JP2865174B2 - Copper oxide conductive compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive compound, specifically, a copper oxide-based conductive compound.

2. Description of the Related Art A conductive compound as an inorganic substance has been used in a wide range of fields as an electrode, a heating element and the like by utilizing its excellent properties such as corrosion resistance and heat resistance. For example, in the chlorine industry, RuO ₂ is particularly suitable as an electrode material because of its characteristics such as low power consumption and excellent corrosion resistance. This RuO ₂ is also recently used for a thermal head of a thermal transfer printer. Further, as another application example of the conductive compound, IT0
Application of (In-Sn-O) compound to transparent electrode, PL
The application field of a ZT (Pb-La-Zn-Ti) compound, such as an optical switch and an optical shutter, is expanding. In addition, conductive compounds are also used as electrodes of various sensors for converting changes in the external environment into electrical signals. Further, considering heat resistance, La
-Cr-O-based or La-Co-O-based conductive compounds are also useful as furnace heating elements and fuel cell electrodes.

[0002]

As described above, since the conductive compound is applied to a wide variety of fields and its usefulness is emphasized, the appearance of a conductive compound which is easy to manufacture and inexpensive is always desired. ing. The present invention has been made in view of the above-described conventional circumstances, and uses a readily available raw material and heats it at a relatively low temperature, so that a copper oxide-based conductive material that can be produced industrially advantageously. It is intended to provide a sex compound.

[0003]

Means for Solving the Problems The present invention has the following general formula:
It relates to the copper oxide-based conductive compound shown. (M_xCu_y)₇O_zA_w  (In the above formula, M is Dy, Ho, Er, Tb, T
at least selected from the group consisting of m, Yb, and Lu
Is also a kind of element, A is a halogen element and / or NO₃To
X + y = 1, 0 <x / y ≦ 10, 6 ≦ Z ≦ 8,
0.5 ≦ w ≦ 9. ) Copper oxide-based conductivity of the present invention
As the peak of the X-ray diffraction spectrum of the compound, 2θ is 1
6.0-16.8 ゜, 29.5-34.0 ゜, 37.8
３９39.5 ゜, 41.0〜43.0 ゜, 54.6-5
The peak at 7.0 ° is characteristic. These peaks
Plane indices 111, 222, 400, 33 of cubic crystals
1,440. The axial length a is about 9.2 to 9.8Å
It is.

According to the X-ray diffraction spectrum pattern of the copper oxide-based conductive compound of the present invention, the copper oxide-based conductive compound of the present invention has a cubic system having a composition similar to that of Ag ₇ O ₈ (NO ₃ ). Recognized as a crystal. In this crystal, cubic oxygen partially deficient is included, and the oxidation number of M and copper is considered to be a mixed valence of +1 to +3.
This is presumed to contribute to conductivity.

[0005] The copper oxide-based conductive compound of the present invention can be produced, for example, as follows. That is, first, Dy (dysprosium), Ho (holmium), E
oxides and / or nitrates and / or chlorides of at least one element selected from the group consisting of r (erbium), Tb (terbium), Tm (thulium), Yb (ytterbium), and Lu (lutetium); A predetermined amount of copper nitrate and / or chloride is mixed, and then the obtained mixture is heated at 200 to 650 ° C, preferably 250 to 450 ° C.
By heating at ° C, the copper oxide-based conductive compound of the present invention is obtained. Here, when the heating temperature exceeds 650 ° C., the insulating compounds CuO and / or Dy, Ho, Er,
Oxide of Tb, Tm, Yb or Lu (M ₂ O ₃ )
Is decomposed and generated, and the generation ratio of the conductive compound is reduced. Further, when the temperature is high, the compound becomes an insulating compound, which is not preferable. On the other hand, when the heating temperature is lower than 200 ° C., the decomposition reaction of nitrate does not proceed efficiently. This heating treatment uses a normal heating device such as an electric furnace, and the heating time is appropriately selected from about 1 minute to 50 hours. The heat treatment can be performed while removing volatile decomposition products by flowing a gas such as oxygen, nitrogen, or air, or can be performed under reduced pressure instead of flowing a gas. The nitrates and chlorides used naturally include hydrates,
Further, as the copper nitrate, basic copper nitrate Cu ₂ (OH) ₃
(NO ₃ ) can also be used. As a method for mixing the raw material compounds of oxides, nitrates and / or chlorides, a method of mixing and pulverizing each raw material compound with a ball mill or the like, or a method of mixing an aqueous solution of each raw material compound, and evaporating to dryness to obtain water. Can be adopted.

[0006]

The copper oxide conductive compound of the present invention is a high-performance conductive compound having both heat resistance, corrosion resistance, mechanical properties and conductivity, and is used as an electrode material for fuel cell electrodes and various sensors. It can be used for applications such as heating elements for furnaces. Also,
It is extremely useful as a raw material for producing a solid catalyst in various chemical reactions or a superconductor in which technical progress has been remarkable in recent years. Such a copper oxide-based conductive compound of the present invention can be efficiently produced at a relatively low heating temperature of 200 to 650 ° C. using easily available raw materials such as nitrates and chlorides.

[0007]

Examples of the present invention will be described below. Example 1 0.552 g (1.44 mmol) of erbium oxide, 3.49 g (14.44 mmol) of copper nitrate trihydrate, and 0.492 g (2.89 mmol) of copper chloride dihydrate were mixed well, and the mixture was mixed. Heated at 450 ° C. for 2 hours under an oxygen stream. As a result, a cubic X-ray diffraction pattern (using CuKα rays) as shown in FIG. 1 (2θ = 16.6 ゜ [11
1], 33.5 ° [222], 38.9 ° [400],
42.5 ° [331], 56.2 ° [440]) were obtained. From the X-ray diffraction spectrum, (Er _1/7 C
It was confirmed that u _6/7 ) ₇ O _z Cl was produced. FIG. 2 shows a temperature-resistivity curve of the copper oxide-based conductive compound. From FIG. 2, the specific resistance at room temperature of the obtained copper oxide-based conductive compound was 4 × 10 ⁻³ Ωcm, and it was revealed that the compound had good conductivity. This compound was paramagnetic at room temperature. FIG. 3 shows the MH magnetization curve.

Example 2 1.22 g (2.75 mmol) of erbium nitrate pentahydrate
l), 3.32 g (13.72 mmol) of copper nitrate trihydrate
l), 0.468 g (2.75 mmol) of copper chloride dihydrate
1) was mixed well and the mixture was heated at 450 ° C. for 2 hours under an oxygen atmosphere. As a result, a cubic X similar to FIG.
Line diffraction pattern (2θ = 16.6 ° [111];
A copper oxide-based conductive compound exhibiting 5 {222}, 38.9} [400], 42.5} [331], and 56.2} [440] was obtained. According to the present example, (Er _{1 / 7} Cu
_6/7 ) ₇ O _z Cl was confirmed to have been formed. The specific resistance (room temperature) of this copper oxide-based conductive compound is 8 × 10
^-3 Ωcm. Example 3 0.603 g (1.60 mmol) of holmium oxide, 3.85 g (15.95 mmol) of copper nitrate trihydrate, and 0.544 g (3.19 mmol) of copper chloride dihydrate were mixed well, and the mixture was mixed. Heated at 450 ° C. for 2 hours in an oxygen atmosphere. As a result, a cubic X-ray diffraction pattern (2θ = 16.5 ° [111], 33.4 ° [2
22], 38.8 {[400], 42.5} [33
1], 56.0 ° [440]), and according to this example, (Ho _1/7 Cu
_6/7 ) ₇ O _z Cl was confirmed to have been formed. FIG. 5 shows a temperature-resistivity curve of the copper oxide-based conductive compound. The specific resistance (room temperature) of the copper oxide-based conductive compound obtained from FIG. 5 was 4.2 × 10 ⁻³ Ωcm, and the compound was paramagnetic at room temperature.

EXAMPLE 4 1.22 g (2.74 m) of dysprosium nitrate pentahydrate
mol), 3.31 g (13.70 mm) of copper nitrate trihydrate
ol), 0.467 g (2.74 mmol) of copper chloride dihydrate
1) was mixed well, and the mixture was heated at 350 ° C. for 2 hours under an oxygen atmosphere. As a result, a cubic X similar to FIG.
Line diffraction pattern (2θ = 16.5 ° [111];
A copper oxide-based conductive compound showing 3 {[222], 38,7} [400], 42.4 {[331], 55.8} [440]) was obtained, and according to the present example, (Dy _{1 / 7} C
It was confirmed that u _6/7 ) ₇ O _z Cl was produced. The specific resistance (room temperature) of this copper oxide-based conductive compound is 1 × 10
⁻² Ωcm. Example 5 0.631 g (1.58 mmol) of lutetium oxide, 3.83 g (15.85 mmol) of copper nitrate trihydrate, and 0.54 g (3.17 mmol) of copper chloride dihydrate were mixed well, and the mixture was mixed. Heated at 450 ° C. for 2 hours in an oxygen atmosphere. As a result, a cubic X-ray diffraction pattern (2θ = 16.6 ° [111], 33.6 ° [22
2], 39.0 ° [400], 42.7 ° [331],
56.4 ([440]), a copper oxide-based conductive compound was obtained. According to this example, (Lu _1/7 Cu _6/7 ) ₇ was obtained.
It was confirmed that O _z Cl was formed. The specific resistance (room temperature) of the copper oxide-based conductive compound was 8 × 10 ⁻³ Ωcm.

Example 6 0.613 g (0.80 mmol) of terbium oxide, 3.87 g (16.01 mmol) of copper nitrate trihydrate, and 0.546 g (3.20 mmol) of copper chloride dihydrate were mixed well. The mixture was heated at 450 ° C. for 2 hours under an oxygen atmosphere. As a result, a cubic X-ray diffraction pattern similar to that of FIG. 1 (2θ = 16.5 ° [111], 33.4 ° [22
2], 38.8 ° [400], 42.5 ° [331],
Thus, a copper oxide-based conductive compound exhibiting 56.0 [[440]) was obtained, and according to this example, (Tb _1/7 Cu _6/7 ) ₇
It was confirmed that O _z Cl was formed. The specific resistance (room temperature) of the copper oxide-based conductive compound was 1 × 10 ⁻² Ωcm. Example 7 1.15 g of ytterbium nitrate trihydrate (2.79 mm
ol), 3.37 g (14.0 mmol) of copper nitrate trihydrate
l), 0.476 g (2.79 mmol) of copper chloride dihydrate
1) was mixed well and the mixture was heated at 450 ° C. for 2 hours under an oxygen atmosphere. As a result, a cubic X similar to FIG.
Line diffraction pattern (2θ = 16.6 ° [111];
6 [222], 39.0 [400], 42.6 [331], 56.3 [440]), a copper oxide-based conductive compound was obtained, and (Yb _{1 / 7} C
It was confirmed that u _6/7 ) ₇ O _z Cl was produced. The specific resistance (room temperature) of this copper oxide-based conductive compound is 6 × 10
^-3 Ωcm.

Example 8 0.540 g (1.40 mmol) of thulium oxide, 3.37 g (14.0 mmol) of copper nitrate trihydrate and 0.476 g (2.79 mmol) of copper chloride dihydrate were mixed well. The mixture was heated at 450 ° C. for 2 hours under an oxygen atmosphere. As a result, a cubic X-ray diffraction pattern similar to that of FIG. 1 (2θ = 16.6 ° [111], 33.5 ° [22
2], 38.9 ° [400], 42.5 ° [331],
A copper oxide-based conductive compound exhibiting 56.2 {[440]) was obtained, and according to the present example, (Tm _1/7 Cu _6/7 ) ₇ was obtained.
It was confirmed that O _z Cl was formed. The specific resistance (room temperature) of the copper oxide-based conductive compound was 1 × 10 ⁻² Ωcm. Example 9 0.35 g (0.914 mmol) of erbium oxide and 2.65 g (11.0 mmol) of copper nitrate trihydrate were mixed well, and the mixture was heated at 330 ° C. for 1 hour in an oxygen atmosphere. As a result, a cubic X-ray diffraction pattern similar to that of FIG. 1 (2θ = 16.4 {[111], 33.1} [22
2], 38.4 ゜ [400], 42.0 ゜ [331],
A copper oxide-based conductive compound exhibiting 55.4 ([440]) was obtained, and according to this example, (Er _1/7 Cu _6/7 ) ₇ was obtained.
The O _z NO ₃ was produced was confirmed. The specific resistance (room temperature) of the copper oxide-based conductive compound is 8 × 10 ⁻² Ωcm.
This compound was paramagnetic at room temperature.

Example 10 0.703 g (1.59 mmol) of erbium nitrate pentahydrate
l) and 2.30 g (9.51 mmol) of copper nitrate trihydrate
Was thoroughly mixed, and the mixture was heated at 330 ° C. for 1 hour under an oxygen atmosphere. As a result, a cubic X-ray diffraction pattern similar to that of FIG. 1 (2θ = 16.4 {[111], 33.1} [222], 38.4} [400], 42.0} [33
1], 55.4 ° [440]), and according to this example, (Er _1/7 Cu
It was confirmed that _6/7 ) ₇ O _z NO ₃ was produced. The specific resistance (room temperature) of this copper oxide-based conductive compound is 8 × 10
⁻² Ωcm. Example 11 0.346 g (0.915 mmol) of holmium oxide and 2.65 g (11.0 mmol) of copper nitrate trihydrate were mixed well, and the mixture was heated at 330 ° C. for 1 hour in an oxygen atmosphere. As a result, a cubic X-ray diffraction pattern similar to FIG. 1 (2θ = 16.3 {[111], 33.0} [22
2], 38.3 {[400], 41.8} [331],
A copper oxide-based conductive compound exhibiting 55.2 ([440]) was obtained, and according to the present example, (Ho _1/7 Cu _6/7 ) ₇ was obtained.
The O _z NO ₃ was produced was confirmed. The specific resistance (room temperature) of the copper oxide-based conductive compound is 5 × 10 ⁻² Ωcm.
Met. The copper oxide conductive compound was paramagnetic at room temperature.

Example 12 0.362 g (0.91 mmol) of lutetium oxide and 2.64 g (10.9 mmol) of copper nitrate trihydrate were mixed well, and the mixture was heated at 330 ° C. for 1 hour in an oxygen atmosphere. As a result, a cubic X-ray diffraction pattern similar to FIG. 1 (2θ = 16.4 {[111], 33.2} [22
2], 38.5 ゜ [400], 42.1 ゜ [331],
A copper oxide-based conductive compound exhibiting 55.6 [[440]) was obtained, and according to this example, (Lu _1/7 Cu _6/7 ) ₇ was obtained.
The O _z NO ₃ was produced was confirmed. The specific resistance (room temperature) of the copper oxide-based conductive compound is 3 × 10 ⁻² Ωcm.
Met. Example 13 0.359 g of ytterbium oxide (0.910 mmol
l) and 2.64 g (10.9 mmol) of copper nitrate trihydrate
Was thoroughly mixed, and the mixture was heated at 330 ° C. for 1 hour under an oxygen atmosphere. As a result, a cubic X-ray diffraction pattern similar to that of FIG. 1 (2θ = 16.5 ° [111], 33.2 ° [222], 38.5 ° [400], 42.2 ° [33]
1], 55.6 ° [440]), and according to this example, (Yb _1/7 Cu
It was confirmed that _6/7 ) ₇ O _z NO ₃ was produced. The specific resistance (room temperature) of the copper oxide conductive compound is 2 × 10
⁻² Ωcm.

Example 14 0.351 g (0.458 mmol) of terbium oxide and 2.66 g (11.0 mmol) of copper nitrate trihydrate were mixed well, and the mixture was heated at 330 ° C. for 1 hour in an oxygen atmosphere. As a result, a cubic X-ray diffraction pattern similar to FIG. 1 (2θ = 16.3 {[111], 33.0} [22
2], 38.2 ゜ [400], 41.8 ゜ [331],
A copper oxide-based conductive compound exhibiting 55.2 {[440]) was obtained, and according to this example, (Tb _1/7 Cu _6/7 ) ₇ was obtained.
The O _z NO ₃ was produced was confirmed. The specific resistance (room temperature) of the copper oxide-based conductive compound is 1 × 10 ⁻¹ Ωcm.
Met. Example 15 0.342 g of dysprosium nitrate (0.917 mmol
l) and 2.66 g (11.0 mmol) of copper nitrate trihydrate
Was thoroughly mixed, and the mixture was heated at 330 ° C. for 1 hour under an oxygen atmosphere. As a result, a cubic X-ray diffraction pattern similar to FIG. 1 (2θ = 16.3 {[111], 32.9} [222], 38.2} [400], 41.8} [33
1], copper oxide-based conductive compound showing a 55.1 ° [440]) is obtained by the present embodiment _(Dy 1/7 Cu
It was confirmed that _6/7 ) ₇ O _z NO ₃ was produced. The specific resistance (room temperature) of this copper oxide-based conductive compound is 1 × 10
^-1 Ωcm. FIG. 6 shows the MH magnetization curve.

EXAMPLE 16 0.352 g (0.911 mmol) of thulium oxide and 2.64 g (10.9 mmol) of copper nitrate trihydrate were mixed well, and the mixture was heated at 330 ° C. for 1 hour in an oxygen atmosphere. As a result, a cubic X-ray diffraction pattern similar to FIG. 1 (2θ = 16.4 {[111], 33.1} [22
2], 38.4 ゜ [400], 42.0 ゜ [331],
A copper oxide-based conductive compound exhibiting 55.4 ([440]) was obtained, and according to this example, (Tm _1/7 Cu _6/7 ) ₇ was obtained.
The O _z NO ₃ was produced was confirmed. The specific resistance (room temperature) of the copper oxide-based conductive compound is 5 × 10 ⁻² Ωcm.
Met. Example 17 0.181 g (0.455 mmol) of lutetium oxide,
0.179 g of ytterbium oxide (0.455 mmol
l), 2.64 g (10.9 mmol) of copper nitrate trihydrate
Was thoroughly mixed, and the mixture was heated at 330 ° C. for 1 hour under an oxygen atmosphere. As a result, a cubic X-ray diffraction pattern similar to that of FIG. 1 (2θ = 16.5 ° [111], 33.2 ° [222], 38.5 ° [400], 42.2 ° [33]
1], 55.6 ゜ [440]), and according to this example, (Lu _1/14 Y
It was confirmed that _1/14 Cu _6/7 ) ₇ O _z NO ₃ was produced. The specific resistance (room temperature) of this copper oxide-based conductive compound was 5 × 10 ⁻² Ωcm. Example 18 0.172 g (0.45 mmol) of erbium oxide and 2.83 g of copper nitrate trihydrate (11. 7 mmol), and the mixture was heated at 330 ° C. for 1 hour under an oxygen atmosphere. As a result, a cubic X-ray diffraction pattern similar to FIG. 1 (2θ = 16.3 {[111], 33.0} [22
2], 38.3 {[400], 41.8} [331],
55.2 ([440]), a copper oxide-based conductive compound was obtained, and (Er _1/14 Cu
_{13/14) 7} that O _z NO ₃ was produced was confirmed. The specific resistance (room temperature) of this copper oxide-based conductive compound is 1
× 10 ^-1 Ωcm.

[Brief description of the drawings]

FIG. 1 shows an X-ray diffraction pattern of a copper oxide-based conductive compound of Example 1.

FIG. 2 shows a temperature-resistivity curve of the copper oxide-based conductive compound of Example 1.

FIG. 3 shows an MH magnetization curve of the copper oxide-based conductive compound of Example 1.

FIG. 4 shows an X-ray diffraction pattern of the copper oxide-based conductive compound of Example 3.

FIG. 5 shows a temperature-resistivity curve of the copper oxide-based conductive compound of Example 3.

FIG. 6 shows MH of the copper oxide-based conductive compound of Example 15.
3 shows a magnetization curve.

Claims (1)

(57) [Claims] 1. A copper oxide-based conductive material represented by the following general formula:
Compound (M_xCu_y)₇O_zA_w  (In the above formula, M is Dy, Ho, Er, Tb, T
at least selected from the group consisting of m, Yb, and Lu
Is also a kind of element, A is a halogen element and / or NO₃To
X + y = 1, 0 <x / y ≦ 10, 6 ≦ Z ≦ 8,
0.5 ≦ w ≦ 9. )