JPH07211945A - P-type thermoelectric material and alloy therefor - Google Patents
P-type thermoelectric material and alloy thereforInfo
- Publication number
- JPH07211945A JPH07211945A JP6002531A JP253194A JPH07211945A JP H07211945 A JPH07211945 A JP H07211945A JP 6002531 A JP6002531 A JP 6002531A JP 253194 A JP253194 A JP 253194A JP H07211945 A JPH07211945 A JP H07211945A
- Authority
- JP
- Japan
- Prior art keywords
- type thermoelectric
- alloy
- thermoelectric material
- solid solution
- powder
- Prior art date
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】この出願の発明は、熱電冷却素子
や熱電発電素子の構成部材として利用されるＰ型熱電材
料用合金およびＰ型熱電材料に関する。特に、ビスマス
・テルル化合物（Ｂｉ2 Ｔｅ3 ）とアンチモン・テルル
化合物（Ｓｂ2 Ｔｅ3 ）またはビスマス・セレン化合物
（Ｂｉ2 Ｓｅ3 ）とを基本組成物とする固溶合金にドー
パントたる銀（Ａｇ）を０．００５〜０．２wt％添加し
て成るＰ型熱電材料用合金と、この合金の粉末を焼結成
形して成るＰ型熱電材料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The invention of the present application relates to a P-type thermoelectric material alloy and a P-type thermoelectric material used as constituent members of thermoelectric cooling elements and thermoelectric power generating elements. In particular, silver (Ag) as a dopant in a solid solution alloy containing a bismuth tellurium compound (Bi 2 Te 3 ) and an antimony tellurium compound (Sb 2 Te 3 ) or a bismuth selenium compound (Bi 2 Se 3 ) as a basic composition. ) 0.005 to 0.2 wt% is added to the alloy for P-type thermoelectric materials, and the P-type thermoelectric material formed by sintering the powder of this alloy.
【０００２】[0002]
【従来の技術】（Ｂｉ2 Ｔｅ3 ）と（Ｓｂ2 Ｔｅ3 ）ま
たは（Ｂｉ2 Ｓｅ3 ）とを基本組成物とする固溶合金で
あるＰ型熱電材料用合金と、このＰ型熱電材料用合金の
粉末を焼結して成るＰ型熱電材料は公知であり、例えば
文献「熱電半導体とその応用」（上村欣一，西田勲夫の
共同著作、昭和６３年１２月２０日、日刊工業新聞社発
行）に記載されている。 2. Description of the Related Art An alloy for a P-type thermoelectric material which is a solid solution alloy having (Bi 2 Te 3 ) and (Sb 2 Te 3 ) or (Bi 2 Se 3 ) as a basic composition, and this P-type thermoelectric material P-type thermoelectric materials formed by sintering powder of alloy for use are well known, for example, "Thermoelectric semiconductor and its application" (Joint work of Kinichi Uemura and Isao Nishida, December 20, 1988, Nikkan Kogyo Shimbun). Issued by the company).
【０００３】前記Ｐ型熱電材料用合金の組成は、一般的
には、（Ｂｉ2 Ｔｅ3 ）1 （Ｓｂ2Ｔｅ3 ）X （ここ
に、X ＝０．５〜４である）、（Ｂｉ2 Ｔｅ3 ）Y （Ｂ
ｉ2 Ｓｅ3 ）1 （ここに、Y ＝５〜２０である）であ
り、代表例としては（Ｂｉ2 Ｔｅ3 ）1 （Ｓｂ2 Ｔ
ｅ3 ）3 、（Ｂｉ2 Ｔｅ3 ）9 （Ｂｉ2 Ｓｅ3 ）1 が挙
げられる。The composition of the alloy for P-type thermoelectric materials is generally (Bi 2 Te 3 ) 1 (Sb 2 Te 3 ) x (where X = 0.5 to 4), (Bi 2 Te 3 ) Y (B
i 2 Se 3 ) 1 (where Y = 5 to 20), and as a typical example, (Bi 2 Te 3 ) 1 (Sb 2 T
e 3) 3, include (Bi 2 Te 3) 9 ( Bi 2 Se 3) 1.
【０００４】前記Ｐ型熱電材料は、近年まで前記Ｐ型熱
電材料用合金の溶製材で成形されていた。この溶製材
は、Ｂｉ，Ｔｅ，Ｓｂ，Ｓｅの各粉末を所定比率で調製
して成る混合粉末を石英管やパイレックスガラス管等の
容器内に真空密封し、加熱により溶融させて良く攪拌し
た後、一方向性凝固を行うことで得られていた。かかる
Ｐ型熱電材料は、高い性能指数Ｚを有する反面、へき開
性のために圧縮強度が低く（（Ｂｉ2 Ｔｅ3 ）1 （Ｓｂ
2 Ｔｅ3 ）3 のものでは圧縮強度が１．２ｋｇ／ｃ
ｍ2 ）、また一方向性凝固に長時間が必要で生産性が低
いと言う問題がある。Until recently, the P-type thermoelectric material was formed by ingot casting of the alloy for the P-type thermoelectric material. This ingot is vacuum-sealed into a container such as a quartz tube or a Pyrex glass tube, which is prepared by mixing powders of Bi, Te, Sb, and Se at a predetermined ratio, is melted by heating, and is well stirred. , Was obtained by performing unidirectional coagulation. Although such a P-type thermoelectric material has a high figure of merit Z, it has a low compressive strength ((Bi 2 Te 3 ) 1 (Sb
2 Te 3 ) 3 has a compressive strength of 1.2 kg / c
m 2 ) and unidirectional solidification requires a long time, resulting in low productivity.
【０００５】そこで、最近では、Ｂｉ，Ｔｅ，Ｓｂまた
はＳｅの各粉末を所定比率で調整して成る混合粉末を石
英管やパイレックスガラス管等の容器内に真空密封し、
加熱により溶融させて良く攪拌し冷却して得たＰ型熱電
材料用合金（一方向性凝固をさせてないもの）の粉末を
焼結成形して成り、性能指数Ｚは溶製材ものよりも低い
が、圧縮強度および生産性は溶製材に比べて格段に高い
Ｐ型熱電材料の実用化が推進されている。Therefore, recently, a mixed powder prepared by adjusting each powder of Bi, Te, Sb or Se at a predetermined ratio is vacuum-sealed in a container such as a quartz tube or a Pyrex glass tube,
It is made by sintering powder of P-type alloy for thermoelectric material (which is not unidirectionally solidified) obtained by melting by heating, stirring well and cooling, and the figure of merit Z is lower than that of ingot material. However, the practical use of P-type thermoelectric materials has been promoted, which are significantly higher in compressive strength and productivity than ingots.
【０００６】今日実用化されている（Ｂｉ2 Ｔｅ3 ）と
（Ｓｂ2 Ｔｅ3 ）または（Ｂｉ2 Ｓｅ3 ）とを基本組成
物とする固溶合金であるＰ型熱電材料用合金の粉末を焼
結成形して成るＰ型熱電材料の性能指数Ｚは高くても
２．２〜２．３である。A powder of an alloy for a P-type thermoelectric material, which is a solid solution alloy containing (Bi 2 Te 3 ) and (Sb 2 Te 3 ) or (Bi 2 Se 3 ) as a basic composition, which has been put into practical use today is prepared. The performance index Z of the P-type thermoelectric material formed by sintering is 2.2 to 2.3 at the highest.
【０００７】[0007]
【発明が解決しようとする課題】この出願の発明は、
（Ｂｉ2 Ｔｅ3 ）と（Ｓｂ2 Ｔｅ3 ）または（Ｂｉ2 Ｓ
ｅ3 ）とを基本組成物とする固溶合金であるＰ型熱電材
料用合金の粉末を焼結成形して成るＰ型熱電材料であっ
て、性能指数Ｚが従来品よりも高いＰ型熱電材料を得る
ことを目的とする。SUMMARY OF THE INVENTION The invention of this application is
(Bi 2 Te 3 ) and (Sb 2 Te 3 ) or (Bi 2 S
e 3 ) is a P-type thermoelectric material formed by sintering a powder of an alloy for P-type thermoelectric material, which is a solid solution alloy having a basic composition, and having a higher figure of merit Z than the conventional product. The purpose is to obtain the material.
【０００８】また、この出願の発明は、かかるＰ型熱電
材料の焼結成形の粉末材料となるＰ型熱電材料用合金を
得ることを目的とする。Another object of the invention of this application is to obtain an alloy for a P-type thermoelectric material which is a powder material for sintering and molding the P-type thermoelectric material.
【０００９】[0009]
【課題を解決するための手段】この出願の発明者は、
（Ｂｉ2 Ｔｅ3 ）と（Ｓｂ2 Ｔｅ3 ）または（Ｂｉ2 Ｓ
ｅ3 ）とを基本組成物とする固溶合金であるＰ型熱電材
料用合金の粉末を焼結成形して成るＰ型熱電材料の性能
指数Ｚを向上させるべく研究を重ねた様々な実験から、
固溶合金にドーパントを添加してないＰ型熱電材料用合
金の粉末を焼結成形してＰ型熱電材料を得る場合、製造
工程の雰囲気中の酸素量の多少により性能指数Ｚが影響
される（酸素量が多くなることで性能指数が低くなる）
ことを知見し、製造工程の雰囲気中の酸素量の影響を受
けにくい性質を与えることで性能指数Ｚの向上を試み、
この出願の発明を完成させたものである。The inventor of this application is
(Bi 2 Te 3 ) and (Sb 2 Te 3 ) or (Bi 2 S
From various experiments that have been repeated to improve the performance index Z of the P-type thermoelectric material formed by sintering the powder of the alloy for P-type thermoelectric material, which is a solid solution alloy having e 3 ) as a basic composition. ,
When a powder of an alloy for a P-type thermoelectric material in which a dopant is not added to a solid solution alloy is sinter-molded to obtain a P-type thermoelectric material, the figure of merit Z is affected by the amount of oxygen in the atmosphere of the manufacturing process. (The figure of merit decreases as the amount of oxygen increases)
Based on this, we tried to improve the figure of merit Z by giving a property that is less susceptible to the amount of oxygen in the atmosphere of the manufacturing process,
The invention of this application has been completed.
【００１０】この出願の請求項１の発明は、（Ｂｉ2 Ｔ
ｅ3 ）と（Ｓｂ2 Ｔｅ3 ）または（Ｂｉ2 Ｓｅ3 ）とを
基本組成物とする固溶合金にドーパントたるＡｇを０．
００５〜０．２wt％添加して成る合金の粉末を焼結して
成ることを特徴とするＰ型熱電材料である。The invention of claim 1 of this application is (Bi 2 T
e 3 ) and (Sb 2 Te 3 ) or (Bi 2 Se 3 ) as a basic composition in a solid solution alloy with Ag as a dopant of 0.
It is a P-type thermoelectric material characterized by being formed by sintering an alloy powder formed by adding 005 to 0.2 wt%.
【００１１】この出願の請求項２の発明は、（Ｂｉ2 Ｔ
ｅ3 ）と（Ｓｂ2 Ｔｅ3 ）または（Ｂｉ2 Ｓｅ3 ）とを
基本組成物とする固溶合金にドーパントたるＡｇを０．
００５〜０．２wt％添加して成るＰ型熱電材料用合金で
ある。The invention of claim 2 of this application is (Bi 2 T
e 3 ) and (Sb 2 Te 3 ) or (Bi 2 Se 3 ) as a basic composition in a solid solution alloy with Ag as a dopant of 0.
It is an alloy for P-type thermoelectric materials formed by adding 005 to 0.2 wt%.
【００１２】上記各発明において、Ａｇの添加量０．０
０５〜０．２wt％は（Ｂｉ2 Ｔｅ3）1 （Ｓｂ2 Ｔ
ｅ3 ）X （ここに、X ＝０．５〜４である）、（Ｂｉ2
Ｔｅ3 ）Y （Ｂｉ2 Ｓｅ3 ）1 （ここに、Y ＝５〜２０
である）なる固溶合金を対象とした値であり、（Ｂｉ2
Ｔｅ3 ）1 （Ｓｂ2 Ｔｅ3 ）X （ここに、X ≒３であ
る）、（Ｂｉ2 Ｔｅ3 ）Y （Ｂｉ2 Ｓｅ3 ）1 （ここ
に、Y ≒９である）の場合には０．００８〜０．１６wt
％が好ましい。In each of the above inventions, the addition amount of Ag is 0.0
05-0.2 wt% is (Bi 2 Te 3 ) 1 (Sb 2 T
e 3 ) X (where X = 0.5 to 4), (Bi 2
Te 3 ) Y (Bi 2 Se 3 ) 1 (where Y = 5 to 20)
In a) a value intended for solid solution alloy comprising, (Bi 2
Te 3 ) 1 (Sb 2 Te 3 ) X (where X ≈ 3), (Bi 2 Te 3 ) Y (Bi 2 Se 3 ) 1 (where Y ≈ 9) 0.008-0.16wt
% Is preferred.
【００１３】[0013]
【作用】この出願の発明に係るＰ型熱電材料は、性能指
数Ｚが従来品よりも高い値を有する。The P-type thermoelectric material according to the invention of this application has a figure of merit Z higher than that of the conventional product.
【００１４】例えば、（Ｂｉ2 Ｔｅ3 ）1 （Ｓｂ2 Ｔｅ
3 ）3 の固溶合金、（Ｂｉ2 Ｔｅ3）1 （Ｂｉ2 Ｓ
ｅ3 ）0.1 の固溶合金にＡｇを０．００８〜０．１６wt
％添加したＰ型熱電材料用合金（一方向性凝固はさせて
ない）を従来と同様にして作成し、これを従来と同様に
して粉末にし焼結成形したＰ型熱電材料は性能指数Ｚが
２．８〜３．１と言う高い値を示した。For example, (Bi 2 Te 3 ) 1 (Sb 2 Te
3 ) 3 solid solution alloy, (Bi 2 Te 3 ) 1 (Bi 2 S
0.008~0.16wt the Ag to e 3) 0.1 solid solution alloy
% P-type thermoelectric material alloy (not unidirectionally solidified) was prepared in the same manner as the conventional one, and the P-type thermoelectric material powdered and sintered in the same manner as the conventional one has a performance index Z of A high value of 2.8 to 3.1 was exhibited.
【００１５】そして、Ａｇを添加しなかった場合には、
合金作成時の真空度を１０-6Torrから１０-2Torrへ変更
することで性能指数Ｚが２．３〜１．９から１．３〜
１．１へ低下したのに対し、Ａｇを添加した場合には合
金作成時の真空度を１０-6Torrから１０-2Torrへ変更し
ても性能指数Ｚは３．１〜２．９から３．０〜２．８へ
低下するのに止まった。And, when Ag is not added,
By changing the degree of vacuum during alloy production from 10 -6 Torr to 10 -2 Torr, the figure of merit Z is 2.3-1.9 to 1.3-
However, when Ag was added, the figure of merit Z was 3.1 to 2.9 even if the degree of vacuum during alloy formation was changed from 10 -6 Torr to 10 -2 Torr. It stopped to drop to 3.0-2.8.
【００１６】この出願の発明に係るＰ型熱電材料用合金
は、一方向性凝固をさせない状態でも性能指数Ｚが２．
４程度であるので、一方向性凝固をさせることにより性
能指数Ｚは焼結成形したＰ型熱電材料の性能指数値を越
えた高さとなり、Ｐ型熱電材料用の溶製材としても利用
できる。The P-type thermoelectric material alloy according to the invention of this application has a figure of merit Z of 2. even when it is not unidirectionally solidified.
Since it is about 4, the figure of merit Z becomes a height exceeding the figure of merit value of the P-type thermoelectric material formed by sintering by unidirectional solidification, and the figure of merit can also be used as an ingot material for the P-type thermoelectric material.
【００１７】[0017]
【実施例】この出願の発明に係るＰ型熱電材料およびＰ
型熱電材料用合金の実施例を以下に説明する。EXAMPLES P-type thermoelectric material and P according to the invention of this application
Examples of alloys for die-type thermoelectric materials will be described below.
【００１８】（実施例１〜６および比較例１，２）実施
例１〜６および比較例１，２は、（Ｂｉ2 Ｔｅ3 ）と
（Ｓｂ2 Ｔｅ3 ）とを基本組成物とする固溶合金である
Ｐ型熱電材料用合金（一方向性凝固はさせてない）と、
その粉末を焼結成形したＰ型熱電材料である。(Examples 1 to 6 and Comparative Examples 1 and 2) Examples 1 to 6 and Comparative Examples 1 and 2 are solid compositions containing (Bi 2 Te 3 ) and (Sb 2 Te 3 ) as basic compositions. An alloy for a P-type thermoelectric material that is a molten alloy (not unidirectionally solidified),
It is a P-type thermoelectric material obtained by sintering the powder.
【００１９】次の表１に記載したように、実施例１にお
いては、Ｂｉ，Ｔｅ，Ｓｂの粉末を表１に記載した基本
組成の固溶合金を得る配合割合に配合するとともにＡｇ
粉末を０．００８wt％添加して良く混合した混合粉末を
作り、この混合粉末を１０-2Torrの真空状態下で石英管
内に封入し、７００℃に加熱して混合粉末を溶融させ均
質化した後、冷却・固化させ、石英管を破壊して固化し
たＰ型熱電材料用合金を得た。As shown in Table 1 below, in Example 1, the powders of Bi, Te, and Sb were blended at the blending ratio to obtain the solid solution alloy having the basic composition shown in Table 1 and Ag.
0.008 wt% of the powder was added and well mixed to prepare a mixed powder, which was enclosed in a quartz tube under a vacuum of 10 -2 Torr and heated to 700 ° C to melt and homogenize the mixed powder. Then, it was cooled and solidified, and the quartz tube was broken to obtain a solidified alloy for P-type thermoelectric material.
【００２０】そして、かかる合金を粉砕し分級して粒径
が１００μｍ以下の粉末を得、この粉末を焼結成形して
Ｐ型熱電材料を得た。焼結は、５００ｋｇ／ｃｍ2 の圧
力にて３５０℃で１時間行い、その後、２００℃で５時
間後処理を行った。Then, the alloy was pulverized and classified to obtain a powder having a particle size of 100 μm or less, and the powder was sintered and molded to obtain a P-type thermoelectric material. Sintering was performed at 350 ° C. for 1 hour at a pressure of 500 kg / cm 2 , and then post-treatment was performed at 200 ° C. for 5 hours.
【００２１】かかるＰ型熱電材料の導電率σ、熱電率
α、および熱伝導率κを測定し、これらから性能指数Ｚ
（Ｚ＝α2 ・σ／κ）を求めた。導電率σは交流四端子
法により測定し、熱電率αは焼結体の両端に４０℃の温
度差をつけてそこに発生する起電圧をデジタルメーター
で測定し、また熱伝導率κはレーザーフラッシュ法によ
り測定した。The electrical conductivity σ, thermoelectric constant α, and thermal conductivity κ of the P-type thermoelectric material were measured, and the figure of merit Z was obtained from these.
(Z = α 2 · σ / κ) was determined. The electrical conductivity σ is measured by the AC four-terminal method, the thermoelectric constant α is measured by a digital meter with the electromotive voltage generated at a temperature difference of 40 ° C. at both ends of the sintered body, and the thermal conductivity κ is measured by a laser. It was measured by the flash method.
【００２２】そして、オートグラフにより圧縮強度を求
めた。Then, the compression strength was determined by an autograph.
【００２３】実施例２〜６は、固溶合金の基本組成、Ａ
ｇ添加量、合金作成時の真空度を表１に記載したように
したことだけが実施例１と異なる。In Examples 2 to 6, the basic composition of the solid solution alloy, A
It differs from Example 1 only in that the addition amount of g and the degree of vacuum at the time of alloy preparation are as described in Table 1.
【００２４】比較例１は、Ａｇを添加しないことだけが
実施例１，２，４と異なり、比較例２はＡｇを添加しな
いことだけが実施例３と異なる。Comparative Example 1 is different from Examples 1, 2 and 4 only in that Ag is not added, and Comparative Example 2 is different from Example 3 in that Ag is not added.
【００２５】[0025]
【表１】 [Table 1]
【００２６】この表１に記載されているように、比較例
１，２のＰ型熱電材料の性能指数が１．３〜２．３であ
るのに対して、実施例１〜６のＰ型熱電材料の性能指数
は２．５〜３．１と格段に向上している。As shown in Table 1, the P-type thermoelectric materials of Comparative Examples 1 and 2 have a performance index of 1.3 to 2.3, while the P-type thermoelectric materials of Examples 1 to 6 have a performance index of 1.3 to 2.3. The figure of merit of the thermoelectric material is significantly improved to 2.5 to 3.1.
【００２７】（実施例７〜１２および比較例３，４）実
施例７〜１２および比較例３，４は、（Ｂｉ2 Ｔｅ3 ）
と（Ｂｉ2 Ｓｅ3 ）とを基本組成物とする固溶合金であ
るＰ型熱電材料用合金（一方向性凝固はさせてない）
と、その粉末を焼結成形したＰ型熱電材料である。(Examples 7 to 12 and Comparative Examples 3 and 4) Examples 7 to 12 and Comparative Examples 3 and 4 are (Bi 2 Te 3 )
And (Bi 2 Se 3 ) as a solid solution alloy for P-type thermoelectric materials (not unidirectionally solidified)
And a P-type thermoelectric material obtained by sintering the powder.
【００２８】次の表２に記載したように、実施例７にお
いては、Ｂｉ，Ｔｅ，Ｓｅの粉末を表２に記載した基本
組成の固溶合金を得る配合割合に配合するとともにＡｇ
粉末を０．００８wt％添加して良く混合した混合粉末を
作り、この混合粉末を１０-2Torrの真空状態下で石英管
内に封入し、７００°Ｃに加熱して混合粉末を溶融させ
均質化した後、冷却・固化させ、石英管を破壊して固化
したＰ型熱電材料用合金を得た。As shown in Table 2 below, in Example 7, the powders of Bi, Te, and Se were blended at the blending ratio to obtain the solid solution alloy having the basic composition shown in Table 2 and Ag.
Add 0.008wt% of powder to make a well-mixed powder, enclose this mixed powder in a quartz tube under vacuum of 10 -2 Torr, and heat to 700 ° C to melt and homogenize the mixed powder. After that, it was cooled and solidified, and the quartz tube was destroyed to obtain a solidified alloy for P-type thermoelectric material.
【００２９】そして、かかる合金を粉砕し分級して粒径
が１００μｍ以下の粉末を得、この粉末を実施例１〜６
と同じ条件で焼結成形してＰ型熱電材料を得た。Then, the alloy is pulverized and classified to obtain a powder having a particle size of 100 μm or less.
Sinter molding was performed under the same conditions as above to obtain a P-type thermoelectric material.
【００３０】かかるＰ型熱電材料の導電率σ、熱電率
α、および熱伝導率κを測定し、これらから性能指数Ｚ
（Ｚ＝α2 ・σ／κ）を実施例１〜６と同様にして求め
た。The electrical conductivity σ, thermoelectric constant α, and thermal conductivity κ of the P-type thermoelectric material are measured, and the figure of merit Z is obtained from these.
(Z = α 2 · σ / κ) was obtained in the same manner as in Examples 1 to 6.
【００３１】実施例８〜１２は、固溶合金の基本組成、
Ａｇ添加量、合金作成時の真空度を表２に記載したよう
にしたことだけが実施例１と異なる。比較例３は、Ａｇ
を添加しないことだけが実施例７，８，１０と異なり、
比較例４はＡｇを添加しないことだけが実施例９と異な
る。Examples 8 to 12 are the basic composition of the solid solution alloy,
It differs from Example 1 only in that the amount of Ag added and the degree of vacuum at the time of alloy preparation were as described in Table 2. Comparative Example 3 is Ag
Differs from Examples 7, 8 and 10 only in that
Comparative Example 4 differs from Example 9 only in that Ag is not added.
【００３２】[0032]
【表２】 [Table 2]
【００３３】この表２に記載されているように、比較例
３，４のＰ型熱電材料の性能指数が１．１〜１．９であ
るのに対して、実施例７〜１２のＰ型熱電材料の性能指
数は２．５〜３．０と格段に向上している。As shown in Table 2, the performance indexes of the P-type thermoelectric materials of Comparative Examples 3 and 4 are 1.1 to 1.9, whereas the P-type thermoelectric materials of Examples 7 to 12 are P-type. The figure of merit of the thermoelectric material is significantly improved to 2.5 to 3.0.
【００３４】[0034]
【発明の効果】以上詳細に説明したように、この出願の
発明に係るＰ型熱電材料は、性能指数値が高く、圧縮強
度が大きく、且つ、製造コストが低い（一方向性凝固を
必要とせず、高い真空度を達成できる高価設備が不要と
なるため）。従って、熱電冷却素子や熱電発電素子の実
用化を促進できる。また、この出願の発明に係るＰ型熱
電材料用合金は、更に、一方向性凝固を行わせて高い性
能指数を有する溶製材としても利用でき、高い圧縮強度
を必要としない高性能のＰ型熱電材料を提供することが
できる。As described in detail above, the P-type thermoelectric material according to the invention of this application has a high figure of merit value, a high compressive strength, and a low manufacturing cost (need to require unidirectional solidification). No need for expensive equipment that can achieve a high degree of vacuum). Therefore, the practical application of the thermoelectric cooling element and the thermoelectric power generating element can be promoted. Further, the alloy for P-type thermoelectric material according to the invention of this application can be used as a melting material having a high figure of merit by performing unidirectional solidification, and is a high-performance P-type alloy that does not require high compressive strength. A thermoelectric material can be provided.
Claims (2)
ｅ3 ）とアンチモン・テルル化合物（Ｓｂ2 Ｔｅ3 ）ま
たはビスマス・セレン化合物（Ｂｉ2 Ｓｅ3 ）とを基本
組成物とする固溶合金にドーパントたる銀（Ａｇ）を
０．００５〜０．２wt％添加して成るＰ型熱電材料用合
金粉末を焼結成形して成ることを特徴とするＰ型熱電材
料。1. A bismuth tellurium compound (Bi 2 T
e 3 ) and antimony tellurium compound (Sb 2 Te 3 ) or bismuth selenium compound (Bi 2 Se 3 ) as a basic composition in a solid solution alloy with 0.005 to 0.2 wt% of silver (Ag) as a dopant. % Of P-type thermoelectric material alloy powder for sinter molding.
ｅ3 ）とアンチモン・テルル化合物（Ｓｂ2 Ｔｅ3 ）ま
たはビスマス・セレン化合物（Ｂｉ2 Ｓｅ3 ）とを基本
組成物とする固溶合金にドーパントたる銀（Ａｇ）を
０．００５〜０．２wt％添加して成るＰ型熱電材料用合
金。2. A bismuth tellurium compound (Bi 2 T
e 3 ) and antimony tellurium compound (Sb 2 Te 3 ) or bismuth selenium compound (Bi 2 Se 3 ) as a basic composition in a solid solution alloy with 0.005 to 0.2 wt% of silver (Ag) as a dopant. % Alloy for P-type thermoelectric materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00253194A JP3528222B2 (en) | 1994-01-14 | 1994-01-14 | P-type thermoelectric material and alloy for P-type thermoelectric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00253194A JP3528222B2 (en) | 1994-01-14 | 1994-01-14 | P-type thermoelectric material and alloy for P-type thermoelectric material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07211945A true JPH07211945A (en) | 1995-08-11 |
| JP3528222B2 JP3528222B2 (en) | 2004-05-17 |
Family
ID=11531973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP00253194A Expired - Lifetime JP3528222B2 (en) | 1994-01-14 | 1994-01-14 | P-type thermoelectric material and alloy for P-type thermoelectric material |
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| Country | Link |
|---|---|
| JP (1) | JP3528222B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002021606A1 (en) * | 2000-09-08 | 2002-03-14 | Korea Institute Of Science And Technology | The method manufacturing p-type bismuth telluride thermoelectric materials for the enhancement of the yield of high quality ingot |
| JP2010118632A (en) * | 2008-11-13 | 2010-05-27 | Korea Electrotechnology Research Inst | Thermoelectric material for lower and medium temperature |
| JP2013157362A (en) * | 2012-01-26 | 2013-08-15 | Toyota Motor Corp | Thermoelectric semiconductor |
| JP2016009857A (en) * | 2014-06-24 | 2016-01-18 | コリア エレクトロテクノロジー リサーチ インスティテュートＫｏｒｅａ Ｅｌｅｃｔｒｏｔｅｃｈｎｏｌｏｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ | Te-BASED THERMOELECTRIC MATERIAL HAVING COMPLEX CRYSTAL STRUCTURE FORMED BY ADDITION OF INTERSTITIAL DOPANT |
| CN113773083B (en) * | 2021-09-13 | 2022-10-04 | 哈尔滨工业大学 | Bismuth telluride-based material with high strength and high thermoelectric property and preparation method thereof |
-
1994
- 1994-01-14 JP JP00253194A patent/JP3528222B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002021606A1 (en) * | 2000-09-08 | 2002-03-14 | Korea Institute Of Science And Technology | The method manufacturing p-type bismuth telluride thermoelectric materials for the enhancement of the yield of high quality ingot |
| JP2010118632A (en) * | 2008-11-13 | 2010-05-27 | Korea Electrotechnology Research Inst | Thermoelectric material for lower and medium temperature |
| JP2013157362A (en) * | 2012-01-26 | 2013-08-15 | Toyota Motor Corp | Thermoelectric semiconductor |
| JP2016009857A (en) * | 2014-06-24 | 2016-01-18 | コリア エレクトロテクノロジー リサーチ インスティテュートＫｏｒｅａ Ｅｌｅｃｔｒｏｔｅｃｈｎｏｌｏｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ | Te-BASED THERMOELECTRIC MATERIAL HAVING COMPLEX CRYSTAL STRUCTURE FORMED BY ADDITION OF INTERSTITIAL DOPANT |
| CN113773083B (en) * | 2021-09-13 | 2022-10-04 | 哈尔滨工业大学 | Bismuth telluride-based material with high strength and high thermoelectric property and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3528222B2 (en) | 2004-05-17 |
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