US20010017152A1 - Complex oxide having high seebeck coefficient and high electric conductivity - Google Patents

Complex oxide having high seebeck coefficient and high electric conductivity Download PDF

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US20010017152A1
US20010017152A1 US09/733,799 US73379900A US2001017152A1 US 20010017152 A1 US20010017152 A1 US 20010017152A1 US 73379900 A US73379900 A US 73379900A US 2001017152 A1 US2001017152 A1 US 2001017152A1
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complex oxide
temperature
electric conductivity
seebeck coefficient
thermoelectric
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Ryoji Funahashi
Ichiro Matsubara
Satoshi Sodeoka
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National Institute of Advanced Industrial Science and Technology AIST
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/66—Cobaltates containing alkaline earth metals, e.g. SrCoO3
    • C01G51/68—Cobaltates containing alkaline earth metals, e.g. SrCoO3 containing rare earth, e.g. La0.3Sr0.7CoO3
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
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    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/854—Thermoelectric active materials comprising inorganic compositions comprising only metals
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
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    • 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
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    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
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    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/32—Thermal properties
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties

Definitions

  • the present invention relates to a complex oxide having a high Seebeck coefficient and a high electric conductivity, and to a thermoelectric material prepared from said complex oxide.
  • thermoelectric conversion for direct conversion of thermal energy to electrical energy is effective means.
  • the thermoelectric conversion which utilizes Seebeck effect, is an energy conversion method for generating electricity by creating a difference in temperature between both ends of a thermoelectric material to produce a difference of electric potential.
  • electricity is generated simply by setting one end of a thermoelectric material at a location heated to a high temperature by waste heat, and the other end thereof in the atmosphere (room temperature) and connecting a leading wire to both ends thereof.
  • This method entirely eliminates a need for a device with moving parts such as a motor or a turbine required in the common generation of power.
  • the method is economical and can be carried out without giving off a gas by combustion.
  • the method can continuously generate electricity until the thermoelectric material is deteriorated.
  • thermoelectric generation is a technique expected to play a share of role for the resolution of energy problems which will be concerned henceforth.
  • thermoelectric generation there is a need for developing thermoelectric materials which have a high thermoelectric conversion efficiency and have excellent heat resistance and chemical durability.
  • thermoelectric conversion efficiency a substance of high thermoelectric conversion efficiency.
  • Bi 2 Te 3 has the highest thermoelectric conversion efficiency.
  • the thermoelectric conversion efficiency of Bi 2 Te 3 is only about 10% at highest.
  • Bi 2 Te 3 can be used only at a temperature of 200° C. or lower.
  • TeAgSb-containing metallic compound has a high thermoelectric conversion efficiency in a temperature range of about 600 to about 1,000 K which falls in the temperature range of waste heat.
  • Te and Sb are rare elements having toxicity and can not be used in the air because they are readily oxidizable. With the above drawbacks, Bi 2 Te 3 and TeAgSb-containing metallic compound are limited in application as a thermoelectric material for use.
  • metallic oxides may be proposed as materials excellent in heat resistance and chemical durability, the metallic oxides are lower in thermoelectric conversion efficiency by an order of magnitude than Bi 2 Te 3 .
  • known oxides having an electric conductivity of 1 ⁇ 10 3 S/m or more show a Seebeck coefficient only as low as tens ⁇ V/K.
  • FIG. 1 shows a powder X-ray diffraction pattern of the complex oxide obtained in Example 1.
  • FIG. 2 schematically shows a thermoelectric module produced using the complex oxide of the invention as a thermoelectric material.
  • FIG. 3 is a graph showing the temperature dependency of Seebeck coefficient of the complex oxide prepared in Example 1.
  • FIG. 4 is a graph showing the temperature dependency of electric conductivity of the complex oxide prepared in Example 1.
  • indicated at 1 is a base plate for a high-temperature location; at 2 , a base plate for a low-temperature location; at 3 , a P-type thermoelectric material; at 4 , an N-type thermoelectric material; at 5 , an electrode; and at 6 , a leading wire.
  • a principal object of the present invention is to provide a material composed of low-toxicity elements, the material being excellent in heat resistance and chemical durability and having a high thermoelectric conversion efficiency.
  • thermoelectric materials conducted extensive research in view of the above-mentioned current situation regarding thermoelectric materials and found that a complex oxide having a specific composition which includes a rare earth element, Ca, Co and O as constituent elements has a high Seebeck coefficient and a high electric conductivity and is useful as a thermoelectric material in a thermoelectric module.
  • the present invention was completed based on this novel finding.
  • the present invention provides the following complex oxides and thermoelectric material.
  • a complex oxide comprising the features of:
  • RE is at least one element selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
  • thermoelectric material prepared from the complex oxide as defined in item 1.
  • the complex oxide of the present invention is represented by the formula: Ca 3-x RE x Co 4 O y .
  • RE is a rare earth element and is at least one element selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
  • the value of x ranges from 0.1 to 0.5, preferably from 0.1 to 0.25.
  • the value of y ranges from 8.5 to 10, preferably from 8.8 to 9.2.
  • Such complex oxide has an oxygen deficient perovskite structure similar to Ca 3 Co 4 O 9 which is a conventional oxygen deficient perovskite.
  • FIG. 1 shows a powder X-ray diffraction pattern of the complex oxide prepared in Example 1 to be described later.
  • a pattern (a) shows an X-ray diffraction pattern of the complex oxide of the invention and a pattern (b) indicates an X-ray diffraction pattern of Ca 3 Co 4 O 9 . From the patterns, it is evident that in the complex oxide of the present invention, the Ca site of Ca 3 Co 4 O 9 is replaced by a rare earth element in view of absence of a peak resulting from an impurity phase.
  • the complex oxide having the above-specified composition according to the invention has a Seebeck coefficient of 100 ⁇ V/K or more and an electric conductivity of 10 3 S/m or more at a temperature of 300° C. or higher.
  • the complex oxide of the invention can exhibit a high thermoelectric conversion efficiency when used as a thermoelectric material for a thermoelectric module, because the oxide has both a high Seebeck coefficient and a high electric conductivity. Further the complex oxide of the invention is excellent in heat resistance and chemical durability and is made of low-toxicity elements so that the oxide is very suitable for use as a thermoelectric material.
  • the complex oxide of the invention can be prepared by mixing the starting materials in the predetermined proportions and sintering them in an oxidizing atmosphere.
  • the starting materials are not limited insofar as they can produce the contemplated complex oxide when sintered. Examples are metals, oxides, compounds (such as carbonate), etc.
  • Examples of compounds as the Ca source are calcium oxide (CaO), calcium chloride (CaCl 2 ), calcium carbonate (CaCO 3 ), calcium nitrate (Ca(NO 3 ) 2 ), calcium hydroxide (Ca(OH) 2 ), dimethoxy calcium (Ca(OCH 3 ) 2 ), diethoxy calcium (Ca(OC 2 H 5 ) 2 ), dipropoxy calcium (Ca(OC 3 H 7 ) 2 ), etc.
  • Examples of compounds as the rare earth element (RE) source are oxides (RE 2 O 3 such as Gd 2 O 3 ), nitrates (RE(NO 3 ) 3 ), chlorides (RECl 3 ), hydroxides (RE(OH) 3 ), alkoxide compounds (RE(OCH 3 ) 3 , RE(OC 2 H 5 ) 3 , RE(OC 3 H 7 ) 3 , etc.).
  • oxides RE 2 O 3 such as Gd 2 O 3
  • nitrates RE(NO 3 ) 3
  • chlorides RECl 3
  • hydroxides RE(OH) 3
  • alkoxide compounds RE(OCH 3 ) 3 , RE(OC 2 H 5 ) 3 , RE(OC 3 H 7 ) 3 , etc.
  • Examples of compounds as the Co source are cobalt oxide (CoO, Co 2 O 3 , Co 3 O 4 , etc.), cobalt chloride (CoCl 2 ), cobalt carbonate (CoCO 3 ), cobalt nitrate (Co(NO 3 ) 2 ), cobalt hydroxide (Co(OH) 2 ), dipropoxy cobalt (Co(OC 3 H 7 ) 2 ), etc.
  • cobalt oxide CoO, Co 2 O 3 , Co 3 O 4 , etc.
  • cobalt chloride CoCl 2
  • cobalt carbonate CoCO 3
  • cobalt nitrate Co(NO 3 ) 2
  • cobalt hydroxide Co(OH) 2
  • dipropoxy cobalt Co(OC 3 H 7 ) 2
  • Sintering means are not limited and can be selected from any desired means such as electric furnaces, gas furnaces and the like, and sintering may be conducted in an oxygen stream, the air or like oxidizing atmosphere.
  • the sintering temperature and sintering time are not limited and are so determined as to meet the conditions which allow the production of contemplated complex oxide.
  • the sintering is performed at about 920 to about 1100° C. for about 20 to about 40 hours.
  • the starting materials are calcined for decomposition prior to sintering and then sintered to give the contemplated complex oxide.
  • carbonate when carbonate is used as the starting material, it is calcined at about 800 to about 900° C. for about 10 hours and then sintered under the above-mentioned conditions.
  • the amount of oxygen in a complex oxide to be produced is controllable depending on the partial pressure of oxygen in sintering, sintering temperature, sintering time and the like.
  • the complex oxide of the invention prepared in this way has both a high Seebeck coefficient and a high electric conductivity so that the oxide can be effectively used as the thermoelectric material for a thermoelectric module.
  • FIG. 2 schematically shows by way of example a thermoelectric module produced using the complex oxide of the invention as the thermoelectric material.
  • Said thermoelectric module has the same structure as conventional thermoelectric modules.
  • the complex oxide of the invention is used as a P-type thermoelectric material in a thermoelectric module which comprises a base plate for a high-temperature location 1 , a base plate for a low-temperature location 2 , a P-type thermoelectric material 3 , an N-type thermoelectric material 4 , an electrode 5 and a leading wire 6 .
  • the complex oxide of the invention has a high Seebeck coefficient and a high electric conductivity and is excellent in heat resistance and chemical durability.
  • the complex oxide of the invention finds applications as a thermoelectric material usable at a high temperature unlike conventional intermetallic compounds which are unsuitable for such applications. Consequently it is expected that the thermal energy heretofore cast away into the atmosphere can be effectively used by incorporating the complex oxide of the invention into a thermoelectric generation system.
  • FIG. 3 is a graph showing the temperature dependency of Seebeck coefficient (S) of the obtained complex oxide at 100 to 700° C.
  • the mark ⁇ represents the measured results of the complex oxide of the invention and the mark ⁇ represents the measured results of Ca 3 Co 4 O 9 . From FIG. 3, it is clear that the obtained complex oxide exhibits a Seebeck coefficient of 100 ⁇ V/K or more in the temperature range of 300 to 700° C.
  • FIG. 4 is a graph showing the temperature dependency of electric conductivity ( ⁇ ) of said complex oxide as determined by a direct current 4-terminal method. It is apparent from FIG. 4 that the electric conductivity of the complex oxide increases with the elevation of temperature, i.e., shows a semiconductor-like behavior and reaches a high value of more than 3 ⁇ 10 3 S/m at 300° C.

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Abstract

This invention provides a complex oxide comprising the features of: (i) being represented by the formula: Ca3-xRExCo4Oy wherein RE is a rare earth element, 0≦x≦0.5 and 8.5≦y≦10, (ii) having a Seebeck coefficient of 100 μV/K or more at a temperature of 300° C. or higher, and (iii) having an electric conductivity of 103 S/m or more at a temperature of 300° C. or higher. The complex oxide is composed of low-toxicity elements, excellent in heat resistance and chemical durability and high in thermoelectric conversion efficiency.

Description

    FIELD OF THE INVENTION
  • The present invention relates to a complex oxide having a high Seebeck coefficient and a high electric conductivity, and to a thermoelectric material prepared from said complex oxide. [0001]
    • BACKGROUND ART
  • In our country, effective energy is obtained at a ratio of only about 30% from the primary supply energy, and about 70% of energy is eventually discarded as heat into the atmosphere. The heat evolved by combustion in plants, garbage-incinerating facilities or the like is thrown away into the atmosphere without conversion into other energy. In this way, we are uselessly casting away a vast amount of thermal energy and are acquiring only a small amount of energy from combustion of fossil fuel or otherwise. [0002]
  • To increase the proportion of acquired energy, the thermal energy to be released into the atmosphere should be effectively utilized. For this purpose, thermoelectric conversion for direct conversion of thermal energy to electrical energy is effective means. The thermoelectric conversion, which utilizes Seebeck effect, is an energy conversion method for generating electricity by creating a difference in temperature between both ends of a thermoelectric material to produce a difference of electric potential. In this thermoelectric generation, electricity is generated simply by setting one end of a thermoelectric material at a location heated to a high temperature by waste heat, and the other end thereof in the atmosphere (room temperature) and connecting a leading wire to both ends thereof. This method entirely eliminates a need for a device with moving parts such as a motor or a turbine required in the common generation of power. As a consequence, the method is economical and can be carried out without giving off a gas by combustion. Moreover, the method can continuously generate electricity until the thermoelectric material is deteriorated. [0003]
  • As set forth above, thermoelectric generation is a technique expected to play a share of role for the resolution of energy problems which will be concerned henceforth. To realize the thermoelectric generation, there is a need for developing thermoelectric materials which have a high thermoelectric conversion efficiency and have excellent heat resistance and chemical durability. [0004]
  • Currently, intermetallic compounds are known as a substance of high thermoelectric conversion efficiency. Among them, Bi[0005] 2Te3 has the highest thermoelectric conversion efficiency. However, the thermoelectric conversion efficiency of Bi2Te3 is only about 10% at highest. Further, Bi2Te3 can be used only at a temperature of 200° C. or lower. TeAgSb-containing metallic compound has a high thermoelectric conversion efficiency in a temperature range of about 600 to about 1,000 K which falls in the temperature range of waste heat. However, Te and Sb are rare elements having toxicity and can not be used in the air because they are readily oxidizable. With the above drawbacks, Bi2Te3 and TeAgSb-containing metallic compound are limited in application as a thermoelectric material for use.
  • In the foregoing situation, it is expected to develop materials composed of low-toxicity elements which have superior heat resistance and chemical durability and a high thermoelectric conversion efficiency. [0006]
  • While metallic oxides may be proposed as materials excellent in heat resistance and chemical durability, the metallic oxides are lower in thermoelectric conversion efficiency by an order of magnitude than Bi[0007] 2Te3. In fact, known oxides having an electric conductivity of 1×103 S/m or more show a Seebeck coefficient only as low as tens μV/K.
    • DESCRIPTION OF THE DRAWINGS
  • FIG. 1 shows a powder X-ray diffraction pattern of the complex oxide obtained in Example 1. FIG. 2 schematically shows a thermoelectric module produced using the complex oxide of the invention as a thermoelectric material. FIG. 3 is a graph showing the temperature dependency of Seebeck coefficient of the complex oxide prepared in Example 1. FIG. 4 is a graph showing the temperature dependency of electric conductivity of the complex oxide prepared in Example 1. In the drawings, indicated at [0008] 1 is a base plate for a high-temperature location; at 2, a base plate for a low-temperature location; at 3, a P-type thermoelectric material; at 4, an N-type thermoelectric material; at 5, an electrode; and at 6, a leading wire.
    • DISCLOSURE OF THE INVENTION
  • A principal object of the present invention is to provide a material composed of low-toxicity elements, the material being excellent in heat resistance and chemical durability and having a high thermoelectric conversion efficiency. [0009]
  • The present inventor conducted extensive research in view of the above-mentioned current situation regarding thermoelectric materials and found that a complex oxide having a specific composition which includes a rare earth element, Ca, Co and O as constituent elements has a high Seebeck coefficient and a high electric conductivity and is useful as a thermoelectric material in a thermoelectric module. The present invention was completed based on this novel finding. [0010]
  • The present invention provides the following complex oxides and thermoelectric material. [0011]
  • 1. A complex oxide comprising the features of: [0012]
  • (i) being represented by the formula: Ca[0013] 3-xRExCo4Oy wherein RE is a rare earth element, 0≦x≦0.5 and 8.5≦y≦10,
  • (ii) having a Seebeck coefficient of 100 μV/K or more at a temperature of 300° C. or higher, and [0014]
  • (iii) having an electric conductivity of 10[0015] 3 S/m or more at a temperature of 300° C. or higher.
  • 2. The complex oxide as defined in item 1, wherein RE is at least one element selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. [0016]
  • 3. The complex oxide as defined in item 1 which has an oxygen deficient perovskite structure. [0017]
  • 4. A P-type thermoelectric material prepared from the complex oxide as defined in item 1. [0018]
  • The complex oxide of the present invention is represented by the formula: Ca[0019] 3-xRExCo4Oy. In the formula, RE is a rare earth element and is at least one element selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. The value of x ranges from 0.1 to 0.5, preferably from 0.1 to 0.25. The value of y ranges from 8.5 to 10, preferably from 8.8 to 9.2.
  • Such complex oxide has an oxygen deficient perovskite structure similar to Ca[0020] 3Co4O9 which is a conventional oxygen deficient perovskite. To clarify this matter, FIG. 1 shows a powder X-ray diffraction pattern of the complex oxide prepared in Example 1 to be described later. In FIG. 1, a pattern (a) shows an X-ray diffraction pattern of the complex oxide of the invention and a pattern (b) indicates an X-ray diffraction pattern of Ca3Co4O9. From the patterns, it is evident that in the complex oxide of the present invention, the Ca site of Ca3Co4O9 is replaced by a rare earth element in view of absence of a peak resulting from an impurity phase.
  • The complex oxide having the above-specified composition according to the invention has a Seebeck coefficient of 100 μV/K or more and an electric conductivity of 10[0021] 3 S/m or more at a temperature of 300° C. or higher. The complex oxide of the invention can exhibit a high thermoelectric conversion efficiency when used as a thermoelectric material for a thermoelectric module, because the oxide has both a high Seebeck coefficient and a high electric conductivity. Further the complex oxide of the invention is excellent in heat resistance and chemical durability and is made of low-toxicity elements so that the oxide is very suitable for use as a thermoelectric material.
  • The complex oxide of the invention can be prepared by mixing the starting materials in the predetermined proportions and sintering them in an oxidizing atmosphere. [0022]
  • The starting materials are not limited insofar as they can produce the contemplated complex oxide when sintered. Examples are metals, oxides, compounds (such as carbonate), etc. Examples of compounds as the Ca source are calcium oxide (CaO), calcium chloride (CaCl[0023] 2), calcium carbonate (CaCO3), calcium nitrate (Ca(NO3)2), calcium hydroxide (Ca(OH)2), dimethoxy calcium (Ca(OCH3)2), diethoxy calcium (Ca(OC2H5)2), dipropoxy calcium (Ca(OC3H7)2), etc. Examples of compounds as the rare earth element (RE) source are oxides (RE2O3 such as Gd2O3), nitrates (RE(NO3)3), chlorides (RECl3), hydroxides (RE(OH)3), alkoxide compounds (RE(OCH3)3, RE(OC2H5)3, RE(OC3H7)3, etc.). Examples of compounds as the Co source are cobalt oxide (CoO, Co2O3, Co3O4, etc.), cobalt chloride (CoCl2), cobalt carbonate (CoCO3), cobalt nitrate (Co(NO3)2), cobalt hydroxide (Co(OH)2), dipropoxy cobalt (Co(OC3H7)2), etc. Also usable as the starting material are compounds containing at least two elements constituting the complex oxide of the invention.
  • Sintering means are not limited and can be selected from any desired means such as electric furnaces, gas furnaces and the like, and sintering may be conducted in an oxygen stream, the air or like oxidizing atmosphere. [0024]
  • The sintering temperature and sintering time are not limited and are so determined as to meet the conditions which allow the production of contemplated complex oxide. For example, the sintering is performed at about 920 to about 1100° C. for about 20 to about 40 hours. When carbonate, an organic compound or the like is used as the starting material, preferably the starting materials are calcined for decomposition prior to sintering and then sintered to give the contemplated complex oxide. For example, when carbonate is used as the starting material, it is calcined at about 800 to about 900° C. for about 10 hours and then sintered under the above-mentioned conditions. [0025]
  • The amount of oxygen in a complex oxide to be produced is controllable depending on the partial pressure of oxygen in sintering, sintering temperature, sintering time and the like. The higher the partial pressure of oxygen is, the higher the value of y in said formula is. [0026]
  • The complex oxide of the invention prepared in this way has both a high Seebeck coefficient and a high electric conductivity so that the oxide can be effectively used as the thermoelectric material for a thermoelectric module. [0027]
  • FIG. 2 schematically shows by way of example a thermoelectric module produced using the complex oxide of the invention as the thermoelectric material. Said thermoelectric module has the same structure as conventional thermoelectric modules. The complex oxide of the invention is used as a P-type thermoelectric material in a thermoelectric module which comprises a base plate for a high-temperature location [0028] 1, a base plate for a low-temperature location 2, a P-type thermoelectric material 3, an N-type thermoelectric material 4, an electrode 5 and a leading wire 6.
  • The complex oxide of the invention has a high Seebeck coefficient and a high electric conductivity and is excellent in heat resistance and chemical durability. [0029]
  • The complex oxide of the invention finds applications as a thermoelectric material usable at a high temperature unlike conventional intermetallic compounds which are unsuitable for such applications. Consequently it is expected that the thermal energy heretofore cast away into the atmosphere can be effectively used by incorporating the complex oxide of the invention into a thermoelectric generation system. [0030]
    • EXAMPLES
  • Examples are given below to further clarify the features of the present invention. [0031]
    • Example 1
  • Using calcium carbonate (CaCO[0032] 3) as the Ca source, gadolinium oxide (Gd2O3) as the Gd source, and cobalt oxide (CO3O4) as the Co source, thorough mixing was conducted at a mixing ratio (mole ratio) of 2.5:9.5:4 of Ca:Gd:Co. The mixture was charged into a crucible made of alumina and was calcined in an electric furnace at a temperature of 800° C. for 10 hours. The calcined product was crushed, press-molded and sintered in an oxygen stream at 920° C. for 40 hours to produce a complex oxide. The obtained complex oxide is one represented by the formula Ca2.5Gd0.5Co4O9.
  • FIG. 3 is a graph showing the temperature dependency of Seebeck coefficient (S) of the obtained complex oxide at 100 to 700° C. In FIG. 3, the mark  represents the measured results of the complex oxide of the invention and the mark ▪ represents the measured results of Ca[0033] 3Co4O9. From FIG. 3, it is clear that the obtained complex oxide exhibits a Seebeck coefficient of 100 μV/K or more in the temperature range of 300 to 700° C.
  • FIG. 4 is a graph showing the temperature dependency of electric conductivity (σ) of said complex oxide as determined by a direct current 4-terminal method. It is apparent from FIG. 4 that the electric conductivity of the complex oxide increases with the elevation of temperature, i.e., shows a semiconductor-like behavior and reaches a high value of more than 3×10[0034] 3 S/m at 300° C.
    • Examples 2-16
  • Complex oxides represented by the formula Ca[0035] 2.5RE0.5Co4O8.8-9.2 were produced in the same manner as in Example 1 with the exception of replacing the rare metal element compound used as the starting material with the compounds shown in Table 1.
  • The Seebeck coefficient (S) and electric conductivity (σ) of the obtained complex oxides were measured with the results shown in Table 1. [0036]
    TABLE 1
    RE Seebeck Electric Measuring
    Ex. Starting Coefficient Conductivity Temperature
    No. Kind Compound (μV/K) (103S/m) (C.°)
    1 Gd Gd2O3 170 4.3 600
    2 Sc Sc2O3 152 4.8 700
    3 Y Y2O3 163 4.5 500
    4 La La2O3 145 4.2 500
    5 Ce CeO 2 140 3.8 500
    6 Pr Pr2O3 155 4.5 500
    7 Nd Nd2O3 160 4.6 500
    8 Sm Sm2O3 154 4.0 500
    9 Eu Eu2O3 120 5.2 600
    10 Tb Tb4O7 135 3.6 600
    11 Dy Dy2O3 147 3.9 600
    12 Ho Ho2O3 150 4.1 700
    13 Er Er2O3 158 4.2 700
    14 Tm Tm2O3 142 4.5 700
    15 Yb Yb2O3 139 4.8 700
    16 Lu Lu2O3 120 5.3 700
    • Examples 17-32
  • Complex oxides represented by the formula Ca[0037] 2.75RE0.25Co4O8.8-9.2 were produced in the same manner as in Example 1 with the exception of replacing the rare metal element compound used as the starting material with the compounds shown in Table 2, using the starting materials in a mixing mole ratio of 2.75:0.25:4 of Ca:RE:Co and sintering them at 1000° C. for 30 hours.
  • The Seebeck coefficient (S) and electric conductivity (σ) of the obtained complex oxides were measured with the results shown in Table 2. [0038]
    TABLE 2
    RE Seebeck Electric Measuring
    Ex. Starting Coefficient Conductivity Temperature
    No. Kind Compound (μV/K) (103S/m) (C.°)
    17 Gd Gd3O3 157 5.2 600
    18 Sc Sc2O3 146 5.6 700
    19 Y Y2O3 160 5.3 500
    20 La La2O3 140 5.8 500
    21 Ce CeO2 138 5.8 500
    22 Pr Pr2O3 142 5.5 500
    23 Nd Nd2O3 156 5.4 500
    24 Sm Sm2O3 150 5.5 500
    25 Eu Eu2O3 115 6.0 600
    26 Tb Tb4O7 127 5.8 600
    27 Dy Dy2O3 136 5.7 600
    28 Ho Ho2O3 145 5.5 700
    29 Er Er2O3 145 5.4 700
    30 Tm Tm2O3 130 5.9 700
    31 Yb Yb2O3 132 5.9 700
    32 Lu Lu2O3 115 6.3 700
    • Examples 33-48
  • Complex oxides represented by the formula Ca[0039] 2.9RE0.1Co4O8.8-9.2 were produced in the same manner as in Example 1 with the exception of replacing the rare metal element compound used as the starting material with the compounds shown in Table 3, using the starting materials in a mixing mole ratio of 2.9:0.1:4 of Ca:RE:Co and sintering them at 1100° C. for 20 hours.
  • The Seebeck coefficient (S) and electric conductivity (σ) of the obtained complex oxides were measured with the results shown in Table 3. [0040]
    TABLE 3
    RE Seebeck Electric Measuring
    Ex. Starting Coefficient Conductivity Temperature
    No. Kind Compound (μV/K) (103S/m) (C.°)
    33 Gd Gd3O3 150 6.5 600
    34 Sc Sc2O3 140 6.8 700
    35 Y Y2O3 155 6.6 500
    36 La La2O3 128 7.2 500
    37 Ce CeO2 128 7.3 500
    38 Pr Pr2O3 130 7.0 500
    39 Nd Nd2O3 147 6.7 500
    40 Sm Sm2O3 137 7.0 500
    41 Eu Eu2O3 105 7.8 600
    42 Tb Tb4O7 114 7.7 600
    43 Dy Dy2O3 127 7.1 600
    44 Ho Ho2O3 136 6.9 700
    45 Er Er2O3 137 6.7 700
    46 Tm Tm2O3 123 7.0 700
    47 Yb Yb2O3 120 7.1 700
    48 Lu Lu2O3 102 8.0 700
  • The results obtained above show that the complex oxides of the present invention have a high Seebeck coefficient and a high electric conductivity. [0041]

Claims (4)

1. A complex oxide comprising the features of:
(i) being represented by the formula: Ca3-xRExCo4Oy wherein RE is a rare earth element, 0≦x≦0.5 and 8.5≦y≦10,
(ii) having a Seebeck coefficient of 100 μV/K or more at a temperature of 300° C. or higher, and
(iii) having an electric conductivity of 103 S/m or more at a temperature of 300° C. or higher.
2. The complex oxide according to
claim 1
, wherein RE is at least one element selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
3. The complex oxide according to
claim 1
 which has an oxygen deficient perovskite structure.
4. A P-type thermoelectric material prepared from the complex oxide as defined in
claim 1
.
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