JPS59195529A - Electrically conductive substance - Google Patents

Abstract

PURPOSE:To provide the titled substance having high ionic conductivity and made of a solid electrolyte having a specified composition consisting of Nd, Y, F and O. CONSTITUTION:This electrically conductive substance in a solid oxyfluoride electrolyte represented by a general formula NdaYbFeOd (where a=4.5-7.5, b=7.5- 4.5, c=14-24, d=11-6, 3a+3b=c+2d, and a+b=12), and it has sufficiently high electric conductivity even at low temp. A powdered mixture consisting of Nd2O3 and YF3 or of NdF3 and Y2O3 by amounts giving said desired composition is well pulverized, mixed, and held at about 1,000-1,200 deg.C in an inert gaseous atmosphere for about 1-3hr. Thus, said electrically conductive substance can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to electrically conductive materials, particularly certain fluorinated oxide solid materials.

In recent years, with the rapid progress of various electronics, the materials used in these electronics have also been produced in amounts of 8JfM each. solid box,
One example of this is solid electrolytes that exhibit high ionic conductivity, such as β-alumina and silver rubidium iodide, and are expected to be applied to various fields.

However, among these solid electrolyte values, ZrO2/Y2O3 and Zr are said to have the highest oxygen ion conductivity.
Even with O2-CaO, a practically operable oxygen ion conductivity can only be obtained at a high temperature of 800 to 1200°C.

As a result of extensive research and consideration with the aim of finding a substance with higher ion tolerance than conventional solid electrolytes, the present inventor has found that fluorinated oxides with a specific composition slow down the above purpose. I discovered what I could accomplish.

Thus, the present invention provides a compound having the general formula NdaYbFcOd (where a = 4.5 to 7.5.b-7,5 to 4.5.
Q=l 4-24, d=11-6 and 3a+3b=c+
2d and a+b-12).

When this is calculated by the respective ion ratios of cations and anions, y/N a = o, 5 to 1.67 degrees F10 = 1.27 to 4.

In the present invention, if the composition deviates from the above-mentioned composition, the conductivity decreases rapidly and the purpose of the present invention is not met, so it is inappropriate.

Of these composition ranges, a=5 to 71b=7 to
5, c = 1'6.5~22. d=9.8~7 and 3 a +3 b = c +2 eL and a 10 b
= 12 is particularly preferable for the platform since it exhibits particularly high isoelectricity. This is Y/Nd=0.7~
1.4, corresponding to F/O=1.7-3.1.

Furthermore, the material according to the present invention has the advantage of having sufficiently higher conductivity at low temperatures than those previously proposed, making it easier to select constituent materials when configuring various systems. .

The method for producing a conductive material according to the present invention involves pulverizing and mixing neodymium oxide and yttrium fluoride, or yttrium oxide and neodymium fluoride, and
It can be obtained by keeping it at 0°C for about 1 to 3 hours.

For example, if you want to obtain Nd'z Y2 Fs Ox, 1
20g of moles of Nd and 2 moles of YF3 or 1 mole of Y
It can be easily obtained by pulverizing and mixing zOa and 2 moles of NdFs and firing the mixture at 1100° C. for about 2 hours in an argon gas atmosphere.

Next, the present invention will be explained by examples.

Example 1 20g Na powder (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) 0,
After thoroughly pulverizing and mixing 5 mol and 1.0 mol of YFs powder, the mixture was filled into a high-purity alumina tube and fired in an argon gas stream. For firing, an annular door using a silicon carbide heating element was used and the heating rate was 10°C/min.
The temperature was raised to 00°C and maintained at the same temperature for about 2 hours. after that,
While maintaining an argon atmosphere, the mixture was slowly cooled to about 100° C. over about 3 hours.

After cooling, the sample was taken out and subjected to X-ray diffraction using a JEOL Ltd.
It was carried out by the powder method with pJRx-x2vA. The X-ray diffraction diagram is shown in FIG. The composition is Nd6YsFxgOo. Next, the 5-air conductivity bar and oxide ion transfer number were measured. 200-250 powder samples
After classifying into mesh, the sample was filled into a thick-walled quartz tube with an inner diameter of 2.5 mm so that the thickness under pressure was 2.5 am I/C, and the sample was separated by 60 to 9/C using a stainless steel pressure rod. Pressure was applied to CD. The pressure rod also serves as an electrode rod. After adjusting the atmosphere surrounding the sample to an oxygen partial pressure of 1 x 10'atm), the sample was heated using L manufactured by Yokogawa Hewlett-Paracard Co., Ltd. at a frequency of I KHz.
Before resistance using the two terminal method using CR Make 4261A
I made a decision.

As a result of measurement, 1. I x 10-2m
h.

/cr11 electrical conductivity is samurai.

Also, from the ratio of the measured value and the theoretical value of the concentration electromotive force, the ion $i
The i and i ratios were determined and were found to be about 0.80 at 650°C.

Example 2 Nd'B3 powder (manufactured by Shin-Etsu Chemical Co., Ltd., Cell 99.9chi) 1.
1jd6Y6Fz80 was carried out under the same conditions except that 0 mol and 0.5 mol of Y2O3 powder were used
゜ was synthesized. As a result of xH diffraction measurement, the structure is shown in Figure 1.
' Nd6Y6FtsO cleaved in Example 1 as shown in
It was the same as o.

The wake conductivity and transference number were measured under the conditions of Example 1 and were found to be 1.2 x 10-2 mho/an, about 0.80.

The results were substantially the same as in Example 1.

Example 3 NazO3 powder (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) 02
After sufficiently pulverizing and mixing 7 moles of YTs powder (same) and 073 moles of YTs powder, a fired product was obtained in the same manner as in Example 1.
X-ray diffraction, electromagnetic radiation, anal and ionic transport numbers were measured under the same conditions as described above.

i M, m of things, NdatYg, 5F2o, soy
, t theal.

The results of the X-center diffraction group 1'' leg are as shown in Figure 2, which shows the tetragonal crystal (&
It was monophase.

Electrical conductivity and ionic transference number are each 2.6X10”mh
o/crn, approximately O,S.

Example 4 N (120a powder (Shin-Etsu Chemical &, purity 999cm) 0.
After sufficiently pulverizing and mixing 37 mol of YFa powder (same) and 0.63-E-L, the fired product was prepared in the same manner as in Example 1, and subjected to X-glue diffraction measurement under the same conditions as in Example 1. Air conductivity and ion transference numbers were measured.

The composition of the fired product is Nc16. , Y5sF1&5Oay OX i7. ! As shown in FIG. 3, the diffraction results showed a single-phase tetragonal structure.

The electric conductor and ionic transference numbers are each 6.4 x 10-
3rr1h, o 7'an was approximately 0.70.

Examples 5-6 From 07 mol of NdYs powder and 03 mol of Y2O3 powder and N
A baked chicken product was obtained from 0.6 mol of dY+ powder and 0.4 mol of Y2O3 powder. The composition of the former (Example 5) is:
Nd6. sY5. sF1 tension 40B.
It is 4010.8.

As shown in FIGS. 4 and 5, the results of X-ray diffraction measurements showed that the specimens were both tetragonal crystals.

As a result of measuring the degree of concentration and ion transfer number, Example 5
In Example 6, 1,3 X 10"-" mho/cm, approximately 0.8, and 2.4 XIO' mho/cm, approximately 0.8.
Met.

Comparative Example 1 ZrOx powder (manufactured by Mitsuso Chemical Co., Ltd., purity 99.9
0.86 mol and Y2O3 powder (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99
．． 9%) o, 14 mol was calcined with 15-An at 1400°C in the same manner as in Example 1 to form (ZrO2)o.
, agfi2os) 0.14 composition was obtained. Electric conductivity and ion transport were measured under the same conditions as in Example 1. The result is 2.7810' mho 76
m and about 0.85.

The electrical conductivity is 1/10 compared to Examples 1 to 6.
It turns out that it is ~1/1ooo.

) Victory 1 1
t /// )60 50,
41) j02θ ) Yari 3 (l/l) ” Kong Tsukushin 1 #j Dogyoku 2 dF (method) November 1981 811 Commissioner of the Patent Office Kazuo Wakasugi 1. 41 items displayed 1988! 2. List of inventions: Electrical materials: 3. It! Doing i+lE - 1 If Notes Patent Application 1 Applicant Address 2-1-2, Chiyo, Tokyo ``■'' Medical University Name ('(104) Asahi Glass Jl-O (Large Company 4, Agent Published 05) Address Tokyo 111S Minato-ku Toranomon-Cho-ro 16-2 Toranomon Chiyo III Hill 6, Amendment 1) Details of the invention in the specification, i:lil explanation column (2)
i1M simple explanation column of drawings by Ming Chaofang (3) Drawing 7, contents of supplementary IF (1) On page 5, line 13 of the specification, Figure 1' is corrected to Figure 1-2.

(2) Akira jjO! ? ! Correct each of F7, 7th fold, and 6.

(:l) I! Insert the following sentence after IQ' 2nd line 1''.

[Brief explanation of drawings]

Figure 19Figure 1-21Figure 21Figure 39Figure 4-11Figure 4-2 is
Examples J-G (!!
Line diffraction diagram 1"C・1) Attachment [The display of p11' on plane 21 is corrected to Figure 1-2. For reference 1:,. Attached is the attached revised iE reference diagram.

Claims (1)

[Claims] General formula Nda Yb Fc Od (where a = 4.
5-7.5. b = 7.5-4.5. c==14-24. (1=1
1 to 6 and 3a+3b=c+2d and a+b=12
) is a conductive substance indicated by