gamma-butyrolactone is 1 to 8 molJ/13. A product.