JP4081547B2 - Terbium multiboride thermoelectric element represented by TbB44Si2 - Google Patents
Terbium multiboride thermoelectric element represented by TbB44Si2 Download PDFInfo
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- JP4081547B2 JP4081547B2 JP2003399282A JP2003399282A JP4081547B2 JP 4081547 B2 JP4081547 B2 JP 4081547B2 JP 2003399282 A JP2003399282 A JP 2003399282A JP 2003399282 A JP2003399282 A JP 2003399282A JP 4081547 B2 JP4081547 B2 JP 4081547B2
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- Prior art keywords
- thermoelectric element
- terbium
- multiboride
- thermoelectric
- polyboride
- 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.)
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Links
- 229910052771 Terbium Inorganic materials 0.000 title claims description 10
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 title claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 150000002910 rare earth metals Chemical class 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- 229910052796 boron Inorganic materials 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 150000001217 Terbium Chemical class 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Description
この発明は、ＴｂＢ ４４ Ｓｉ ２ で示されるテルビウム多ホウ化物からなる熱電素子に関す
るものである。
The present invention relates to a thermoelectric element made of a terbium polyboride represented by TbB 44 Si 2 .
従来、熱電素子については、現代社会で効率的にエネルギーを使用するために盛んな材料
研究が行われており、信頼性の高い静かな冷却装置や発電機に使用するための大きな需要
が築かれた。一方で、多ホウ化物は、特徴として、高融点を有し、高温においても極めて
安定であるという劣悪環境下での魅力的な特性を有するけれども、電子的性質において機
能に結び付く興味深い性質は見つかってなかった。しかし、最近、希土類多ホウ化物が熱
電素子材料、分光素子材料、発光材料として有用であることが見出された（例えば、特許
文献１〜７）。
Conventionally, for the thermoelectric device, thriving materials research in order to use efficiently the energy in modern society has been performed, a great demand for use in reliable quiet cooling system and the generator are built It was. On the other hand, polyboride has a characteristic that it has a high melting point and has an attractive property in a poor environment that it is extremely stable even at high temperatures, but an interesting property that is linked to a function in an electronic property has been found. There wasn't. However, recently, it has been found that rare earth polyboride is useful as a thermoelectric element material, a spectroscopic element material, and a light emitting material (for example,
従来の熱電材料は、高温（800K以上）で性能の鈍化を示さず、安定性に優れた材料がない
のが現状であり、特に、そうした高温、劣悪な環境下で排熱を利用したような発電が資源
や環境の保護に重点が置かれている現代社会で必要であり、その目的のために新しい素材
を見出すことが期待されている状況にある。
Conventional thermoelectric materials do not show a slowdown in performance at high temperatures (800K or higher), and there is no material with excellent stability, especially when exhaust heat is used at such high temperatures and in poor environments. Power generation is necessary in modern societies where the emphasis is on the protection of resources and the environment, and it is expected to find new materials for that purpose.
この発明は、以上の通りの事情に鑑みてなされたものであり、従来、希土類多ホウ化物に
は得られていない新しい機能として、高温で優れた熱電的性質を有する新しい機能を示す
多ホウ化物を提供することを目的としている。
The present invention has been made in view of the circumstances as described above. Conventionally, as a new function that has not been obtained in rare earth multiboride, a multiboride exhibiting a new function having excellent thermoelectric properties at high temperatures. The purpose is to provide.
我々は、多ホウ化物がクラスター固体として低い熱伝導率を持つことに注目して、また、
伝導機構がホッピング則に従うために高温で急速に抵抗率が低くなることにも注目して、
高温における熱電素子の可能性を考えた。そして、特に注目した希土類ホウ素クラスター
化合物の中で、ＴｂＢ ４４ Ｓｉ ２ で示されるテルビウム多ホウ化物が800K以上においても
200mV/K以上の高いゼ−ベック係数を示すことを発見した。そして、熱電素子としての性
能指数を表すZTも高温に行くほど急速に上昇して行くことを確認した。また、極めて優れ
た耐酸性を有し、硝酸や硫酸環境下でも安定であるという性質を発見した。
We note that polyboride has low thermal conductivity as a cluster solid,
Note also that the resistivity decreases rapidly at high temperatures because the conduction mechanism follows the hopping law,
The possibility of thermoelectric elements at high temperature was considered. Among the rare-earth boron cluster compounds that have been particularly focused on, the terbium polyboride represented by TbB 44 Si 2 is present even at 800K or higher.
It was found to show a high Seebeck coefficient of 200 mV / K or higher. It was also confirmed that ZT, which represents the figure of merit as a thermoelectric element, increases rapidly as the temperature increases. Also very good
We have found that it has acid resistance and is stable in nitric acid and sulfuric acid environments.
このテルビウム多ホウ化物は２０００K以上という高融点を有し、高温下に曝しても安定
であり、また、極めて優れた耐酸性を有し、硝酸や硫酸環境下でも安定であるという性質
と、高温や酸性下で高いゼーベック係数、低抵抗、低熱伝導率を示す性質を利用して、高
温や酸性雰囲気下で使用され、特に、極めて高温や劣悪な酸性環境においても使用可能な
熱電素子を提供できる。
This terbium polyboride has a high melting point of 2000K or higher, is stable even when exposed to high temperatures, has extremely excellent acid resistance, and is stable in nitric acid and sulfuric acid environments, Utilizing the properties of high Seebeck coefficient, low resistance, and low thermal conductivity under acidic conditions, it is possible to provide thermoelectric elements that can be used in high temperatures and acidic atmospheres, especially in extremely high temperatures and in poor acidic environments. .
ＴｂＢ ４４ Ｓｉ ２ で示される希土類多ホウ化物の好ましい製造方法を以下に示す。
（方法１）
Ｔｂに対するホウ素の比が44で、Ｔｂに対するケイ素の比が２となるように、既知のＴｂ
ホウ化物(ＴｂB2、ＴｂB4、ＴｂB8、ＴｂB12等)にホウ素とケイ素を混合し、その混合物
を真空下または不活性ガス下で1400℃温度以上2200℃以下で固相反応する。
A preferred method for producing a rare earth polyboride represented by TbB 44 Si 2 is shown below.
(Method 1)
The ratio of
Boron ( Tb B 2 , Tb B 4 , Tb B 8 , Tb B 12, etc.) is mixed with boron and silicon, and the mixture is subjected to a solid phase reaction at a temperature of 1400 ° C. to 2200 ° C. under vacuum or inert gas. To do.
（方法２）
Ｔｂに対するホウ素の比が44で、Ｔｂに対するケイ素の比が２となるように、既知のＴｂ
ホウ化物(ＴｂB2、ＴｂB4、ＴｂB8、ＴｂB12等)にホウ素とケイ素を混合し、その混合物
を真空下または不活性ガス下で溶融する。
(Method 2)
The ratio of
Boron and silicon were mixed boride (Tb B 2, Tb B 4 , Tb B 8, Tb B 12 , etc.), mixtures thereof you melted under vacuum or an inert gas.
（方法３）
Ｔｂに対するホウ素の比が44で、Ｔｂに対するケイ素の比が２で、かつ酸素とホウ素の比
が１となるように、Ｔｂ酸化物にホウ素とケイ素を混合し、その混合物を不活性ガス下で
アーク溶融する。
(Method 3)
The ratio of
以下実施例を示し、さらにこの発明について詳しく説明する。
Tb4O7とBをTbに対するBの比が50で、かつOとBの比が１となる割合で混合し、これを加圧
成形したものを真空中、1750℃で4時間加熱して得られたものを粉砕して、Tbに対するSi
の比が2になるように混合し、これを加圧成形したものを真空中、1900℃で10時間加熱す
る。化学分析と粉末X線回折による測定では、[B]/[Tb] =44.0、[Si] / [Tb] =2.0となり
、TbB44+XSi1.8+Y(X=0,Y=0.2)のほぼ所望の組成と近似するテルビウム多ホウ化物を得た
ことが確認された。そして、粉末X線回折より、格子定数a=16.75A,b=17.73 A, c=9.57 A
の斜方晶で指数付けすることができた。
Hereinafter, the present invention will be described in detail with reference to examples.
Tb 4 O 7 and B were mixed at a ratio of B to Tb of 50 and a ratio of O to B of 1, and this was pressure-molded and heated in vacuum at 1750 ° C. for 4 hours. The obtained material is crushed and Si against Tb
The mixture is mixed so that the ratio of 2 is 2 and this is pressure-molded and heated in vacuum at 1900 ° C. for 10 hours. In chemical analysis and powder X-ray diffraction measurement, [B] / [Tb] = 44.0, [Si] / [Tb] = 2.0, and TbB 44 + X Si 1.8 + Y (X = 0, Y = 0.2) It was confirmed that a terbium polyboride having an approximate composition desired was obtained. And from powder X-ray diffraction, lattice constant a = 16.75A, b = 17.73 A, c = 9.57 A
It was possible to index with orthorhombic crystals.
図１に、得られた希土類多ホウ化物熱電材料のゼーベック係数の温度依存性を示す。また
、図２に、得られた希土類多ホウ化物熱電材料の性能指数の温度依存性を示す。TbB44+XS
i1.8+Y(X=0,Y=0.2)は800K以上においても200mV/K以上の高いゼ−ベック係数を示し、性能
指数ZTも高温に行くほど上昇して行くことが確認された。そして、硝酸、硫酸下でも安定
であることが確認された。
FIG. 1 shows the temperature dependence of the Seebeck coefficient of the obtained rare earth polyboride thermoelectric material. FIG. 2 shows the temperature dependence of the figure of merit of the obtained rare earth polyboride thermoelectric material. TbB 44 + X S
i 1.8 + Y (X = 0, Y = 0.2) showed a high Seebeck coefficient of 200 mV / K or higher even at 800 K or higher, and it was confirmed that the figure of merit ZT increased as the temperature increased. And it was confirmed that it is stable even under nitric acid and sulfuric acid.
以上詳しく説明した通り、この発明によって、いままでには存在しなかったテルビウム多
ホウ化物において高温の熱電素子が提供される。融点も高く、高温2000Kに至るまで安定
であり、温度上昇に伴い熱電素子としての性能が高くなるので、800K以上で使用できる熱
電素子、また、酸性雰囲気下でも使用できる熱電素子として有望視される。将来的には劣
悪な環境、例えば、他惑星無人探索等においての使用も考えられる。実際に、木星の月Eu
ropa上などにおいては硫酸が充満している環境である。当テルビウム多ホウ化物はそのよ
うな環境下でも安定であり、熱電材料として魅力的な特性が備わった化合物であるので、
特異性があり、素子として使用可能である。
As explained in detail above, the present invention provides a high-temperature thermoelectric element in terbium polyboride that has not existed so far. It has a high melting point and is stable up to high temperature 2000K, and its performance as a thermoelectric element increases as the temperature rises. Therefore, it is promising as a thermoelectric element that can be used at 800K or higher, and also in an acidic atmosphere. . In the future, it may be used in a poor environment such as unattended search for other planets. Actually, Jupiter Moon Eu
On ropa, etc., the environment is full of sulfuric acid. Since this terbium polyboride is a compound that is stable under such circumstances and has attractive properties as a thermoelectric material,
It has specificity and can be used as an element.
Claims (3)
ｍＶ／Ｋ以上のゼーベック係数を示す高温特性を有することを特徴とする希土類多ホウ化
物熱電素子。 It consists of terbium polyboride represented by TbB 44 Si 2 and is 200 at 800 K or more.
rare earth, characterized in Rukoto to have a high-temperature characteristic shows the Seebeck coefficient of more mV / K multi borides thermoelectric elements.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003399282A JP4081547B2 (en) | 2003-11-28 | 2003-11-28 | Terbium multiboride thermoelectric element represented by TbB44Si2 |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003399282A JP4081547B2 (en) | 2003-11-28 | 2003-11-28 | Terbium multiboride thermoelectric element represented by TbB44Si2 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005159242A JP2005159242A (en) | 2005-06-16 |
| JP4081547B2 true JP4081547B2 (en) | 2008-04-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003399282A Expired - Lifetime JP4081547B2 (en) | 2003-11-28 | 2003-11-28 | Terbium multiboride thermoelectric element represented by TbB44Si2 |
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| Country | Link |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4854215B2 (en) * | 2005-04-26 | 2012-01-18 | 旭化成株式会社 | Thermoelectric material and manufacturing method thereof |
| JP5051412B2 (en) * | 2005-08-18 | 2012-10-17 | 独立行政法人物質・材料研究機構 | Rare earth polyboride-based high-temperature acid-resistant n-type thermoelectric material doped with carbon and nitrogen and method for producing the same |
| JP4840755B2 (en) * | 2005-11-11 | 2011-12-21 | 独立行政法人物質・材料研究機構 | Rare earth polyboride-based thermoelectric conversion material doped with metal low boride and its production method |
| JP5429863B2 (en) * | 2009-07-23 | 2014-02-26 | 独立行政法人物質・材料研究機構 | Thermoelectric element |
| JP5382707B2 (en) * | 2009-07-24 | 2014-01-08 | 独立行政法人物質・材料研究機構 | Thermoelectric semiconductor and thermoelectric power generation element using it |
| JP5273685B2 (en) * | 2011-10-06 | 2013-08-28 | 独立行政法人物質・材料研究機構 | N-type thermoelectric conversion element using rare earth polyboride-based high-temperature acid-resistant n-type thermoelectric material doped with carbon and nitrogen |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2810980B2 (en) * | 1995-10-02 | 1998-10-15 | 科学技術庁無機材質研究所長 | Yttrium borosilicate and its rare earth substitutes |
| JP3624244B2 (en) * | 2001-10-30 | 2005-03-02 | 独立行政法人物質・材料研究機構 | Rare earth borosilicate and method for producing the same |
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- 2003-11-28 JP JP2003399282A patent/JP4081547B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JP2005159242A (en) | 2005-06-16 |
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