JP4867618B2 - 熱電変換材料 - Google Patents
熱電変換材料 Download PDFInfo
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- JP4867618B2 JP4867618B2 JP2006319695A JP2006319695A JP4867618B2 JP 4867618 B2 JP4867618 B2 JP 4867618B2 JP 2006319695 A JP2006319695 A JP 2006319695A JP 2006319695 A JP2006319695 A JP 2006319695A JP 4867618 B2 JP4867618 B2 JP 4867618B2
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- thermoelectric conversion
- conversion material
- sintered body
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- metal
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- 238000006243 chemical reaction Methods 0.000 title claims description 93
- 239000000463 material Substances 0.000 title claims description 69
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000013078 crystal Substances 0.000 claims description 18
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 description 22
- 239000000203 mixture Substances 0.000 description 20
- 239000010949 copper Substances 0.000 description 18
- 239000002184 metal Substances 0.000 description 17
- 238000005245 sintering Methods 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 150000002736 metal compounds Chemical class 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 229910006404 SnO 2 Inorganic materials 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000010248 power generation Methods 0.000 description 6
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910007717 ZnSnO Inorganic materials 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- -1 organic acid salt Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 238000004857 zone melting Methods 0.000 description 1
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- 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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Description
すなわち、本発明は、下記の発明を提供する。
<1>金属元素として、M1、M2AおよびM2B[ここで、M1はLa、Yおよびランタノイドからなる群より選ばれる1種以上の元素(M1A)を必須の元素とし、さらにアルカリ土類金属元素から選ばれる1種以上の元素(M1B)を含有してもよい元素であり、M2Aは、原子価が2価となり得る金属元素からなる群から選ばれる1種以上の元素であり、M2Bは原子価が4価となり得る金属元素からなる群から選ばれる1種以上の元素であり、M1、M2AおよびM2Bは相異なる元素である。]を有する複合金属酸化物であって、M1:M2A:M2Bのモル比が2:1:1であり、結晶構造がペロブスカイト型結晶構造である複合金属酸化物からなることを特徴とする熱電変換材料。
<2>形状が焼結体であり、該焼結体の相対密度が60%以上である前記<1>記載の熱電変換材料。
<3>焼結体の表面の少なくとも一部が、ガス不透過膜でコーティングされている前記<2>記載の熱電変換材料。
<4>前記<1>〜<3>のいずれかに記載の熱電変換材料を有する熱電変換素子。
また、例えば、上記のLaの一部を上記の3価の金属元素で置換した場合、すなわち例えば、Laの40%をEuで置換したような場合には、(La0.6Eu0.4)2CuSnO6、(La0.6Eu0.4)2CuTiO6、(La0.6Eu0.4)2NiSnO6、(La0.6Eu0.4)2ZnSnO6、(La0.6Eu0.4)2ZnTiO6、(La0.6Eu0.4)2ZnZrO6、(La0.6Eu0.4)2Ba2Cu2Sn2O11、(La0.6Eu0.4)2Ba2Cu2Ti2O11、(La0.6Eu0.4)2Ba2Zn2Sn2O11、(La0.6Eu0.4)2Ba2Zn2Ti2O11、(La0.6Eu0.4)2Ba2Ni2Sn2O11となる。
本発明の熱電変換材料を焼結体の形状で用いる場合を例に挙げて、本発明の熱電変換材料を製造する方法について説明する。本発明の熱電変換材料は、複合金属酸化物からなり、該複合金属酸化物は、焼結により本発明における複合金属酸化物となる金属化合物混合物を焼結することにより製造することができ、すなわち、M1:M2A:M2Bのモル比が2:1:1となるように含有する金属化合物混合物を焼結することにより本発明の熱電変換材料を製造することができる。具体的には、対応する金属元素を含有する化合物を所定の組成となるように秤量し、混合した後に得られる金属化合物混合物を焼結することにより製造することができる。例えば、好ましい組成の一つであるY2CuSnO6で表される化合物は、Y2O3とCuOとSnO2を、Y:Cu:Snのモル比が2:1:1となるように秤量し、混合した後に得られる金属化合物混合物を焼結することにより製造することができる。
1.電気伝導度
焼結体試料を角柱状に加工し、銀ペーストで白金線を装着し、直流四端子法により測定した。測定は空気中で室温〜1073Kの範囲で温度を変化させながら行った。
2.ゼーベック係数
電気伝導度測定時と同様の形状に加工した焼結体試料の両端に、銀ペーストでR熱電対および白金線を装着して、焼結体試料の温度および熱起電力を測定した。測定は空気中で室温〜1073Kの範囲で温度を変化させながら行った。焼結体試料の片面にエアを流入したガラス管を接触させて低温部を作り、焼結体試料両端の温度をR熱電対で測定し、同時に焼結体試料の両端面間に生じている熱起電力(ΔV)も測定した。焼結体試料両端の温度差(ΔT)は、エアの流量を制御することで1〜10℃の範囲で制御し、ΔTとΔVの傾きからゼーベック係数の値(α)を算出した。
3.熱伝導度
真空中、室温で、レーザーフラッシュ法により焼結体試料の比熱および、熱拡散率を測定した。測定には真空理工株式会社製レーザーフラッシュ法熱伝導度測定装置TC−7000型を用いた。
4.構造解析
焼成品、焼結体資料の結晶構造は、株式会社リガク製X線回折測定装置RINT2500TTR型を用いて、CuKαを線源とする粉末X線回折法により分析した。
5.焼結体の密度
焼結体試料の相対密度はアルキメデス法により算出した。
CuO(株式会社高純度化学研究所製)を3.074g、SnO2(株式会社高純度化学研究所製)を5.825g、La2O3(株式会社高純度化学研究所製)を12.593g、秤取し、ジルコニア製のボールを用い、湿式ボールミルにより20時間混合した。該混合物を空気中において1100℃で24時間保持して焼成し、得られた焼成品をジルコニア製のボールを用い、湿式ボールミルにより20時間解砕し、1軸プレス(成形圧は1000kg/cm2)により円盤状に成形し、得られた成形体を100%酸素雰囲気中において1100℃で24時間保持して焼結した。得られた焼結体(焼結体1、La:Cu:Snは2:1:1)のX線回折図形を図1に示す。図1より、焼結体1の結晶構造は、ペロブスカイト型結晶構造であることがわかった。また、焼結体1の焼結体密度は相対密度で95%であった。
CuO(株式会社高純度化学研究所製)を1.537g、SnO2(株式会社高純度化学研究所製)を2.912g、La2O3(株式会社高純度化学研究所製)を6.139g、CaCO3(宇部マテリアル株式会社製、CS3N−A(商品名))0.097g秤取し、実施例1と同様の方法で焼結体(焼結体2、La:Ca:Cu:Snは1.95:0.05:1:1)を作製した。焼結体2の粉末X線回折により、焼結体2の結晶構造はペロブスカイト型結晶構造であることがわかった。
CuO(株式会社高純度化学研究所製)を1.537g、SnO2(株式会社高純度化学研究所製)を2.912g、La2O3(株式会社高純度化学研究所製)を6.139g、BaCO3(日本化学工業株式会社製、LC−1(商品名))0.191g秤取し、実施例1と同様の方法で焼結体(焼結体3、La:Ba:Cu:Snは1.95:0.05:1:1)を作製した。焼結体3の粉末X線回折により、焼結体3の結晶構造はペロブスカイト型結晶構造であることがわかった。
CuO(株式会社高純度化学研究所製)を1.537g、SnO2(株式会社高純度化学研究所製)を2.912g、La2O3(株式会社高純度化学研究所製)を6.139g、SrCO3(SrCO3、堺化学株式会社製、SW−K)0.143g秤取し、実施例1と同様の方法で焼結体(焼結体4、La:Sr:Cu:Snは1.95:0.05:1:1)を作製した。焼結体4の粉末X線回折により、焼結体4の結晶構造はペロブスカイト型結晶構造であることがわかった。
CuO(株式会社高純度化学研究所製)を1.537g、SnO2(株式会社高純度化学研究所製)を2.767g、La2O3(株式会社高純度化学研究所製)を6.297g、MgO(和光純薬株式会社製)0.039g秤取し、実施例1と同様の方法で焼結体(焼結体5、La:Cu:Sn:Mgは2:1:0.95:0.05)を作製した。焼結体5の粉末X線回折により、焼結体5の結晶構造はペロブスカイト型結晶構造であることがわかった。
Claims (4)
- 金属元素として、M1、M2AおよびM2B[ここで、M1はLa、Yおよびランタノイドからなる群より選ばれる1種以上の元素(M1A)を必須の元素とし、さらにアルカリ土類金属元素から選ばれる1種以上の元素(M1B)を含有してもよい元素であり、M2Aは、原子価が2価となり得る金属元素からなる群から選ばれる1種以上の元素であり、M2BはSnであり、M1、M2AおよびM2Bは相異なる元素である。]を有する複合金属酸化物であって、M1:M2A:M2Bのモル比が2:1:1であり、結晶構造がペロブスカイト型結晶構造である複合金属酸化物からなることを特徴とするp型熱電変換材料。
- 形状が焼結体であり、該焼結体の相対密度が60%以上である請求項1記載のp型熱電変換材料。
- 焼結体の表面の少なくとも一部が、ガス不透過膜でコーティングされている請求項2記載のp型熱電変換材料。
- 請求項1〜3のいずれかに記載のp型熱電変換材料を有するp型熱電変換素子。
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TW096144707A TW200832768A (en) | 2006-11-28 | 2007-11-26 | Thermoelectric conversion material and thermoelectric conversion element |
CN200780043906XA CN101542762B (zh) | 2006-11-28 | 2007-11-26 | 热电转换材料和热电转换元件 |
US12/513,574 US20100031993A1 (en) | 2006-11-28 | 2007-11-26 | Thermoelectric conversion material and thermoelectric conversion device |
EP07849967A EP2096687A4 (en) | 2006-11-28 | 2007-11-26 | THERMOELECTRIC WALLER MATERIAL AND THERMOELECTRIC CONVERTER ELEMENT |
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JP6424736B2 (ja) * | 2015-05-22 | 2018-11-21 | コニカミノルタ株式会社 | 圧電体、その製造方法、圧電組成物、超音波トランスデューサーおよび超音波撮像装置 |
JP2017143090A (ja) * | 2016-02-08 | 2017-08-17 | Tdk株式会社 | 半導体磁器組成物およびptcサーミスタ |
JPWO2018056368A1 (ja) * | 2016-09-21 | 2019-07-11 | 日産化学株式会社 | 熱電変換層形成用組成物及び熱電変換層の製造方法 |
JP7478414B2 (ja) * | 2020-03-02 | 2024-05-07 | 国立研究開発法人産業技術総合研究所 | 非晶質複合金属酸化物、ガーネット型リチウム複合金属酸化物、焼結体、固体電解質層、電気化学デバイス用電極、電気化学デバイス |
CN113036027A (zh) * | 2021-03-10 | 2021-06-25 | 杭州安誉科技有限公司 | 实时荧光定量pcr仪热电模块用半导体元件 |
TWI792310B (zh) * | 2021-05-13 | 2023-02-11 | 國立中興大學 | 高效能熱電材料 |
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US2330018A (en) * | 1940-10-29 | 1943-09-21 | Leeds & Northrup Co | Thermocouple element |
JPH05315657A (ja) | 1992-05-12 | 1993-11-26 | Hitachi Ltd | 熱電変換素子と熱電変換装置 |
JPH08186293A (ja) | 1994-12-28 | 1996-07-16 | Seibu Gas Kk | 熱発電材料 |
JPH08231223A (ja) | 1995-02-28 | 1996-09-10 | Denki Kagaku Kogyo Kk | 熱電変換材料 |
GB9716718D0 (en) * | 1997-08-08 | 1997-10-15 | Delta Theta Ltd | Thermoelectric cooling |
JP2003008086A (ja) * | 2001-06-22 | 2003-01-10 | Idemitsu Kosan Co Ltd | 複合酸化物及びそれを用いた熱電変換素子 |
US7326851B2 (en) * | 2003-04-11 | 2008-02-05 | Basf Aktiengesellschaft | Pb-Ge-Te-compounds for thermoelectric generators or Peltier arrangements |
WO2005093864A1 (ja) * | 2004-03-25 | 2005-10-06 | National Institute Of Advanced Industrial Science And Technology | 熱電変換素子及び熱電変換モジュール |
JP2006100683A (ja) * | 2004-09-30 | 2006-04-13 | Sumitomo Chemical Co Ltd | チタン酸化物熱電変換材料 |
JP2006062951A (ja) * | 2004-07-27 | 2006-03-09 | Sumitomo Chemical Co Ltd | 熱電変換材料およびその製造方法 |
JP2006108598A (ja) * | 2004-10-08 | 2006-04-20 | Murata Mfg Co Ltd | 熱電酸化物材料 |
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- 2007-11-26 WO PCT/JP2007/073262 patent/WO2008066189A1/ja active Application Filing
- 2007-11-26 TW TW096144707A patent/TW200832768A/zh unknown
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JP2008135501A (ja) | 2008-06-12 |
TW200832768A (en) | 2008-08-01 |
CN101542762B (zh) | 2012-01-18 |
CN101542762A (zh) | 2009-09-23 |
EP2096687A1 (en) | 2009-09-02 |
WO2008066189A1 (fr) | 2008-06-05 |
US20100031993A1 (en) | 2010-02-11 |
EP2096687A4 (en) | 2011-07-27 |
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