JP2018152464A - Segment type thermoelectric power module - Google Patents
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 150000001875 compounds Chemical class 0.000 claims abstract description 48
- 238000010248 power generation Methods 0.000 claims description 46
- 229910052733 gallium Inorganic materials 0.000 claims description 33
- 229910052732 germanium Inorganic materials 0.000 claims description 25
- 229910052718 tin Inorganic materials 0.000 claims description 21
- 229910052738 indium Inorganic materials 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 abstract description 4
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 abstract description 4
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 abstract description 4
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- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 33
- 229910052792 caesium Inorganic materials 0.000 description 4
- 229910052701 rubidium Inorganic materials 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 3
- 229940125758 compound 15 Drugs 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N11/00—Generators or motors not provided for elsewhere; Alleged perpetua mobilia obtained by electric or magnetic means
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- 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
- H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
- H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
-
- 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
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- 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
- H10N10/857—Thermoelectric active materials comprising compositions changing continuously or discontinuously inside the material
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Abstract
Description
この発明は、クラスレート化合物を利用したセグメント型熱電発電モジュールに関するものである。 The present invention relates to a segment type thermoelectric power generation module using a clathrate compound.
熱電発電モジュールの単位構造は、図４に示すように高温側電極１と低温側電極２、３との間にｐ型熱電変換素子４とｎ型熱電変換素子５を配置したものである。
このような熱電発電モジュールへの熱入力Ｑにより、両電極に温度差をつけたまま保持すると、ｐ型熱電変換素子４では正孔が、ｎ型熱電変換素子５では電子が、高温側から低温側に移動し、ｐ型熱電変換素子４が配置された低温側電極２からｎ型熱電変換素子５が配置された低温側電極３に向かって電流が流れ電気出力Ｐが得られる。
この時、熱電発電モジュールの変換効率ηは、η＝Ｐ／Ｑとなる。
なお、通常は昇圧のために、この組み合わせを多段に直接接続する。
The unit structure of the thermoelectric power generation module is such that a p-type thermoelectric conversion element 4 and an n-type thermoelectric conversion element 5 are arranged between the high temperature side electrode 1 and the low temperature side electrodes 2 and 3 as shown in FIG.
When the two electrodes are held with a temperature difference due to the heat input Q to the thermoelectric power generation module, holes are generated in the p-type thermoelectric conversion element 4, electrons are transferred in the n-type thermoelectric conversion element 5, and the temperature is lowered from the high temperature side. The current flows from the low temperature side electrode 2 where the p-type thermoelectric conversion element 4 is arranged toward the low temperature side electrode 3 where the n type thermoelectric conversion element 5 is arranged, and an electric output P is obtained.
At this time, the conversion efficiency η of the thermoelectric power generation module is η = P / Q.
Normally, this combination is directly connected in multiple stages for boosting.
熱電発電モジュールの変換効率ηは、概して温度差ΔＴと熱電変換素子の性能指数ＺＴの積に比例する。
ここで、熱電変換素子の性能指数ＺＴは、通常図５のように山型の温度依存性を有するとともに、材料によってＺＴが最大となる温度が異なっている。
したがって、図６のようにｐ型熱電変換素子４とｎ型熱電変換素子５の高温側に高温帯でＺＴが最大となる材料６、８を配置し、低温側に低温帯でＺＴが最大となる材料７、９を配置するとΔＴとＺＴの積が大きくなり、図４のような単一の材料を用いる熱電発電モジュールよりも変換効率ηが高くなる。
このような熱電発電モジュールをセグメント型熱電発電モジュールと呼んでおり、特許文献１（特開２００２−８４００５号公報）にも開示されている（特に、段落００４０〜００４１及び図１０、１１を参照）。
また、その後の研究により、種々の熱電材料を組み合わせることによって、１１〜１２％の高い変換効率の得られるセグメント型熱電発電モジュールも開発されてきている。
The conversion efficiency η of the thermoelectric power generation module is generally proportional to the product of the temperature difference ΔT and the performance index ZT of the thermoelectric conversion element.
Here, the figure of merit ZT of the thermoelectric conversion element usually has a mountain-shaped temperature dependence as shown in FIG. 5, and the temperature at which ZT becomes maximum differs depending on the material.
Therefore, as shown in FIG. 6, the materials 6 and 8 having the maximum ZT in the high temperature zone are arranged on the high temperature side of the p-type thermoelectric conversion element 4 and the n-type thermoelectric conversion element 5, and the ZT is maximum in the low temperature zone on the low temperature side. When the materials 7 and 9 are arranged, the product of ΔT and ZT is increased, and the conversion efficiency η is higher than that of the thermoelectric power generation module using a single material as shown in FIG.
Such a thermoelectric power generation module is called a segment type thermoelectric power generation module, and is also disclosed in Patent Document 1 (Japanese Patent Laid-Open No. 2002-84005) (see particularly paragraphs 0040 to 0041 and FIGS. 10 and 11). .
Further, as a result of subsequent research, segment-type thermoelectric power generation modules that can obtain high conversion efficiency of 11 to 12% by combining various thermoelectric materials have been developed.
本発明者らは、この発明に先立ち図７に示すように、ｐ型熱電変換素子４とｎ型熱電変換素子５の高温側に、材料６、８としてクラスレート化合物であるＢａ8(Ｇａ,Ｇｅ)46（ＢＧＧ、タイプ１）を用いるとともに、ｐ型熱電変換素子４とｎ型熱電変換素子５の低温側に材料７、９として同じくクラスレート化合物であるＢａ8(Ｇａ,Ｓｎ)46（ＢＧＴ、タイプ８）を用いたセグメント型熱電発電モジュール（非特許文献１を参照）を開発した。
なお、ＢＧＧにおいてはＧａとＧｅの配合比率によって、ＢＧＴにおいてはＧａとＳｎの配合比率によって、ｐ型となるかｎ型となるかが決まる。
例えば、Ｂａ8Ｇａ16Ｇｅ30及びＢａ8Ｇａ18Ｇｅ28はｐ型、Ｂａ8Ｇａ14Ｇｅ32及びＢａ8Ｇａ15Ｇｅ31はｎ型となり、Ｂａ8Ｇａ16Ｓｎ30及びＢａ8Ｇａ18Ｓｎ28はｐ型、Ｂａ8Ｇａ14Ｓｎ32及びＢａ8Ｇａ15Ｓｎ31はｎ型となる。
そして、このセグメント型熱電発電モジュールは、ΔＴ＝５７０Ｋにおいてη＝７．４％の変換効率を達成している。
Prior to the present invention, as shown in FIG. 7, the inventors of the present invention formed Ba 8 (Ga, which is a clathrate compound as materials 6 and 8 on the high temperature side of the p-type thermoelectric conversion element 4 and the n-type thermoelectric conversion element 5. Ge) 46 (BGG, type 1) is used, and Ba 8 (Ga, Sn) 46 (which is also a clathrate compound as materials 7 and 9 on the low temperature side of the p-type thermoelectric conversion element 4 and the n-type thermoelectric conversion element 5 ( A segment type thermoelectric power generation module (see Non-Patent Document 1) using BGT, type 8) was developed.
In BGG, whether it is p-type or n-type is determined by the mixing ratio of Ga and Ge, and in BGT, the mixing ratio of Ga and Sn.
For example, Ba 8 Ga 16 Ge 30 and Ba 8 Ga 18 Ge 28 is p-type, Ba 8 Ga 14 Ge 32 and Ba 8 Ga 15 Ge 31 becomes n-type, Ba 8 Ga 16 Sn 30 and Ba 8 Ga 18 Sn 28 Are p-type, and Ba 8 Ga 14 Sn 32 and Ba 8 Ga 15 Sn 31 are n-type.
This segment type thermoelectric power generation module achieves a conversion efficiency of η = 7.4% at ΔT = 570K.
しかし、これまでのところ、高い変換効率の得られるセグメント型熱電発電モジュールは、いずれもＰｂ、Ｔｅ、Ｓｂ等の環境負荷物質を母体元素とする熱電材料を利用しているため実用化が困難であった。
この発明は、環境負荷物質を含まないクラスレート化合物を用いるセグメント型熱電発電モジュールでありながら、環境負荷物質を含むセグメント型熱電発電モジュールに匹敵する変換効率の達成を課題としてなされたものである。
However, so far, all segment type thermoelectric power generation modules that can obtain high conversion efficiency are difficult to put into practical use because they use thermoelectric materials whose main elements are environmental load substances such as Pb, Te, and Sb. there were.
An object of the present invention is to achieve a conversion efficiency comparable to that of a segment type thermoelectric power generation module including an environmental load substance, although it is a segment type thermoelectric power generation module using a clathrate compound that does not include an environmental load substance.
請求項１に係る発明は、ｐ型熱電変換素子とｎ型熱電変換素子よりなるセグメント型熱電発電モジュールであって、前記ｎ型熱電変換素子は、低温側にタイプ２クラスレート化合物を用い、高温側にタイプ１クラスレート化合物又はタイプ９クラスレート化合物を用いたことを特徴とする。 The invention according to claim 1 is a segment type thermoelectric power generation module comprising a p-type thermoelectric conversion element and an n-type thermoelectric conversion element, wherein the n-type thermoelectric conversion element uses a type 2 clathrate compound on the low temperature side, A type 1 clathrate compound or a type 9 clathrate compound is used on the side.
請求項２に係る発明は、請求項１に記載のセグメント型熱電発電モジュールにおいて、前記ｐ型熱電変換素子は、低温側にタイプ８クラスレート化合物を用い、高温側にタイプ１クラスレート化合物を用いたことを特徴とする。 The invention according to claim 2 is the segment type thermoelectric power generation module according to claim 1, wherein the p-type thermoelectric conversion element uses a type 8 clathrate compound on the low temperature side and a type 1 clathrate compound on the high temperature side. It is characterized by that.
請求項３に係る発明は、請求項１又は２に記載のセグメント型熱電発電モジュールにおいて、前記ｎ型熱電変換素子の高温側に用いるタイプ１クラスレート化合物は、下記組成式（１）又は（２）で表されることを特徴とする。
Ｂａ8(Ｇａ,Ｇｅ)46・・・・（１）
Ｂａ8(Ｇａ,Ｓｉ)46・・・・（２）
The invention according to claim 3 is the segment type thermoelectric power generation module according to claim 1 or 2, wherein the type 1 clathrate compound used on the high temperature side of the n-type thermoelectric conversion element has the following composition formula (1) or (2 ).
Ba 8 (Ga, Ge) 46 (1)
Ba 8 (Ga, Si) 46 (2)
請求項４に係る発明は、請求項１〜３のいずれかに記載のセグメント型熱電発電モジュールにおいて、前記タイプ９クラスレート化合物は、下記組成式（３）〜（５）のいずれかで表されることを特徴とする。
Ｂａ24(Ｇａ,Ｇｅ)100・・・・・（３）
Ｂａ24(Ｉｎ,Ｇｅ)100・・・・・（４）
Ｂａ24(Ｇａ,Ｉｎ,Ｇｅ)100・・・（５）
The invention according to claim 4 is the segment type thermoelectric power generation module according to any one of claims 1 to 3, wherein the type 9 clathrate compound is represented by any one of the following composition formulas (3) to (5). It is characterized by that.
Ba 24 (Ga, Ge) 100 (3)
Ba 24 (In, Ge) 100 (4)
Ba 24 (Ga, In, Ge) 100 (5)
請求項５に係る発明は、請求項１〜４のいずれかに記載のセグメント型熱電発電モジュールにおいて、前記タイプ２クラスレート化合物は、下記組成式（６）〜（８）のいずれかで表されることを特徴とする。
(Ｋ,Ｂａ)24(Ｇａ,Ｓｎ)136・・・・・（６）
(Ｋ,Ｂａ)24(Ａｌ,Ｓｎ)136・・・・・（７）
(Ｋ,Ｂａ)24(Ｇａ,Ｓｎ,Ｇｅ)136・・・（８）
The invention according to claim 5 is the segment type thermoelectric power generation module according to any one of claims 1 to 4, wherein the type 2 clathrate compound is represented by any one of the following composition formulas (6) to (8). It is characterized by that.
(K, Ba) 24 (Ga, Sn) 136 (6)
(K, Ba) 24 (Al, Sn) 136 (7)
(K, Ba) 24 (Ga, Sn, Ge) 136 (8)
請求項１又は請求項１を引用する請求項３〜５のいずれかに係る発明によれば、従来のクラスレート化合物を利用したセグメント型熱電発電モジュールより変換効率の高いセグメント型熱電発電モジュールを提供することができる。
特に、高温側をタイプ９クラスレート化合物とした場合、低温側に配置してあるタイプ２クラスレート化合物との接触抵抗を非常に小さくすることができるので、変換効率の高いセグメント型熱電発電モジュールを提供できる可能性がある。
また、ｎ型熱電変換素子の低温側に用いたタイプ２クラスレート化合物は、無次元性能指数が大きく、４５０℃を超える高い温度域での使用に耐えるので、低温側電極の温度を低くできない環境下でも変換効率の高いセグメント型熱電発電モジュールを提供することができる。
According to the invention according to any one of claims 3 to 5 which cites claim 1 or claim 1, a segment type thermoelectric power generation module having higher conversion efficiency than a segment type thermoelectric power generation module using a conventional clathrate compound is provided. can do.
In particular, when the high temperature side is a type 9 clathrate compound, the contact resistance with the type 2 clathrate compound arranged on the low temperature side can be very small, so a segment type thermoelectric power generation module with high conversion efficiency can be obtained. There is a possibility to provide.
The type 2 clathrate compound used on the low temperature side of the n-type thermoelectric conversion element has a large dimensionless figure of merit and can withstand use in a high temperature range exceeding 450 ° C. It is possible to provide a segment type thermoelectric power generation module with high conversion efficiency even under.
請求項２又は請求項２を引用する請求項３〜５のいずれかに係る発明によれば、請求項１に係る発明による効果に加え、ｐ型熱電変換素子の低温側をタイプ８クラスレート化合物とし、高温側をタイプ１クラスレート化合物としているので、さらに変換効率の高いセグメント型熱電発電モジュールを提供することができる。 According to the invention according to any one of claims 3 to 5 that cites claim 2 or claim 2, in addition to the effect of the invention according to claim 1, the low temperature side of the p-type thermoelectric conversion element is a type 8 clathrate compound. Since the high temperature side is a type 1 clathrate compound, a segment type thermoelectric power generation module with higher conversion efficiency can be provided.
以下、実施例によって本発明の実施形態を説明する。 Hereinafter, embodiments of the present invention will be described by way of examples.
図１は実施例１のセグメント型熱電発電モジュールの単位構造を示す図である。
実施例１のセグメント型熱電発電モジュールのｐ型熱電変換素子４は、高温側にＢａ8Ｇａ16Ｇｅ30又はＢａ8Ｇａ16Ｓｉ30からなるタイプ１クラスレート化合物１０を用い、低温側にＢａ8Ｇａ16Ｓｎ30であるタイプ８クラスレート化合物１１を用いている。
また、同モジュールのｎ型熱電変換素子５は、高温側にＢａ8Ｇａ16Ｇｅ30又はＢａ8Ｇａ16Ｓｉ30であるタイプ１クラスレート化合物１２を用い、低温側に(Ｋ,Ｂａ)24(Ｇａ,Ｓｎ)136、(Ｋ,Ｂａ)24(Ａｌ,Ｓｎ)136、(Ｋ,Ｂａ)24(Ｇａ,Ｓｎ,Ｇｅ)136又はそれらの一部をＲｂ，Ｃｓ，Ｓｒ，Ａｌ，Ｉｎ若しくはＧｅで置換したものからなるタイプ２クラスレート化合物１３を用いている。
FIG. 1 is a diagram illustrating a unit structure of a segment type thermoelectric power generation module according to the first embodiment.
The p-type thermoelectric conversion element 4 of the segment type thermoelectric power generation module of Example 1 uses a type 1 clathrate compound 10 made of Ba 8 Ga 16 Ge 30 or Ba 8 Ga 16 Si 30 on the high temperature side, and Ba 8 on the low temperature side. A type 8 clathrate compound 11 which is Ga 16 Sn 30 is used.
The n-type thermoelectric conversion element 5 of the same module uses a type 1 clathrate compound 12 which is Ba 8 Ga 16 Ge 30 or Ba 8 Ga 16 Si 30 on the high temperature side, and (K, Ba) 24 ( Ga, Sn) 136 , (K, Ba) 24 (Al, Sn) 136 , (K, Ba) 24 (Ga, Sn, Ge) 136, or a part thereof may be converted to Rb, Cs, Sr, Al, In or Ge. The type 2 clathrate compound 13 consisting of the compound substituted with is used.
図２は実施例２のセグメント型熱電発電モジュールの単位構造を示す図である。
実施例２のセグメント型熱電発電モジュールのｐ型熱電変換素子４は、実施例１と同様、高温側にＢａ8Ｇａ16Ｇｅ30又はＢａ8Ｇａ16Ｓｉ30からなるタイプ１クラスレート化合物１０を用い、低温側にＢａ8Ｇａ16Ｓｎ30であるタイプ８クラスレート化合物１１を用いている。
また、同モジュールのｎ型熱電変換素子５は、高温側にＢａ24Ｇａ15Ｇｅ85、Ｂａ24Ｉｎ16Ｇｅ84又はそれらの混晶化物であるＢａ24(Ｇａ,Ｉｎ,Ｇｅ)100からなるタイプ９クラスレート化合物１４を用い、低温側に(Ｋ,Ｂａ)24(Ｇａ,Ｓｎ)136、(Ｋ,Ｂａ)24(Ａｌ,Ｓｎ)136、(Ｋ,Ｂａ)24(Ｇａ,Ｓｎ,Ｇｅ)136又はそれらの一部をＲｂ，Ｃｓ，Ｓｒ，Ａｌ，Ｉｎ若しくはＧｅで置換したものからなるタイプ２クラスレート化合物１５を用いている。
FIG. 2 is a diagram illustrating a unit structure of the segment type thermoelectric power generation module according to the second embodiment.
As in Example 1, the p-type thermoelectric conversion element 4 of the segment type thermoelectric power generation module of Example 2 uses a type 1 clathrate compound 10 made of Ba 8 Ga 16 Ge 30 or Ba 8 Ga 16 Si 30 on the high temperature side. On the low temperature side, the type 8 clathrate compound 11 which is Ba 8 Ga 16 Sn 30 is used.
Further, the n-type thermoelectric conversion element 5 of the same module is a type comprising Ba 24 Ga 15 Ge 85 , Ba 24 In 16 Ge 84 or Ba 24 (Ga, In, Ge) 100 which is a mixed crystal thereof on the high temperature side. Using 9 clathrate compound 14, (K, Ba) 24 (Ga, Sn) 136 , (K, Ba) 24 (Al, Sn) 136 , (K, Ba) 24 (Ga, Sn, Ge) on the low temperature side A type 2 clathrate compound 15 comprising 136 or a part thereof substituted with Rb, Cs, Sr, Al, In or Ge is used.
図３は、図７に示した従来例（ｐ型熱電変換素子４及びｎ型熱電変換素子５：低温側がタイプ８／高温側がタイプ１）、図１に示した実施例１（ｐ型熱電変換素子４：低温側がタイプ８／高温側がタイプ１、ｎ型熱電変換素子５：低温側がタイプ２／高温側がタイプ１）及び図２に示した実施例２（ｐ型熱電変換素子４：低温側がタイプ８／高温側がタイプ１、ｎ型熱電変換素子５：低温側がタイプ２／高温側がタイプ９）について、高温側電極と低温側電極との温度差（ΔＴ[Ｋ]）と変換効率（η[％]）の関係を示したグラフである。
なお、実施例１の測定値は□で、実施例２の測定値は△で、従来例の測定値は◇でプロットしてある。
3 shows the conventional example shown in FIG. 7 (p-type thermoelectric conversion element 4 and n-type thermoelectric conversion element 5: type 8 on the low temperature side / type 1 on the high temperature side), and Example 1 (p-type thermoelectric conversion on the high temperature side). Element 4: type 8 on the low temperature side / type 1 on the high temperature side, n-type thermoelectric conversion element 5: type 2 on the low temperature side / type 1 on the high temperature side) and Example 2 shown in FIG. 2 (p-type thermoelectric conversion element 4: type on the low temperature side) 8 / High temperature side is type 1, n-type thermoelectric conversion element 5: low temperature side is type 2 / high temperature side is type 9), temperature difference (ΔT [K]) between high temperature side electrode and low temperature side electrode and conversion efficiency (η [%] ]).
In addition, the measured value of Example 1 is plotted with □, the measured value of Example 2 is plotted with Δ, and the measured value of the conventional example is plotted with ◇.
このグラフから分かるように、実施例１及び２のセグメント型熱電発電モジュールの変換効率は、いずれの温度差においても従来例のセグメント型熱電発電モジュールの変換効率より高くなっており、実施例１の最大変換効率は約１０％、実施例２の最大変換効率は約９％と、従来例の最大変換効率より１．５％〜２．５％向上している。 As can be seen from this graph, the conversion efficiency of the segment type thermoelectric power generation modules of Examples 1 and 2 is higher than the conversion efficiency of the segment type thermoelectric power generation module of the conventional example at any temperature difference. The maximum conversion efficiency is about 10%, and the maximum conversion efficiency of Example 2 is about 9%, which is 1.5% to 2.5% higher than the maximum conversion efficiency of the conventional example.
次に、実施例１におけるｎ型熱電変換素子５の高温側材料に(Ｋ,Ｂａ)8(Ｇａ,Ｇｅ)46のタイプ１クラスレート化合物を用い、Ｋの組成比率を2.7、3.1、6.2に調整して、低温側材料との接触抵抗を測定した。
この測定は、クラスレート化合物を用いるセグメント型熱電発電モジュールにおいて、変換効率を上げるにはｎ型熱電変換素子の高温側材料と低温側材料との接触抵抗の低減が重要であることを考慮して行った。
その結果、Ｋ＝2.7では0.1〜0.2Ω、Ｋ＝3.1では0.1Ω、Ｋ＝6.2では0.04〜0.06Ωとなり、Ｋ＝6.2とすることで接触抵抗を最も小さくできることが分かった。
また、実施例２におけるｎ型熱電変換素子５についても、低温側材料（タイプ２クラスレート化合物）と高温側材料（タイプ９クラスレート化合物）との接触抵抗を測定したところ、0.003〜0.01Ωと接触抵抗が非常に小さいことも分かった。
Next, a type 1 clathrate compound of (K, Ba) 8 (Ga, Ge) 46 is used as the high temperature side material of the n-type thermoelectric conversion element 5 in Example 1, and the composition ratio of K is set to 2.7, 3.1, and 6.2. Adjustment was made to measure the contact resistance with the low temperature side material.
This measurement takes into account the reduction of the contact resistance between the high-temperature side material and the low-temperature side material of the n-type thermoelectric conversion element in order to increase the conversion efficiency in the segment type thermoelectric power generation module using a clathrate compound. went.
As a result, it was found that the resistance was 0.1 to 0.2Ω at K = 2.7, 0.1Ω at K = 3.1, 0.04 to 0.06Ω at K = 6.2, and the contact resistance could be minimized by setting K = 6.2.
Further, for the n-type thermoelectric conversion element 5 in Example 2, the contact resistance between the low-temperature side material (type 2 clathrate compound) and the high-temperature side material (type 9 clathrate compound) was measured and found to be 0.003 to 0.01Ω. It was also found that the contact resistance was very small.
実施例１及び２のセグメント型熱電発電モジュールに関する変形例を列記する。
（１）実施例１及び２においては、ｐ型熱電変換素子の材料として、高温側に他のＢａ8(Ｇａ,Ｇｅ)46又はＢａ8(Ｇａ,Ｓｉ)46からなるタイプ１クラスレート化合物を用い、低温側に他のＢａ8(Ｇａ,Ｓｎ)46からなるタイプ８クラスレート化合物を用いても良い。
また、これらにＡｕ、Ｃｕ等を０〜２部添加したタイプ１クラスレート化合物やタイプ８クラスレート化合物を用いても良い。
さらに、タイプ１とタイプ８との組み合わせ以外の２つのタイプを組み合わせたクラスレート化合物を用いても良い。
（２）実施例１及び２においては、ｐ型熱電変換素子では高温側の材料と低温側の材料の厚さをほぼ同じとし、ｎ型熱電変換素子では高温側の材料の厚さを低温側の材料の厚さより薄くしたが、ｐ型熱電変換素子及びｎ型熱電変換素子のいずれにおいても、高温側と低温側に用いる材料やセグメント型熱電発電モジュールの利用環境等に応じて、それぞれの材料の厚さを調整すると良い。
具体的には、熱電変換素子の温度分布が、高温側の材料の中央部においてＺＴが最大となる温度になるとともに、低温側の材料の中央部においてもＺＴが最大となる温度になるようにすると良い。
（３）実施例１におけるｎ型熱電変換素子５の高温側材料と低温側材料との接触抵抗を測定した結果からみて、実施例１のセグメント型熱電発電モジュールにおいて、ｎ型熱電変換素子５の高温側材料を、Ｋ6.2Ｂａ1.8(Ｇａ,Ｇｅ)46のタイプ１クラスレート化合物に変更すれば、変換効率が上がると予想される。
The modification regarding the segment type thermoelectric power generation module of Example 1 and 2 is listed.
(1) In Examples 1 and 2, a type 1 clathrate compound comprising Ba 8 (Ga, Ge) 46 or Ba 8 (Ga, Si) 46 on the high temperature side is used as the material of the p-type thermoelectric conversion element. It is also possible to use another type 8 clathrate compound composed of Ba 8 (Ga, Sn) 46 on the low temperature side.
Moreover, you may use the type 1 clathrate compound and the type 8 clathrate compound which added 0-2 parts of Au, Cu, etc. to these.
Furthermore, a clathrate compound in which two types other than the combination of type 1 and type 8 are combined may be used.
(2) In Examples 1 and 2, in the p-type thermoelectric conversion element, the high-temperature side material and the low-temperature side material have substantially the same thickness, and in the n-type thermoelectric conversion element, the high-temperature side material thickness is set to the low-temperature side. The thickness of the material is less than the thickness of the material, but in both the p-type thermoelectric conversion element and the n-type thermoelectric conversion element, depending on the material used on the high temperature side and the low temperature side, the usage environment of the segment type thermoelectric power generation module, etc. It is good to adjust the thickness.
Specifically, the temperature distribution of the thermoelectric conversion element is such that the temperature at which ZT is maximized in the central portion of the material on the high temperature side and the temperature at which ZT is maximized also in the central portion of the material on the low temperature side. Good.
(3) From the result of measuring the contact resistance between the high temperature side material and the low temperature side material of the n-type thermoelectric conversion element 5 in Example 1, in the segment type thermoelectric power generation module of Example 1, the n-type thermoelectric conversion element 5 If the high temperature side material is changed to a type 1 clathrate compound of K 6.2 Ba 1.8 (Ga, Ge) 46 , the conversion efficiency is expected to increase.
（４）実施例１においては、ｎ型熱電変換素子５の高温側にＢａ8Ｇａ16Ｇｅ30又はＢａ8Ｇａ16Ｓｉ30であるタイプ１クラスレート化合物１２を用い、低温側に(Ｋ,Ｂａ)24(Ｇａ,Ｓｎ)136、(Ｋ,Ｂａ)24(Ａｌ,Ｓｎ)136、(Ｋ,Ｂａ)24(Ｇａ,Ｓｎ,Ｇｅ)136又はそれらの一部をＲｂ，Ｃｓ，Ｓｒ，Ａｌ，Ｉｎ若しくはＧｅで置換したものからなるタイプ２クラスレート化合物１３を用いているが、高温側の材料は他の組成式で表されるタイプ１クラスレート化合物としても良く、低温側の材料は他の組成式で表されるタイプ２クラスレート化合物としても良い。
また、Ｂａ8Ｇａ16Ｇｅ30又はＢａ8Ｇａ16Ｓｉ30は、それぞれＢａ8(Ｇａ,Ｇｅ)46又はＢａ8(Ｇａ,Ｓｉ)46で表されるｎ型のタイプ１クラスレート化合物としても良い。
（５）実施例２においては、ｎ型熱電変換素子５の高温側にＢａ24Ｇａ15Ｇｅ85、Ｂａ24Ｉｎ16Ｇｅ84又はそれらの混晶化物であるＢａ24(Ｇａ,Ｉｎ,Ｇｅ)100からなるタイプ９クラスレート化合物１４を用い、低温側に(Ｋ,Ｂａ)24(Ｇａ,Ｓｎ)136、(Ｋ,Ｂａ)24(Ａｌ,Ｓｎ)136、(Ｋ,Ｂａ)24(Ｇａ,Ｓｎ,Ｇｅ)136又はそれらの一部をＲｂ，Ｃｓ，Ｓｒ，Ａｌ，Ｉｎ若しくはＧｅで置換したものからなるタイプ２クラスレート化合物１５を用いているが、高温側の材料は他の組成式で表されるタイプ９クラスレート化合物としても良く、低温側の材料は他の組成式で表されるタイプ２クラスレート化合物としても良い。
また、Ｂａ24Ｇａ15Ｇｅ85又はＢａ24Ｉｎ16Ｇｅ84は、それぞれＢａ24(Ｇａ,Ｇｅ)100又はＢａ24(Ｉｎ,Ｇｅ)100で表されるｎ型のタイプ９クラスレート化合物としても良い。
(4) In Example 1, the type 1 clathrate compound 12 which is Ba 8 Ga 16 Ge 30 or Ba 8 Ga 16 Si 30 is used on the high temperature side of the n-type thermoelectric conversion element 5, and (K, Ba ) 24 (Ga, Sn) 136 , (K, Ba) 24 (Al, Sn) 136 , (K, Ba) 24 (Ga, Sn, Ge) 136 or a part of them may be replaced with Rb, Cs, Sr, Al, The type 2 clathrate compound 13 made of In or Ge is used, but the high temperature side material may be a type 1 clathrate compound represented by another composition formula, and the low temperature side material may be other A type 2 clathrate compound represented by a composition formula may be used.
Ba 8 Ga 16 Ge 30 or Ba 8 Ga 16 Si 30 may be an n-type type 1 clathrate compound represented by Ba 8 (Ga, Ge) 46 or Ba 8 (Ga, Si) 46 , respectively. .
(5) In Example 2, Ba 24 Ga 15 Ge 85 , Ba 24 In 16 Ge 84 or a mixed crystal Ba 24 (Ga, In, Ge) 100 on the high temperature side of the n-type thermoelectric conversion element 5 is used. And (K, Ba) 24 (Ga, Sn) 136 , (K, Ba) 24 (Al, Sn) 136 , (K, Ba) 24 (Ga, Sn) , Ge) 136 or a type 2 clathrate compound 15 composed of Rb, Cs, Sr, Al, In, or Ge substituted at part thereof, is used, but the material on the high temperature side is represented by another composition formula. The type 9 clathrate compound may be used, and the material on the low temperature side may be a type 2 clathrate compound represented by another composition formula.
Further, Ba 24 Ga 15 Ge 85 or Ba 24 In 16 Ge 84 may be an n-type type 9 clathrate compound represented by Ba 24 (Ga, Ge) 100 or Ba 24 (In, Ge) 100 , respectively. .
１ 高温側電極 ２、３ 低温側電極 ４ ｐ型熱電変換素子
５ ｎ型熱電変換素子 ６、８ 高温帯でＺＴが最大となる材料
７、９ 低温帯でＺＴが最大となる材料
１０ タイプ１クラスレート化合物 １１ タイプ８クラスレート化合物
１２ タイプ１クラスレート化合物 １３ タイプ２クラスレート化合物
１４ タイプ９クラスレート化合物 １５ タイプ２クラスレート化合物
Ｐ 電気出力 Ｑ 熱入力 η 変換効率
ΔＴ 温度差 ＺＴ 性能指数
DESCRIPTION OF SYMBOLS 1 High temperature side electrode 2, 3 Low temperature side electrode 4 p-type thermoelectric conversion element 5 n-type thermoelectric conversion element 6, 8 Material where ZT becomes maximum in high temperature zone 7, 9 Material where ZT becomes maximum in low temperature zone 10 Type 1 class Rate compound 11 Type 8 clathrate compound 12 Type 1 clathrate compound 13 Type 2 clathrate compound 14 Type 9 clathrate compound 15 Type 2 clathrate compound P Electrical output Q Heat input η Conversion efficiency ΔT Temperature difference ZT Performance index
Claims (5)
前記ｎ型熱電変換素子は、低温側にタイプ２クラスレート化合物を用い、高温側にタイプ１クラスレート化合物又はタイプ９クラスレート化合物を用いた
ことを特徴とするセグメント型熱電発電モジュール。 A segment type thermoelectric power generation module comprising a p-type thermoelectric conversion element and an n-type thermoelectric conversion element,
The segment type thermoelectric power generation module, wherein the n-type thermoelectric conversion element uses a type 2 clathrate compound on the low temperature side and a type 1 clathrate compound or a type 9 clathrate compound on the high temperature side.
ことを特徴とする請求項１に記載のセグメント型熱電発電モジュール。 The segment type thermoelectric power generation module according to claim 1, wherein the p-type thermoelectric conversion element uses a type 8 clathrate compound on a low temperature side and a type 1 clathrate compound on a high temperature side.
ことを特徴とする請求項１又は２に記載のセグメント型熱電発電モジュール。
Ｂａ8(Ｇａ,Ｇｅ)46・・・・（１）
Ｂａ8(Ｇａ,Ｓｉ)46・・・・（２） The segment type thermoelectric power generation module according to claim 1 or 2, wherein the type 1 clathrate compound used on the high temperature side of the n-type thermoelectric conversion element is represented by the following composition formula (1) or (2): .
Ba 8 (Ga, Ge) 46 (1)
Ba 8 (Ga, Si) 46 (2)
ことを特徴とする請求項１〜３のいずれかに記載のセグメント型熱電発電モジュール。
Ｂａ24(Ｇａ,Ｇｅ)100・・・・・（３）
Ｂａ24(Ｉｎ,Ｇｅ)100・・・・・（４）
Ｂａ24(Ｇａ,Ｉｎ,Ｇｅ)100・・・（５） The segment type thermoelectric power generation module according to any one of claims 1 to 3, wherein the type 9 clathrate compound is represented by any one of the following composition formulas (3) to (5).
Ba 24 (Ga, Ge) 100 (3)
Ba 24 (In, Ge) 100 (4)
Ba 24 (Ga, In, Ge) 100 (5)
ことを特徴とする請求項１〜４のいずれかに記載のセグメント型熱電発電モジュール。
(Ｋ,Ｂａ)24(Ｇａ,Ｓｎ)136・・・・・（６）
(Ｋ,Ｂａ)24(Ａｌ,Ｓｎ)136・・・・・（７）
(Ｋ,Ｂａ)24(Ｇａ,Ｓｎ,Ｇｅ)136・・・（８） The segment type thermoelectric power generation module according to any one of claims 1 to 4, wherein the type 2 clathrate compound is represented by any one of the following composition formulas (6) to (8).
(K, Ba) 24 (Ga, Sn) 136 (6)
(K, Ba) 24 (Al, Sn) 136 (7)
(K, Ba) 24 (Ga, Sn, Ge) 136 (8)
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