JPH0543228A - Copper oxide-based electric conductive compound - Google Patents
Copper oxide-based electric conductive compoundInfo
- Publication number
- JPH0543228A JPH0543228A JP11421191A JP11421191A JPH0543228A JP H0543228 A JPH0543228 A JP H0543228A JP 11421191 A JP11421191 A JP 11421191A JP 11421191 A JP11421191 A JP 11421191A JP H0543228 A JPH0543228 A JP H0543228A
- Authority
- JP
- Japan
- Prior art keywords
- copper oxide
- conductive compound
- based conductive
- copper
- mmol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/006—Compounds containing, besides copper, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、導電性化合物、具体的
には銅酸化物系の導電性化合物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive compound, specifically a copper oxide-based conductive compound.
【従来の技術】無機物としての導電性化合物は、耐食
性、耐熱性等の優れた特性を利用して、従来より、電
極、発熱体等として広い分野で使用されている。例え
ば、塩素工業において、RuO2は電力消費量が小さ
く、しかも耐腐食性等に優れるなどの特性から、電極材
料として特に好適である。このRuO2はまた、最近で
は熱転写プリンターのサーマルヘッドにも利用されてい
る。更に、導電性化合物の他の用途例としては、IT0
(In−Sn−O系)化合物の透明電極への適用、PL
ZT(Pb−La−Zn−Ti系)化合物の光スイッ
チ、光シャッターへの適用など、その応用分野は拡大し
つつある。その他、導電性化合物は、外部環境の変化を
電気的な信号に変換するための各種センサーの電極とし
ても利用されている。また、耐熱性を考慮すれば、La
−Cr−O系又はLa−Co−O系導電性化合物は、炉
用発熱体、燃料電池電極としても有用である。2. Description of the Related Art A conductive compound as an inorganic material has been used in a wide range of fields as an electrode, a heating element, etc., due to 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. Furthermore, as another application example of the conductive compound, IT0
Application of (In-Sn-O) compound to transparent electrode, PL
The application fields of ZT (Pb-La-Zn-Ti based) compounds such as optical switches and optical shutters are expanding. In addition, conductive compounds are also used as electrodes of various sensors for converting changes in the external environment into electrical signals. Also, considering heat resistance, La
The -Cr-O-based or La-Co-O-based conductive compound is also useful as a heating element for a furnace and a fuel cell electrode.
【0002】[0002]
【発明が解決しようとする課題】このように導電性化合
物の適用分野は多岐にわたり、その有用性が重視されて
いることから、さらに製造が容易で、安価な導電性化合
物の出現が常に望まれている。本発明は上記従来の実情
に鑑みてなされたものであり、容易に入手可能な原料を
用いて、比較的低温で加熱することにより、工業的に有
利に製造することができる銅酸化物系導電性化合物を提
供することを目的とする。As described above, since the fields of application of conductive compounds are diverse and importance is placed on their usefulness, the advent of conductive compounds that are easier to manufacture and cheaper is always desired. ing. The present invention has been made in view of the above conventional circumstances, by using a readily available raw material, by heating at a relatively low temperature, it is possible to industrially advantageously produce a copper oxide-based conductive It aims at providing a sex compound.
【0003】[0003]
【課題を解決するための手段】本発明は、下記一般式で
示される銅酸化物系導電性化合物に関する。 (MxCuy)7OzAw (上記式において、Mは、Dy、Ho、Er、Tb、T
m、Yb、及びLuよりなる群より選択される少なくと
も一種の元素、Aは、ハロゲン元素及び/又はNO3を
表わし、x+y=1、0<x/y≦10、6≦Z≦8、
0.5≦w≦9である。)本発明の銅酸化物系導電性化
合物のX線回折スペクトルのピークとしては、2θが1
6.0〜16.8゜、29.5〜34.0゜、37.8
〜39.5゜、41.0〜43.0゜、54.6〜5
7.0゜のピークが特徴的である。これらのピークは、
立方晶系の結晶の面指数111、222、400、33
1、440に帰属される。軸長aは約9.2〜9.8Å
である。The present invention has the following general formula.
The present invention relates to the copper oxide-based conductive compound shown. (MxCuy)7OzAw (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 NOThreeTo
, X + y = 1, 0 <x / y ≦ 10, 6 ≦ Z ≦ 8,
0.5 ≦ w ≦ 9. ) Copper oxide-based conductivity of the present invention
As for the peak of the X-ray diffraction spectrum of the compound, 2θ is 1
6.0-16.8 °, 29.5-34.0 °, 37.8
~ 39.5 °, 41.0-43.0 °, 54.6-5
The 7.0 ° peak is characteristic. These peaks are
Cubic crystal plane index 111, 222, 400, 33
Belonging to 1,440. Axle length a is about 9.2-9.8Å
Is.
【0004】本発明の銅酸化物系導電性化合物のX線回
折スペクトルのパターンから、本発明の銅酸化物系導電
性化合物は、Ag7O8(NO3)類似組成を有する立
方晶系の結晶であると認められる。この結晶において
は、立方晶の酸素が一部欠損したものも含まれ、M及び
銅の酸化数は+1〜+3の混合価数であると考えられ、
これが導電性に寄与するものと推定される。From the pattern of the X-ray diffraction spectrum of the copper oxide-based conductive compound of the present invention, the copper oxide-based conductive compound of the present invention is a cubic system having a composition similar to Ag 7 O 8 (NO 3 ). Recognized as crystalline. In this crystal, cubic oxygen partially deficient in oxygen is also included, and the oxidation numbers of M and copper are considered to have a mixed valence of +1 to +3.
It is presumed that this contributes to conductivity.
【0005】本発明の銅酸化物系導電性化合物は、例え
ば、以下のようにして製造することができる。即ち、ま
ずDy(ディスプロシウム)、Ho(ホルミウム)、E
r(エルビウム)、Tb(テルビウム)、Tm(ツリウ
ム)、Yb(イッテルビウム)、及びLu(ルテチウ
ム)よりなる群より選択される少なくとも一種の元素の
酸化物及び/又は硝酸塩及び/又は塩化物と、銅の硝酸
塩及び/又は塩化物を所定量混合し、ついで、得られた
混合物を200〜650℃、好ましくは250〜450
℃で加熱することにより、本発明の銅酸化物系導電性化
合物を得る。ここで、加熱温度が650℃を越えると絶
縁性化合物であるCuO及び/又はDy、Ho、Er、
Tb、Tm、Yb、あるいはLuの酸化物(M2O3)
が分解生成し、導電性化合物の生成割合が減少し、さら
に高温の場合には全て絶縁性化合物となるため好ましく
ない。一方、加熱温度が200℃未満では硝酸塩の分解
反応が効率的に進行しない。この加熱処理は電気炉等の
通常の加熱装置を用い、加熱時間は1分〜50時間程度
の間で適宜選定される。また、加熱処理は、酸素、窒
素、あるいは空気などのガスを流通させて、揮発性分解
物を除去しながら行うことも、あるいは、ガスを流通さ
せる代わりに、減圧下で行うこともできる。なお、使用
される硝酸塩及び塩化物にはその水和物も当然含まれ、
また、硝酸銅としては、塩基性硝酸銅Cu2(OH)3
(NO3)も使用可能である。酸化物、硝酸塩及び/又
は塩化物の原料化合物の混合法としては、各々の原料化
合物をボールミル等で混合粉砕する方法、又は、各々の
原料化合物の水溶液を混合した後、蒸発乾固して水を除
去する方法等を採用することができる。The copper oxide type conductive compound of the present invention can be produced, for example, as follows. That is, first, Dy (dysprosium), Ho (holmium), E
an oxide and / or a nitrate and / or a chloride 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 200 to 650 ° C, preferably 250 to 450.
By heating at ℃, the copper oxide-based conductive compound of the present invention is obtained. Here, when the heating temperature exceeds 650 ° C., CuO and / or Dy, Ho, Er, which are insulating compounds,
Oxide of Tb, Tm, Yb, or Lu (M 2 O 3 )
Are decomposed and produced, the production ratio of the conductive compound is reduced, and when the temperature is high, all become an insulating compound, which is not preferable. On the other hand, if the heating temperature is less than 200 ° C., the decomposition reaction of nitrate does not proceed efficiently. For this heat treatment, an ordinary heating device such as an electric furnace is used, and the heating time is appropriately selected from about 1 minute to 50 hours. The heat treatment can be performed while circulating a gas such as oxygen, nitrogen, or air to remove volatile decomposition products, or can be performed under reduced pressure instead of passing the gas. It should be noted that the nitrates and chlorides used naturally include their hydrates,
Further, as 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, each raw material compound is mixed and pulverized by a ball mill or the like, or an aqueous solution of each raw material compound is mixed and then evaporated to dryness to obtain water. Can be adopted.
【0006】[0006]
【発明の効果】本発明の銅酸化物系導電性化合物は、耐
熱性、耐腐食性、機械的特性と導電性を兼備する高特性
導電性化合物であり、燃料電池電極、各種センサーの電
極材料、炉用発熱体等の用途に使用可能である。また、
各種の化学反応における固体触媒、あるいは近年技術進
歩の著しい超伝導体を製造するための原料としても極め
て有用である。このような本発明の銅酸化物系導電性化
合物は、硝酸塩や塩化物といった容易に入手可能な原料
を用いて、200〜650℃といった比較的低い加熱温
度で効率的に製造することができる。The copper oxide-based conductive compound of the present invention is a high-performance conductive compound having 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 also extremely useful as a solid catalyst in various chemical reactions or as a raw material for producing superconductors, which have undergone remarkable technological progress 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】[0007]
【実施例】以下に本発明の実施例を示す。 実施例1 酸化エルビウム0.552g(1.44mmol)、硝
酸銅三水和物3.49g(14.44mmol)、塩化
銅二水和物0.492g(2.89mmol)を良く混
合し、混合物を酸素気流下、450℃で2時間加熱し
た。その結果、図1に示すような立方晶系のX線回折パ
ターン(CuKα線使用)(2θ=16.6゜[11
1]、33.5゜[222]、38.9゜[400]、
42.5゜[331]、56.2゜[440])を有す
る銅酸化物系導電性化合物が得られた。このX線回折ス
ペクトルから、本実施例により(Er1/7C
u6/7)7OzClが生成したことが確認された。こ
の銅酸化物系導電性化合物の温度・比抵抗曲線を図2に
示す。図2より得られた銅酸化物系導電性化合物の室温
での比抵抗は4×10−3Ωcmであり、良好な導電性
を有することが明らかになった。また、この化合物は室
温で常磁性であった。図3はM・H磁化曲線を示す。EXAMPLES Examples of the present invention will be shown 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. It heated at 450 degreeC under oxygen stream for 2 hours. 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],
A copper oxide type conductive compound having 42.5 ° [331] and 56.2 ° [440]) was obtained. From this X-ray diffraction spectrum, (Er 1/7 C
It was confirmed that u 6/7 ) 7 O z Cl was produced. The temperature / resistivity curve of this copper oxide-based conductive compound is shown in FIG. The specific resistance at room temperature of the copper oxide-based conductive compound obtained from FIG. 2 was 4 × 10 −3 Ωcm, demonstrating that it has good conductivity. Also, this compound was paramagnetic at room temperature. FIG. 3 shows the MH magnetization curve.
【0008】実施例2 硝酸エルビウム五水和物1.22g(2.75mmo
l)、硝酸銅三水和物3.32g(13.72mmo
l)、塩化銅二水和物0.468g(2.75mmo
l)を良く混合し、混合物を酸素雰囲気下、450℃で
2時間加熱した。その結果、図1と類似の立方晶系のX
線回折パターン(2θ=16.6゜[111]、33.
5゜[222]、38.9゜[400]、42.5゜
[331]、56.2゜[440]を示す銅酸化物系導
電性化合物が得られ、本実施例により(Er1/7Cu
6/7)7OzClが生成したことが確認された。この
銅酸化物系導電性化合物の比抵抗(室温)は8×10
−3Ωcmであった。 実施例3 酸化ホルミウム0.603g(1.60mmol)、硝
酸銅三水和物3.85g(15.95mmol)、塩化
銅二水和物0.544g(3.19mmol)を良く混
合し、混合物を酸素雰囲気下、450℃で2時間加熱し
た。その結果、図4に示すような立方晶系のX線回折パ
ターン(2θ=16.5゜[111]、33.4゜[2
22]、38.8゜[400]、42.5゜[33
1]、56.0゜[440])を有する銅酸化物系導電
性化合物が得られ、本実施例により(Ho1/7Cu
6/7)7OzClが生成したことが確認された。この
銅酸化物系導電性化合物の温度・比抵抗曲線を図5に示
す。図5より得られたこの銅酸化物系導電性化合物の比
抵抗(室温)は4.2×10−3Ωcmであり、この化
合物は室温で常磁性であった。Example 2 1.22 g (2.75 mmo) of erbium nitrate pentahydrate
l), 3.32 g (13.72 mmo) of copper nitrate trihydrate
l), 0.468 g (2.75 mmo) 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 system X similar to that shown in FIG.
Line diffraction pattern (2θ = 16.6 ° [111], 33.
Copper oxide-based conductive compounds showing 5 ° [222], 38.9 ° [400], 42.5 ° [331] and 56.2 ° [440] were obtained, and according to this example, (Er 1 / 7 Cu
It was confirmed that 6/7 ) 7 O z Cl was produced. The specific resistance (room temperature) of this copper oxide-based conductive compound is 8 × 10.
It was −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. It heated at 450 degreeC in oxygen atmosphere for 2 hours. As a result, a cubic X-ray diffraction pattern (2θ = 16.5 ° [111], 33.4 ° [2] as shown in FIG.
22], 38.8 ° [400], 42.5 ° [33
1], 56.0 ° [440]), and a copper oxide-based conductive compound is obtained, and according to this example, (Ho 1/7 Cu)
It was confirmed that 6/7 ) 7 O z Cl was produced. The temperature / resistivity curve of this copper oxide type conductive compound is shown in FIG. The specific resistance (room temperature) of this copper oxide-based conductive compound obtained from FIG. 5 was 4.2 × 10 −3 Ωcm, and this compound was paramagnetic at room temperature.
【0009】実施例4 硝酸ディスプロシウム五水和物1.22g(2.74m
mol)、硝酸銅三水和物3.31g(13.70mm
ol)、塩化銅二水和物0.467g(2.74mmo
l)を良く混合し、混合物を酸素雰囲気下、350℃で
2時間加熱した。その結果、図1と類似の立方晶系のX
線回折パターン(2θ=16.5゜[111]、33.
3゜[222]、38,7゜[400]、42.4゜
[331]、55.8゜[440])を示す銅酸化物系
導電性化合物が得られ、本実施例により(Dy1/7C
u6/7)7OzClが生成したことが確認された。こ
の銅酸化物系導電性化合物の比抵抗(室温)は1×10
−2Ωcmであった。 実施例5 酸化ルテチウム0.631g(1.58mmol)、硝
酸銅三水和物3.83g(15.85mmol)、塩化
銅二水和物0.54g(3.17mmol)を良く混合
し、混合物を酸素雰囲気下、450℃で2時間加熱し
た。その結果、図1と類似の立方晶系のX線回折パター
ン(2θ=16.6゜[111]、33.6゜[22
2]、39.0゜[400]、42.7゜[331]、
56.4゜[440])を示す銅酸化物系導電性化合物
が得られ、本実施例により(Lu1/7Cu6/7)7
OzClが生成したことが確認された。この銅酸化物系
導電性化合物の比抵抗(室温)は8×10−3Ωcmで
あった。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 of copper chloride dihydrate (2.74 mmo)
1) was mixed well and the mixture was heated at 350 ° C. for 2 hours under oxygen atmosphere. As a result, a cubic system X similar to that shown in FIG.
Line diffraction pattern (2θ = 16.5 ° [111], 33.
3 ° [222], 38,7 ° [400], 42.4 ° [331], 55.8 ° [440]) was obtained, and a copper oxide-based conductive compound was obtained according to this 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.
It was −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. It heated at 450 degreeC in oxygen atmosphere for 2 hours. As a result, a cubic X-ray diffraction pattern (2θ = 16.6 ° [111], 33.6 ° [22] similar to that of FIG. 1 was obtained.
2], 39.0 ° [400], 42.7 ° [331],
A copper oxide-based conductive compound exhibiting 56.4 ° [440]) was obtained, and (Lu 1/7 Cu 6/7 ) 7 was obtained according to this example.
It was confirmed that O z Cl was generated. The specific resistance (room temperature) of this copper oxide-based conductive compound was 8 × 10 −3 Ωcm.
【0010】実施例6 酸化テルビウム0.613g(0.80mmol)、硝
酸銅三水和物3.87g(16.01mmol)、塩化
銅二水和物0.546g(3.20mmol)を良く混
合し、混合物を酸素雰囲気下、450℃で2時間加熱し
た。その結果、図1と類似の立方晶系のX線回折パター
ン(2θ=16.5゜[111]、33.4゜[22
2]、38.8゜[400]、42.5゜[331]、
56.0゜[440])を示す銅酸化物系導電性化合物
が得られ、本実施例により(Tb1/7Cu6/7)7
OzClが生成したことが確認された。この銅酸化物系
導電性化合物の比抵抗(室温)は1×10−2Ωcmで
あった。 実施例7 硝酸イッテルビウム三水和物1.15g(2.79mm
ol)、硝酸銅三水和物3.37g(14.0mmo
l)、塩化銅二水和物0.476g(2.79mmo
l)を良く混合し、混合物を酸素雰囲気下、450℃で
2時間加熱した。その結果、図1と類似の立方晶系のX
線回折パターン(2θ=16.6゜[111]、33.
6゜[222]、39.0゜[400]、42.6゜
[331]、56.3゜[440])を示す銅酸化物系
導電性化合物が得られ、本実施例により(Yb1/7C
u6/7)7OzClが生成したことが確認された。こ
の銅酸化物系導電性化合物の比抵抗(室温)は6×10
−3Ωcmであった。Example 6 Terbium oxide 0.613 g (0.80 mmol), copper nitrate trihydrate 3.87 g (16.01 mmol), and copper chloride dihydrate 0.546 g (3.20 mmol) were mixed well. The mixture was heated at 450 ° C. for 2 hours under oxygen atmosphere. As a result, a cubic X-ray diffraction pattern (2θ = 16.5 ° [111], 33.4 ° [22] similar to that of FIG. 1 was obtained.
2], 38.8 ° [400], 42.5 ° [331],
A copper oxide-based conductive compound exhibiting 56.0 ° [440]) was obtained, and (Tb 1/7 Cu 6/7 ) 7 was obtained according to this example.
It was confirmed that O z Cl was generated. The specific resistance (room temperature) of this copper oxide-based conductive compound was 1 × 10 −2 Ωcm. Example 7 1.15 g (2.79 mm) of ytterbium nitrate trihydrate
ol), copper nitrate trihydrate 3.37 g (14.0 mmo
l), 0.476 g (2.79 mmo) 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 system X similar to that shown in FIG.
Line diffraction pattern (2θ = 16.6 ° [111], 33.
6 ° [222], 39.0 ° [400], 42.6 ° [331], 56.3 ° [440]) was obtained, and a copper oxide-based conductive compound was obtained according to this example (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.
It was −3 Ωcm.
【0011】実施例8 酸化ツリウム0.540g(1.40mmol)、硝酸
銅三水和物3.37g(14.0mmol)、塩化銅二
水和物0.476g(2.79mmol)を良く混合
し、混合物を酸素雰囲気下、450℃で2時間加熱し
た。その結果、図1と類似の立方晶系のX線回折バター
ン(2θ=16.6゜[111]、33.5゜[22
2]、38.9゜[400]、42.5゜[331]、
56.2゜[440])を示す銅酸化物系導電性化合物
が得られ、本実施例により(Tm1/7Cu6/7)7
OzClが生成したことが確認された。この銅酸化物系
導電性化合物の比抵抗(室温)は1×10−2Ωcmで
あった。 実施例9 酸化エルビウム0.35g(0.914mmol)と硝
酸銅三水和物2.65g(11.0mmol)を良く混
合し、混合物を酸素雰囲気下、330℃で1時間加熱し
た。その結果、図1と類似の立方晶系のX線回折パター
ン(2θ=16.4゜[111]、33.1゜[22
2]、38.4゜[400]、42.0゜[331]、
55.4゜[440])を示す銅酸化物系導電性化合物
が得られ、本実施例により(Er1/7Cu6/7)7
OzNO3が生成したことが確認された。この銅酸化物
系導電性化合物の比抵抗(室温)は8×10−2Ωcm
であり、この化合物は室温で常磁性であった。EXAMPLE 8 Thulium oxide (0.540 g, 1.40 mmol), copper nitrate trihydrate (3.37 g, 14.0 mmol) and copper chloride dihydrate (0.476 g, 2.79 mmol) were mixed well. The mixture was heated at 450 ° C. for 2 hours under oxygen atmosphere. As a result, a cubic X-ray diffraction pattern (2θ = 16.6 ° [111], 33.5 ° [22] similar to that of FIG.
2], 38.9 ° [400], 42.5 ° [331],
A copper oxide-based conductive compound exhibiting 56.2 ° [440]) was obtained, and (Tm 1/7 Cu 6/7 ) 7 was obtained according to this example.
It was confirmed that O z Cl was generated. The specific resistance (room temperature) of this copper oxide-based conductive compound was 1 × 10 −2 Ωcm. Example 9 0.35 g (0.914 mmol) of erbium oxide was mixed well with 2.65 g (11.0 mmol) of copper nitrate trihydrate, and the mixture was heated at 330 ° C. for 1 hour under an oxygen atmosphere. As a result, a cubic X-ray diffraction pattern (2θ = 16.4 ° [111], 33.1 ° [22] similar to that of FIG. 1 was obtained.
2], 38.4 ° [400], 42.0 ° [331],
A copper oxide-based conductive compound exhibiting 55.4 ° [440]) was obtained, and (Er 1/7 Cu 6/7 ) 7 was obtained according to this example.
It was confirmed that O z NO 3 was produced. The specific resistance (room temperature) of this copper oxide-based conductive compound is 8 × 10 −2 Ωcm.
And this compound was paramagnetic at room temperature.
【0012】実施例10 硝酸エルビウム五水和物0.703g(1.59mmo
l)と硝酸銅三水和物2.30g(9.51mmol)
を良く混合し、混合物を酸素雰囲気下、330℃で1時
間加熱した。その結果、図1と類似の立方晶系のX線回
折パターン(2θ=16.4゜[111]、33.1゜
[222]、38.4゜[400]、42.0゜[33
1]、55.4゜[440])を示す銅酸化物系導電性
化合物が得られ、本実施例により(Er1/7Cu
6/7)7OzNO3が生成したことが確認された。こ
の銅酸化物系導電性化合物の比抵抗(室温)は8×10
−2Ωcmであった。 実施例11 酸化ホルミウム0.346g(0.915mmol)と
硝酸銅三水和物2.65g(11.0mmol)を良く
混合し、混合物を酸素雰囲気下、330℃で1時間加熱
した。その結果、図1と類似の立方晶系のX線回折パタ
ーン(2θ=16.3゜[111]、33.0゜[22
2]、38.3゜[400]、41.8゜[331]、
55.2゜[440])を示す銅酸化物系導電性化合物
が得られ、本実施例により(Ho1/7Cu6/7)7
OzNO3が生成したことが確認された。この銅酸化物
系導電性化合物の比抵抗(室温)は5×10−2Ωcm
であった。また、この銅酸化物系導電性化合物は室温で
常磁性であった。Example 10 Erbium nitrate pentahydrate 0.703 g (1.59 mmo)
l) and copper nitrate trihydrate 2.30 g (9.51 mmol)
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 (2θ = 16.4 ° [111], 33.1 ° [222], 38.4 ° [400], 42.0 ° [33] similar to that of FIG.
1], 55.4 ° [440]) was obtained, and according to this example, (Er 1/7 Cu) was obtained.
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.
It was −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 well 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 (2θ = 16.3 ° [111], 33.0 ° [22] similar to that of FIG.
2], 38.3 ° [400], 41.8 ° [331],
A copper oxide-based conductive compound exhibiting 55.2 ° [440]) was obtained, and according to this example, (Ho 1/7 Cu 6/7 ) 7
It was confirmed that O z NO 3 was produced. The specific resistance (room temperature) of this copper oxide-based conductive compound is 5 × 10 −2 Ωcm.
Met. Further, this copper oxide-based conductive compound was paramagnetic at room temperature.
【0013】実施例12 酸化ルテチウム0.362g(0.91mmol)と硝
酸銅三水和物2.64g(10.9mmol)を良く混
合し、混合物を酸素雰囲気下、330℃で1時間加熱し
た。その結果、図1と類似の立方晶系のX線回折パター
ン(2θ=16.4゜[111]、33.2゜[22
2]、38.5゜[400]、42.1゜[331]、
55.6゜[440])を示す銅酸化物系導電性化合物
が得られ、本実施例により(Lu1/7Cu6/7)7
OzNO3が生成したことが確認された。この銅酸化物
系導電性化合物の比抵抗(室温)は3×10−2Ωcm
であった。 実施例13 酸化イッテルビウム0.359g(0.910mmo
l)と硝酸銅三水和物2.64g(10.9mmol)
を良く混合し、混合物を酸素雰囲気下、330℃で1時
間加熱した。その結果、図1と類似の立方晶系のX線回
折パターン(2θ=16.5゜[111]、33.2゜
[222]、38.5゜[400]、42.2゜[33
1]、55.6゜[440])を示す銅酸化物系導電性
化合物が得られ、本実施例により(Yb1/7Cu
6/7)7OzNO3が生成したことが確認された。こ
の銅酸化物系導電性化合物の比抵抗(室温)は2×10
−2Ωcmであった。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 under an oxygen atmosphere. As a result, a cubic X-ray diffraction pattern (2θ = 16.4 ° [111], 33.2 ° [22] similar to that of FIG. 1 was obtained.
2], 38.5 ° [400], 42.1 ° [331],
A copper oxide-based conductive compound exhibiting 55.6 ° [440]) was obtained, and (Lu 1/7 Cu 6/7 ) 7 was obtained according to this example.
It was confirmed that O z NO 3 was produced. The specific resistance (room temperature) of this copper oxide-based conductive compound is 3 × 10 −2 Ωcm.
Met. Example 13 Ytterbium oxide 0.359 g (0.910 mmo
l) and copper nitrate trihydrate 2.64 g (10.9 mmol)
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 (2θ = 16.5 ° [111], 33.2 ° [222], 38.5 ° [400], 42.2 ° [33] similar to that of FIG.
1], 55.6 ° [440]), and a copper oxide-based conductive compound was obtained, and according to this example, (Yb 1/7 Cu) was obtained.
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 2 × 10.
It was −2 Ωcm.
【0014】実施例14 酸化テルビウム0.351g(0.458mmol)と
硝酸銅三水和物2.66g(11.0mmol)を良く
混合し、混合物を酸素雰囲気下、330℃で1時間加熱
した。その結果、図1と類似の立方晶系のX線回折パタ
ーン(2θ=16.3゜[111]、33.0゜[22
2]、38.2゜[400]、41.8゜[331]、
55.2゜[440])を示す銅酸化物系導電性化合物
が得られ、本実施例により(Tb1/7Cu6/7)7
OzNO3が生成したことが確認された。この銅酸化物
系導電性化合物の比抵抗(室温)は1×10−1Ωcm
であった。 実施例15 硝酸ディスプロシウム0.342g(0.917mmo
l)と硝酸銅三水和物2.66g(11.0mmol)
を良く混合し、混合物を酸素雰囲気下、330℃で1時
間加熱した。その結果、図1に類似の立方晶系のX線回
折パターン(2θ=16.3゜[111]、32.9゜
[222]、38.2゜[400]、41.8゜[33
1]、55.1゜[440])を示す銅酸化物系導電性
化合物が得られ、本実施例により(Dy1/7Cu
6/7)7OzNO3が生成したことが確認された。こ
の銅酸化物系導電性化合物の比抵抗(室温)は1×10
−1Ωcmであった。図6はM・H磁化曲線を示す。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 under an oxygen atmosphere. As a result, a cubic X-ray diffraction pattern (2θ = 16.3 ° [111], 33.0 ° [22] similar to that of FIG.
2], 38.2 ° [400], 41.8 ° [331],
A copper oxide-based conductive compound exhibiting 55.2 ° [440]) was obtained, and (Tb 1/7 Cu 6/7 ) 7 was obtained according to this example.
It was confirmed that O z NO 3 was produced. The specific resistance (room temperature) of this copper oxide-based conductive compound is 1 × 10 −1 Ωcm.
Met. Example 15 Dysprosium nitrate 0.342 g (0.917 mmo
l) and copper nitrate trihydrate 2.66 g (11.0 mmol)
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 (2θ = 16.3 ° [111], 32.9 ° [222], 38.2 ° [400], 41.8 ° [33] similar to that of FIG. 1 was obtained.
1], 55.1 ° [440]), and a copper oxide-based conductive compound was obtained. According to this example, (Dy 1/7 Cu) was obtained.
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.
It was -1 Ωcm. FIG. 6 shows the MH magnetization curve.
【0015】実施例16 酸化ツリウム0.352g(0.911mmol)と硝
酸銅三水和物2.64g(10.9mmol)を良く混
合し、混合物を酸素雰囲気下、330℃で1時間加熱し
た。その結果、図1に類似の立方晶系のX線回折パター
ン(2θ=16.4゜[111]、33.1゜[22
2]、38.4゜[400]、42.0゜[331]、
55.4゜[440])を示す銅酸化物系導電性化合物
が得られ、本実施例により(Tm1/7Cu6/7)7
OzNO3が生成したことが確認された。この銅酸化物
系導電性化合物の比抵抗(室温)は5×10−2Ωcm
であった。 実施例17 酸化ルテチウム0.181g(0.455mmol)、
酸化イッテルビウム0.179g(0.455mmo
l)、硝酸銅三水和物2.64g(10.9mmol)
を良く混合し、混合物を酸素雰囲気下、330℃で1時
間加熱した。その結果、図1と類似の立方晶系のX線回
折パターン(2θ=16.5゜[111]、33.2゜
[222]、38.5゜[400]、42.2゜[33
1]、55・6゜[440])を示す銅酸化物系導電性
化合物が得られ、本実施例により(Lu1/14Y
1/14Cu6/7)7OzNO3が生成したことが確
認された。この銅酸化物系導電性化合物の比抵抗(室
温)は5×10−2Ωcmであった 実施例18 酸化エルビウム0.172g(0.45mmol)と硝
酸銅三水和物2.83g(11.7mmol)を良く混
合し、混合物を酸素雰囲気下、330℃で1時間加熱し
た。その結果、図1と類似の立方晶系のX線回折パター
ン(2θ=16.3゜[111]、33.0゜[22
2]、38.3゜[400]、41.8゜[331]、
55.2゜[440])を示す銅酸化物系導電性化合物
が得られ、本実施例により(Er1/14Cu
13/14)7OzNO3が生成したことが確認され
た。この銅酸化物系導電性化合物の比抵抗(室温)は1
×10−1Ωcmであった。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 under an oxygen atmosphere. As a result, a cubic X-ray diffraction pattern (2θ = 16.4 ° [111], 33.1 ° [22] similar to that of FIG. 1 was obtained.
2], 38.4 ° [400], 42.0 ° [331],
A copper oxide-based conductive compound exhibiting 55.4 ° [440]) was obtained, and (Tm 1/7 Cu 6/7 ) 7 was obtained according to this example.
It was confirmed that O z NO 3 was produced. The specific resistance (room temperature) of this copper oxide-based conductive compound is 5 × 10 −2 Ωcm.
Met. Example 17 0.181 g (0.455 mmol) of lutetium oxide,
Ytterbium oxide 0.179 g (0.455 mmo
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 (2θ = 16.5 ° [111], 33.2 ° [222], 38.5 ° [400], 42.2 ° [33] similar to that of FIG.
1], 55.6 ° [440]), and a copper oxide-based conductive compound was obtained, and according to this example, (Lu 1/14 Y) was obtained.
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 (11. 7 mmol) was mixed well and the mixture was heated at 330 ° C. for 1 hour under oxygen atmosphere. As a result, a cubic X-ray diffraction pattern (2θ = 16.3 ° [111], 33.0 ° [22] similar to that of FIG.
2], 38.3 ° [400], 41.8 ° [331],
A copper oxide-based conductive compound exhibiting 55.2 ° [440]) was obtained, and according to this example, (Er 1/14 Cu) was obtained.
It was confirmed that 13/14 ) 7 O z NO 3 was produced. The specific resistance (room temperature) of this copper oxide-based conductive compound is 1
It was × 10 -1 Ωcm.
【図1】実施例1の銅酸化物系導電性化合物のX線回折
パターンを示す。1 shows an X-ray diffraction pattern of a copper oxide-based conductive compound of Example 1. FIG.
【図2】実施例1の銅酸化物系導電性化合物の温度・比
抵抗曲線を示す。FIG. 2 shows a temperature / specific resistance curve of the copper oxide-based conductive compound of Example 1.
【図3】実施例1の銅酸化物系導電性化合物のM・H磁
化曲線を示す。FIG. 3 shows the M · H magnetization curve of the copper oxide-based conductive compound of Example 1.
【図4】実施例3の銅酸化物系導電性化合物のX線回折
パターンを示す。FIG. 4 shows an X-ray diffraction pattern of the copper oxide-based conductive compound of Example 3.
【図5】実施例3の銅酸化物系導電性化合物の温度・比
抵抗曲線を示す。5 shows a temperature / resistivity curve of the copper oxide-based conductive compound of Example 3. FIG.
【図6】実施例15の銅酸化物系導電性化合物のM・H
磁化曲線を示す。FIG. 6 MH of the copper oxide-based conductive compound of Example 15
The magnetization curve is shown.
Claims (1)
合物 (MxCuy)7OzAw (上記式において、Mは、Dy、Ho、Er、Tb、T
m、Yb、及びLuよりなる群より選択される少なくと
も一種の元素、Aは、ハロゲン元素及び/又はNO3を
表わし、x+y=1、0<x/y≦10、6≦Z≦8、
0.5≦w≦9である。)1. A copper oxide-based conductive material represented by the following general formula
Compound (MxCuy)7OzAw (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 NOThreeTo
, X + y = 1, 0 <x / y ≦ 10, 6 ≦ Z ≦ 8,
0.5 ≦ w ≦ 9. )
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