JP2000252526A5 - - Google Patents

Claims (43)

  A thermoelectric material, wherein the scutteldite-based thermoelectric material is a sintered body comprising Sb-containing scutteldite compound crystal grains and metal oxides dispersed at grain boundaries of the crystals.   The thermoelectric material according to claim 1, wherein an average crystal grain size of the scutteldite compound is 20 µm or less.   The thermoelectric material according to claim 2, wherein the metal oxide is an oxide of a rare earth metal. The discussions ether phosphoramidite compound (wherein, Ln is a rare earth metal, <X ≦ 4,0 <y ≦ 1) Ln y Fe x Co 4-x Sb 12 that is filled discussions ether phosphoramidite compound of the composition of The thermoelectric material according to claim 1 or 2, characterized in that   The thermoelectric material according to claim 4, wherein the composition is 3≤X≤4 and 0.8≤y≤1.   The thermoelectric material according to claim 4, wherein the Ln contains two or more kinds of rare earth metals.   The thermoelectric material according to any one of claims 4 to 6, wherein the Ln is Hf instead of the rare earth metal. Discussions ether phosphoramidite compound crystals, a CoSb ₃ based compound mainly Co and Sb, crystals CoSb ₃ based compound, claims 1, characterized in that it comprises a transition metal other than the Co-group metal 3 The thermoelectric material according to any one of the above.   The thermoelectric material according to claim 8, wherein the transition metal is Cr, Mn, Fe, or Ru, or Ni, Pa, Pt, or Cu. 9. The sintered body formed by sintering a compact made of Co and Sb powder or the CoSb ₃ -based compound powder and a transition metal dispersed in the powder. Thermoelectric material. Off I field discussions ether phosphoramidite crystalline phase in FeSb ₂ phase, an intensity ratio of the peak diffraction intensity of FeSb ₂ phase to the peak diffraction intensity of filled discussions ether phosphoramidite compound crystal phase by X-ray diffraction, it was 1% or less The thermoelectric material according to claim 4 . The thermoelectric material according to claim 4, characterized in that the oxygen content of 1 wt% or less in full I field discussions ether phosphoramidite compound crystal phase. The thermoelectric material according to claim 11 or 12, wherein the composition is 3 ≦ X ≦ 4 and 0.8 ≦ y ≦ 1. Discussions ether Daito-based _{compound, Hf y Fe x Co 4-} x Sb 12 ( where, 0 <X ≦ 4,0 <y ≦ 1) according to claim 1 comprising a filled discussions ether phosphoramidite compound having the composition heat conductive material. 15. The thermoelectric material according to claim 14, wherein the composition is 3 ≦ X ≦ 4 and 0.8 ≦ y ≦ 1. Discussions ether Daito-based thermoelectric _{material, Ln y Fe x M 4-} x Sb 12 ( here, Ln is a rare earth metal, 1 ≦ X ≦ 4,0 ≦ y ≦ 1) filled discussions ether phosphoramidite compound having a composition ratio of The thermoelectric material according to claim 1 , wherein M is any one of Ni, Pd, and Pt.   The thermoelectric material according to claim 16, wherein 3 ≦ X ≦ 4 and 0.8 ≦ y ≦ 1.   A method for producing a skutterudite-based thermoelectric material comprising a crystal of an Sb-containing skutterudite compound and a metal oxide dispersed in a grain boundary thereof, comprising mixing a skutterudite compound or a component thereof and a metal oxide A method for producing a thermoelectric material, comprising sintering powder. The Sb-containing discussions ether phosphoramidite _{compound, Ln y Fe x Co 4-} x Sb 12 ( here, Ln is a rare earth metal, 0 <X ≦ 4,0 <y ≦ 1) is filled discussions ether Daito compound of composition The method for producing a thermoelectric material according to claim 18.   20. The method for producing a thermoelectric material according to claim 19, wherein the composition is 3 ≦ X ≦ 4 and 0.8 ≦ y ≦ 1.   The mixed powder is characterized in that the metal-containing precipitate is dispersed in the skaterdite compound powder by precipitation from a metal-containing aqueous solution, and then thermally decomposed to disperse the metal oxide in the compound powder. The method for producing a thermoelectric material according to any one of claims 18 to 20. The scutteldite compound crystal is a CoSb ₃ -based compound containing Co and Sb as main components, and the mixed powder is sintered by mixing the scutteldite compound crystal with a transition metal excluding a Co group metal. The method for producing a thermoelectric material according to claim 18. The method for producing a thermoelectric material according to claim 22, wherein the mixed powder is obtained by electroless plating a transition metal on a CoSb ₃ -based compound powder. Method for producing a thermoelectric material according to claim 22 in which the mixed powder powder, characterized by comprising a mixture of a transition metal by mechanical alloying on the surface of the mixed powder or CoSb ₃ based compound powder of Co and Sb. The mixed powder powder is present in aqueous solution of a transition metal of Co and Sb powder or CoSb ₃ based compound powder dispersed, according to claim 22 as a mixed powder by hydrogen reduction of an aqueous solution after evaporation to dryness Thermoelectric material manufacturing method.   The method for producing a thermoelectric material according to any one of claims 18 to 25, wherein the transition metal is Mn, Cr, Fe, or Ru, or Ni, Pd, Pt, or Cu. The method for producing a thermoelectric material according to any one of claims 18 to 20, wherein the method of sintering the mixed powder is a discharge plasma sintering method. The discussions ether phosphoramidite compound (here, Ln is a rare earth metal, 0 ≦ X ≦ 4,0 ≦ y ≦ 1) Ln y Fe x M 4-x Sb 12 thermoelectric material is filled discussions ether Daito compound of the composition ratio The method of manufacturing a thermoelectric material according to claim 18, wherein the pretreatment step from the formation of the filled scutteldite compound to the sintering of the filled scutteldite compound powder is performed in a non-oxidizing atmosphere. Production method.   29. The pretreatment step includes a step of grinding the filled scutteldite compound, preforming the compound powder, charging the compact into a sintering die, and sintering the compact. Manufacturing method of thermoelectric material. The method for producing a thermoelectric material according to claim 28 or 29, wherein the method for sintering the compound powder is a discharge plasma sintering method. The Sb-containing discussions ether phosphoramidite based thermoelectric material as p-type thermoelectric material and the n-type thermoelectric material, both thermoelectric material by bonding sintered together, a thermoelectric couple was formed a p-n junction plane,
A thermoelectric couple, wherein the p-type electric material is the thermoelectric material according to claim 1.   32. The thermoelectric couple according to claim 31, wherein the n-type thermoelectric material is an Sb-containing skutterudite-based thermoelectric material substituted with Ni, Pd, or Pt. The composition of the n-type CoSb ₃ -based thermoelectric material is Ln _y Fe _x M _4−x Sb ₁₂ (where Ln is a rare earth metal, 0 ≦ X ≦ 4, 0 ≦ y ≦ 1, M is Ni, Pd, or Pt). is an n-type filled discussions ether phosphoramidite based thermoelectric material made of specific thermoelectric couple according to claim 3 1, characterized in that it comprises a junction joined by sintering. a p-type Sb content filled discussions ether phosphoramidite based molded layer +6 raw mixed powder powder of the thermoelectric material, a mixed powder powder of the molded layer of n-type Sb content filled discussions ether phosphoramidite based thermoelectric material is bonded by pressure, Next, a method of manufacturing a thermoelectric couple having a pn junction by sintering by integrally sintering ,
The raw material mixed powder is a mixed powder of a skutterudite compound or a constituent thereof and a metal oxide, and is a thermoelectric power composed of a crystal of an Sb-containing skutterudite compound and a metal oxide dispersed in the crystal grain boundary. How to make a couple . The Sb-containing discussions ether phosphoramidite _{compound, Ln y Fe x Co 4-} x Sb 12 ( here, Ln is a rare earth metal, 0 <X ≦ 4,0 <y ≦ 1) is filled discussions ether Daito compound of composition method of manufacturing a thermoelectric couple according to claim 3 4, characterized in that. The composition, in particular, 3 ≦ with X ≦ 4, and 0.8 ≦ y ≦ 1 thermoelectric method for producing a couple of claim 35 which is. The mixed powder is characterized in that the metal-containing precipitate is dispersed in the skaterdite compound powder by sedimentation from a metal-containing aqueous solution, and then thermally decomposed to disperse the metal oxide in the compound powder. method of manufacturing a thermoelectric couple according to claim 3 4. The p-type Sb-containing scutteldite compound crystal is a CoSb ₃ compound containing Co and Sb as main components, and the mixed powder is mixed with a transition metal excluding a Co group metal in the scutteldite compound crystal. method of manufacturing a thermoelectric couple according to claim 3 4, characterized in. The method for producing a thermoelectric couple according to claim 34 , wherein the method for sintering the formed phase layer of the mixed powder is a discharge plasma sintering method. The p-type Sb-containing skutterudite compound is a filled skutterudite compound having a composition ratio of Ln _y Fe _x M _4-x Sb ₁₂ (where Ln is a rare earth metal, 0 ≦ X ≦ 4, 0 ≦ y ≦ 1). The method for producing a thermoelectric couple according to claim 34, wherein the pretreatment process from the formation of the filled scutteldite compound to the sintering of the filled scutteldite compound powder is performed in a non-oxidizing atmosphere. . The n-type Sb-containing skutterudite compound is Ln _y Fe _x M _4-x Sb ₁₂ (where Ln is a rare earth metal, 0 ≦ X ≦ 4, 0 ≦ y ≦ 1, M is Ni, Pd or Pt). The method for producing a thermoelectric couple according to claim 34, wherein the composition is n-type filled scutteldite having a composition ratio. The composition, in particular, 3 ≦ X ≦ 4, and 0.8 ≦ y ≦ 1 a method of manufacturing a thermoelectric couple according to Claim 4 0 or 4 1. 34. A thermoelectric module comprising the plurality of thermoelectric couples according to claim 31 and a conductive electrode, wherein each thermoelectric couple is connected in series.