JPH09172202A - Thermoelectric element - Google Patents
Thermoelectric elementInfo
- Publication number
- JPH09172202A JPH09172202A JP7332409A JP33240995A JPH09172202A JP H09172202 A JPH09172202 A JP H09172202A JP 7332409 A JP7332409 A JP 7332409A JP 33240995 A JP33240995 A JP 33240995A JP H09172202 A JPH09172202 A JP H09172202A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- thermoelectric element
- seebeck coefficient
- electric conductivity
- type thermoelectric
- 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.)
- Pending
Links
- 239000000956 alloy Substances 0.000 claims abstract description 90
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 85
- 239000000843 powder Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 abstract description 44
- 239000000463 material Substances 0.000 abstract description 7
- 229910016273 Bi2 Se3 Inorganic materials 0.000 abstract 3
- 229910016272 Bi2 Te3 Inorganic materials 0.000 abstract 3
- 238000000034 method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 229910016339 Bi—Sb—Te Inorganic materials 0.000 description 3
- 229910001370 Se alloy Inorganic materials 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 229910002665 PbTe Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 2
- 230000005676 thermoelectric effect Effects 0.000 description 2
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- 230000005679 Peltier effect Effects 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 229910001215 Te alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、熱電素子に係るも
のであり、特に、性能指数が向上した熱電素子に関する
ものである。TECHNICAL FIELD The present invention relates to a thermoelectric element, and more particularly to a thermoelectric element having an improved figure of merit.
【０００２】[0002]
【従来の技術】熱電素子は、ゼーベック効果、ペルチェ
効果等の熱電効果を有し、この熱電効果により、熱エネ
ルギーを電気エネルギーに変換し、或いは電気エネルギ
ーを熱エネルギーに変換し得る半導体素子である。この
熱電効果を利用して、熱電素子に電流を流し、熱電素子
の両端面間で温度勾配を生じさせ、冷却装置等に用いら
れる、いわゆるペルチェ素子が開発されている。これら
熱電素子の開発の中心は、熱電素子の最大温度差を増加
させて冷却能力を向上させることであり、そのため最大
吸熱量に正比例的に影響する性能指数Ｚを向上させるこ
とに帰着する。2. Description of the Related Art A thermoelectric element is a semiconductor element having thermoelectric effects such as Seebeck effect and Peltier effect, which can convert thermal energy into electric energy or electric energy into thermal energy. . Utilizing this thermoelectric effect, a so-called Peltier element has been developed, in which a current is passed through the thermoelectric element to generate a temperature gradient between both end surfaces of the thermoelectric element and which is used in a cooling device or the like. The focus of the development of these thermoelectric elements is to increase the maximum temperature difference of the thermoelectric elements to improve the cooling capacity, and thus to improve the performance index Z that directly proportionally affects the maximum heat absorption.
【０００３】性能指数Ｚは、数１のように表される。The figure of merit Z is expressed by the following equation 1.
【０００４】[0004]
【数１】 [Equation 1]
【０００５】ここで、αはゼーベック係数、σは電気伝
導度、κは熱伝導率である。Here, α is the Seebeck coefficient, σ is the electrical conductivity, and κ is the thermal conductivity.
【０００６】キャリアが電子であるＮ型熱電素子の代表
的な合金材料として、Ｂｉ2 Ｔｅ3がある。このＢｉ2
Ｔｅ3 の性能指数Ｚを更に向上させる目的で、Ｔｅの一
部をＳｅで置換したＢｉ−Ｔｅ−Ｓｅ系合金が近年注目
されている。また、キャリアが正孔であるＰ型熱電素子
についても、性能指数Ｚを更に向上させる目的で、Ｂｉ
2 Ｔｅ3 合金のうちＢｉの一部をＳｂで置換したＢｉ−
Ｓｂ−Ｔｅ系合金が近年注目されている。Bi 2 Te 3 is a typical alloy material for an N-type thermoelectric element whose carrier is an electron. This Bi 2
For the purpose of further improving the figure of merit Z of Te 3 , Bi-Te-Se based alloy in which a part of Te is replaced with Se has been attracting attention in recent years. In addition, for a P-type thermoelectric element in which the carrier is a hole, Bi is used for the purpose of further improving the figure of merit Z.
Bi-in which a part of Bi in the 2 Te 3 alloy is replaced with Sb
Recently, Sb-Te based alloys have been receiving attention.
【０００７】[0007]
【発明が解決しようとする課題】Ｂｉ−Ｔｅ−Ｓｅ系合
金及び、Ｂｉ−Ｓｂ−Ｔｅ系合金は、通常は、固溶体合
金の粉末焼結体として形成される。即ち、所定の組成比
で用意された各種金属（Ｎ型熱電素子の場合はＢｉ，Ｔ
ｅ，Ｓｅ，Ｐ型熱電素子の場合はＳｂ，Ｔｅ，Ｂｉ）を
調合し、加熱溶融させて混合した後、粉末化し、圧縮、
焼結して成形する。このようにして、固溶体合金の粉末
焼結体が得られる。Bi-Te-Se based alloys and Bi-Sb-Te based alloys are usually formed as powder sintered bodies of solid solution alloys. That is, various metals prepared with a predetermined composition ratio (in the case of an N-type thermoelectric element, Bi, T
e, Se, Sb, Te, Bi in the case of a P-type thermoelectric element, mixed by heating and melting, and then powdered, compressed,
Sinter and shape. In this way, a powder sintered body of the solid solution alloy is obtained.
【０００８】このような固溶体合金の粉末焼結体の性能
指数を、比較例と共に、表１に示す。The performance index of the powder sintered body of such solid solution alloy is shown in Table 1 together with the comparative example.
【０００９】[0009]
【表１】 [Table 1]
【００１０】ここで、ｎ−Ｂｉ2 Ｔｅ3 とは、Ｎ型熱電
素子として使用される合金を示し、ｐ−Ｂｉ2 Ｔｅ3 と
は、Ｐ型熱電素子として使用される合金を示す。Here, n-Bi 2 Te 3 means an alloy used as an N-type thermoelectric element, and p-Bi 2 Te 3 means an alloy used as a P-type thermoelectric element.
【００１１】上記表より明らかなように、Ｂｉ−Ｔｅ−
Ｓｅ系合金は、他の合金と比較して性能指数Ｚこそ大き
いものの、ゼーベック係数α（絶対値）はＢｉ2 Ｓｅ3
よりも小さく、また電気伝導率σはｎ−Ｂｉ2 Ｔｅ3 よ
りも小さい。このためＢｉ−Ｔｅ−Ｓｅ系合金にしたこ
とによる相乗的な効果は得られず、性能指数Ｚにおいて
も顕著な向上は望めない。又同様に、Ｂｉ−Ｓｂ−Ｔｅ
系合金は、他の合金と比較して性能指数Ｚこそ大きいも
のの、ゼーベック係数αはｐ−Ｂｉ2 Ｓｅ3 よりも小さ
く、電気伝導率σはＳｂ2 Ｔｅ3 よりも小さい。このた
めＳｂ−Ｔｅ−Ｂｉ系合金にしたことによる相乗的な効
果は得られず、性能指数Ｚにおいても顕著な向上は望め
ない。As is clear from the above table, Bi-Te-
The Se-based alloy has a larger figure of merit Z than other alloys, but the Seebeck coefficient α (absolute value) is Bi 2 Se 3
And the electrical conductivity σ is smaller than n-Bi 2 Te 3 . Therefore, the synergistic effect obtained by using the Bi-Te-Se based alloy cannot be obtained, and the performance index Z cannot be expected to be significantly improved. Similarly, Bi-Sb-Te
Although the system alloy has a larger figure of merit Z than other alloys, the Seebeck coefficient α is smaller than p-Bi 2 Se 3 and the electrical conductivity σ is smaller than Sb 2 Te 3 . For this reason, the Sb-Te-Bi-based alloy does not have a synergistic effect, and the performance index Z cannot be expected to be significantly improved.
【００１２】本発明は、上記実情に鑑みてなされたもの
であり、熱電素子の性能指数を更に向上させることを技
術的課題とするものである。The present invention has been made in view of the above circumstances, and an object thereof is to further improve the figure of merit of a thermoelectric element.
【００１３】[0013]
【課題を解決するための手段】上記技術的課題を解決す
るために、本発明の請求項１において講じた技術的手段
は、２種以上の合金を組み合わせて形成する粉末焼結体
であり、相対的に電気伝導度の大きい合金の粒界に、相
対的にゼーベック係数の大きい合金が配置された、熱電
素子としたことである。In order to solve the above technical problems, the technical means taken in claim 1 of the present invention is a powder sintered body formed by combining two or more kinds of alloys, This is a thermoelectric element in which an alloy having a relatively large Seebeck coefficient is arranged at a grain boundary of an alloy having a relatively large electrical conductivity.
【００１４】上記構成とすることにより、１つの熱電素
子の内部において、電気伝導度の大きい部分と小さい部
分が存在することになる。電流は、電気伝導度が大きい
部分を選択的に通過するため、電気伝導度の大きい合金
の粒内を選択的に通過する。それ故、熱電素子全体とし
てみたときの電気伝導度は、電気伝導度の大きい粒子の
ものが支配的となり、電気伝導度を向上させることがで
きる。又、相対的に電気伝導度が小さい合金は、電気伝
導度が大きい合金の粒界に存在しているのみであるた
め、電流が電気伝導度の小さい合金を通過する部分はご
くわずかである。このため更に熱電素子の電気伝導度を
大きくすることができる。更に、相対的にゼーベック係
数が大きい合金は、ゼーベック係数の小さい合金の粒界
に配置されている。このため熱電素子の両端に配置され
る電極に接している合金は、相対的にゼーベック係数の
大きい合金である。ゼーベック係数は、両電極に接して
いる物質によって決定されるものであるため、本発明に
おける熱電素子のゼーベック係数は、相対的にゼーベッ
ク係数が大きい合金のものが支配的となる。このため、
ゼーベック係数も大きくすることができる。With the above structure, there are a portion having high electric conductivity and a portion having small electric conductivity inside one thermoelectric element. The electric current selectively passes through a portion having a high electrical conductivity, and therefore selectively passes through the grain of the alloy having a high electrical conductivity. Therefore, the electrical conductivity of the thermoelectric element as a whole is dominated by particles having a large electrical conductivity, and the electrical conductivity can be improved. Further, since an alloy having a relatively low electric conductivity exists only at grain boundaries of an alloy having a high electric conductivity, only a small portion of the current passes through the alloy having a low electric conductivity. Therefore, the electric conductivity of the thermoelectric element can be further increased. Further, an alloy having a relatively large Seebeck coefficient is arranged at a grain boundary of an alloy having a small Seebeck coefficient. Therefore, the alloy in contact with the electrodes arranged at both ends of the thermoelectric element has a relatively large Seebeck coefficient. Since the Seebeck coefficient is determined by the substance in contact with both electrodes, the Seebeck coefficient of the thermoelectric element of the present invention is dominated by the alloy having a relatively large Seebeck coefficient. For this reason,
The Seebeck coefficient can also be increased.
【００１５】上記技術的課題を解決するために、本発明
の請求項２において講じた技術的手段は、前記相対的に
電気伝導度の大きい合金はＢｉ2 Ｔｅ3 であり、前記相
対的にゼーベック係数の大きい合金はＢｉ2 Ｓｅ3 であ
ることを特徴とする、請求項１に記載の熱電素子とした
ことである。In order to solve the above technical problem, the technical means taken in claim 2 of the present invention is as follows. The alloy having a relatively high electric conductivity is Bi 2 Te 3 , and the relatively Seebeck. The thermoelectric element according to claim 1, wherein the alloy having a large coefficient is Bi 2 Se 3 .
【００１６】上記構成とすることにより、Ｎ型熱電素子
全体としてみたときの電気伝導度はＢｉ2 Ｔｅ3 の有す
る電気伝導度に近くなり、ゼーベック係数はＢｉ2 Ｓｅ
3 の有するゼーベック係数に近くなる。このため電気伝
導度、ゼーベック係数ともに従来のＢｅ−Ｔｅ−Ｓｅ系
合金の熱電素子よりも大きくなり、性能指数も従来のも
のと比較して飛躍的に向上する。With the above structure, the electric conductivity of the entire N-type thermoelectric element is close to that of Bi 2 Te 3 , and the Seebeck coefficient is Bi 2 Se.
It is close to the Seebeck coefficient of 3 . For this reason, both the electric conductivity and the Seebeck coefficient are larger than those of the conventional Be-Te-Se alloy thermoelectric element, and the figure of merit is significantly improved as compared with the conventional one.
【００１７】上記技術的課題を解決するために、本発明
の請求項３において講じた技術的手段は、前記相対的に
電気伝導度の大きい合金はＳｂ2 Ｔｅ3 であり、前記相
対的にゼーベック係数の大きい合金はＢｉ2 Ｔｅ3 であ
ることを特徴とする、請求項１に記載の熱電素子とした
ことである。In order to solve the above technical problem, the technical means taken in claim 3 of the present invention is that the alloy having a relatively high electric conductivity is Sb 2 Te 3 , and the relatively Seebeck. The thermoelectric element according to claim 1, wherein the alloy having a large coefficient is Bi 2 Te 3 .
【００１８】上記構成とすることにより、Ｐ型熱電素子
全体としてみたときの電気伝導度はＳｂ2 Ｔｅ3 の有す
る電気伝導度に近くなり、ゼーベック係数はＢｉ2 Ｔｅ
3 の有するゼーベック係数に近くなる。このため電気伝
導度、ゼーベック係数ともに従来のＳｂ−Ｔｅ−Ｂｉ系
合金の熱電素子よりも大きくなり、性能指数も従来のも
のと比較して飛躍的に向上する。With the above structure, the electric conductivity of the P-type thermoelectric element as a whole is close to that of Sb 2 Te 3 , and the Seebeck coefficient is Bi 2 Te.
It is close to the Seebeck coefficient of 3 . For this reason, both the electric conductivity and the Seebeck coefficient become larger than those of the conventional Sb-Te-Bi alloy thermoelectric element, and the figure of merit is dramatically improved as compared with the conventional one.
【００１９】[0019]
【発明の実施の形態】以下、本発明の実施の形態を、図
面に基づいて説明する。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to the drawings.
【００２０】図１は、本発明のＮ型熱電素子の組織の断
面を示す図である。図において、Ｎ型熱電素子１は、比
較的大きな粒子で形成されるｎ−Ｂｉ2 Ｔｅ3 合金粒子
２と、ｎ−Ｂｉ2 Ｔｅ3 合金粒子２の粒界に配置された
比較的小さな粒子で形成されるＢｉ2 Ｓｅ3 合金粒子３
からなる。このＮ型熱電素子１の製造方法については種
々の方法があるが、本実施形態においては、以下の方法
により製造した。即ち、公知の方法により、比較的大き
い粒径をもつｎ−Ｂｉ2 Ｔｅ3 合金粒子及び、比較的小
さな粒径をもつＢｉ2 Ｓｅ3 合金粒子を製造する。その
後、これらを混合し、圧縮、焼結する。混合、圧縮の過
程において、比較的小さい粒径をもつＢｉ2 Ｓｅ3 合金
粒子は、比較的大きい粒径をもつｎ−Ｂｉ2 Ｔｅ3 合金
粒子間に生じる隙間に入り込む。この状態で焼結を行う
ことにより、図１に示す構造のＮ型熱電素子１が製造で
きる。FIG. 1 is a view showing a cross section of the structure of the N-type thermoelectric element of the present invention. In the figure, the N-type thermoelectric element 1 is composed of n-Bi 2 Te 3 alloy particles 2 formed of relatively large particles and relatively small particles arranged at the grain boundaries of the n-Bi 2 Te 3 alloy particles 2. Bi 2 Se 3 alloy particles 3 formed
Consists of There are various methods for manufacturing the N-type thermoelectric element 1, but in the present embodiment, the following method is used. That is, n-Bi 2 Te 3 alloy particles having a relatively large particle diameter and Bi 2 Se 3 alloy particles having a relatively small particle diameter are manufactured by a known method. After that, these are mixed, compressed and sintered. During the mixing and compression processes, the Bi 2 Se 3 alloy particles having a relatively small particle size enter a gap generated between the n-Bi 2 Te 3 alloy particles having a relatively large particle size. By performing sintering in this state, the N-type thermoelectric element 1 having the structure shown in FIG. 1 can be manufactured.
【００２１】図１に示すＮ型熱電素子１において、電流
を図示左方向から右方向に流すと、電流は、より電気伝
導度の良い部分を選択して流れる。即ち、比較的大きな
合金粒子であるｎ−Ｂｉ2 Ｔｅ3 合金粒子２の粒内を選
択的に流れる。このため、本実施形態におけるＮ型熱電
素子の電気伝導度はｎ−Ｂｉ2 Ｔｅ3 合金の電気伝導度
に近い値となり、従来のＢｉ−Ｔｅ−Ｓｅ系合金の電気
伝導度よりも大きくなる。In the N-type thermoelectric element 1 shown in FIG. 1, when a current is made to flow from the left side to the right side in the figure, the current flows by selecting a portion having a higher electric conductivity. That is, the n-Bi 2 Te 3 alloy particles 2, which are relatively large alloy particles, selectively flow in the particles. Therefore, the electrical conductivity of the N-type thermoelectric element in the present embodiment has a value close to the electrical conductivity of the n-Bi 2 Te 3 alloy, which is higher than the electrical conductivity of the conventional Bi-Te-Se alloy.
【００２２】又、ｎ−Ｂｉ2 Ｔｅ3 合金粒子２の表面
は、Ｂｉ2 Ｓｅ3 合金粒子３に覆われている。このた
め、電極に接触する部分はＢｉ2 Ｓｅ3 合金粒子３であ
る。このため、電極との接触面の材質で決定されるゼー
ベック係数はＢｉ2 Ｓｅ3 のゼーベック係数に近い値と
なり、従来のＢｉ−Ｔｅ−Ｓｅ系合金のゼーベック係数
よりも大きくなる。電気伝導度とゼーベック係数が向上
したことにより、性能指数が飛躍的に向上する。The surface of the n-Bi 2 Te 3 alloy particles 2 is covered with the Bi 2 Se 3 alloy particles 3. Therefore, the portion contacting the electrode is the Bi 2 Se 3 alloy particles 3. Therefore, the Seebeck coefficient determined by the material of the contact surface with the electrode is a value close to the Seebeck coefficient of Bi 2 Se 3 , which is larger than the Seebeck coefficient of the conventional Bi-Te-Se alloy. The figure of merit is dramatically improved by improving the electrical conductivity and Seebeck coefficient.
【００２３】図２は、本発明のＰ型熱電素子の断面図で
ある。図において、Ｐ型熱電素子４は、比較的大きな粒
子で形成されるＳｂ2 Ｔｅ3 合金粒子５と、Ｓｂ2 Ｔｅ
3 合金粒子５の粒界に形成されるｐ−Ｂｉ2 Ｔｅ3 合金
６からなる。このＰ型熱電素子４の製造方法については
種々の方法があるが、本実施形態においては、以下の方
法により製造した。即ち、公知の方法により、比較的大
きい粒径をもつＳｂ2Ｔｅ3 合金粒子及び、比較的小さ
な粒径をもつｐ−Ｂｉ2 Ｔｅ3 合金粒子を製造する。そ
の後、Ｓｂ2 Ｔｅ3 合金粒子を圧縮してＳｂ2 Ｔｅ3 の
バルクとし、このＳｂ2 Ｔｅ3 のバルクを、加熱して液
状としたｐ−Ｂｉ2 Ｔｅ3 液中に浸漬させる。すると、
Ｂｉ2 Ｔｅ3 がＳｂ2 Ｔｅ3 のバルク中に拡散する。所
定時間浸漬後、バルクを引上げ、冷却する。このように
して、図２に示すＰ型熱電素子４が製造できる。FIG. 2 is a sectional view of the P-type thermoelectric element of the present invention. In Figure, P-type thermoelectric element 4, and Sb 2 Te 3 alloy particles 5 formed by a relatively large particle, Sb 2 Te
It consists of p-Bi 2 Te 3 alloy 6 formed at the grain boundaries of 3 alloy particles 5. Although there are various methods for manufacturing the P-type thermoelectric element 4, in the present embodiment, the P-type thermoelectric element 4 is manufactured by the following method. That is, Sb 2 Te 3 alloy particles having a relatively large particle diameter and p-Bi 2 Te 3 alloy particles having a relatively small particle diameter are manufactured by a known method. After that, the Sb 2 Te 3 alloy particles are compressed into a bulk of Sb 2 Te 3 , and this bulk of Sb 2 Te 3 is immersed in a liquid p-Bi 2 Te 3 liquid which is heated. Then
Bi 2 Te 3 diffuses into the bulk of Sb 2 Te 3 . After soaking for a predetermined time, the bulk is pulled up and cooled. In this way, the P-type thermoelectric element 4 shown in FIG. 2 can be manufactured.
【００２４】図２に示すＰ型熱電素子４において、電流
を図示左方向から右方向に流すと、電流は、より電気伝
導度の大きい部分を選択して流れる。即ち、比較的大き
な合金粒子であるＳｂ2 Ｔｅ3 合金粒子５の粒内を選択
的に流れる。このため、本実施形態におけるＰ型熱電素
子の電気伝導度はＳｂ2 Ｔｅ3 合金の電気伝導度に近い
値となり、従来のＢｉ−Ｓｂ−Ｔｅ系合金の電気伝導度
よりも大きくなる。In the P-type thermoelectric element 4 shown in FIG. 2, when a current is made to flow from the left side to the right side in the figure, the current flows by selecting a portion having a higher electric conductivity. That is, the Sb 2 Te 3 alloy particles 5, which are relatively large alloy particles, selectively flow within the particles. Therefore, the electric conductivity of the P-type thermoelectric element in this embodiment is a value close to the electric conductivity of the Sb 2 Te 3 alloy, which is higher than the electric conductivity of the conventional Bi—Sb—Te alloy.
【００２５】又、Ｓｂ2 Ｔｅ3 合金粒子５の表面は、ｐ
−Ｂｉ2 Ｔｅ3 合金に覆われている。このため、電極に
接触する部分はＢｉ2 Ｔｅ3 合金である。このため、電
極との接触面の材質で決定されるゼーベック係数はＢｉ
2 Ｔｅ3 のゼーベック係数に近い値となり、従来のＢｉ
−Ｓｂ−Ｔｅ系合金のゼーベック係数よりも大きくな
る。電気伝導度とゼーベック係数が向上したことによ
り、性能指数が飛躍的に向上する。The surface of the Sb 2 Te 3 alloy particles 5 has p
Covered with Bi 2 Te 3 alloy. Therefore, the portion that contacts the electrode is Bi 2 Te 3 alloy. Therefore, the Seebeck coefficient determined by the material of the contact surface with the electrode is Bi
The value is close to the Seebeck coefficient of 2 Te 3 and the Bi
It becomes larger than the Seebeck coefficient of the -Sb-Te alloy. The figure of merit is dramatically improved by improving the electrical conductivity and Seebeck coefficient.
【００２６】以上、本発明を示す実施形態を説明した
が、本発明は上記実施形態に限定されるものではない。
例えば、電気伝導度の大きい物質の表面にゼーベック係
数の大きい物質をコーティングしたものを焼結して熱電
素子を形成することも可能である。又、粉末状又は冷間
プレスした電気伝導率の大きい材料をゼーベック係数の
大きい材料の蒸気中に置くことで、拡散によりこのよう
な熱電素子を形成することも可能である。このように、
本発明の趣旨を逸脱しない限りにおいては如何なる場合
も適用可能である。Although the embodiments showing the present invention have been described above, the present invention is not limited to the above embodiments.
For example, it is also possible to form a thermoelectric element by sintering a material having a large electric conductivity coated with a material having a large Seebeck coefficient. It is also possible to form such a thermoelectric element by diffusion by placing a powdery or cold-pressed material having a large electric conductivity in vapor of a material having a large Seebeck coefficient. in this way,
Any case is applicable without departing from the spirit of the present invention.
【００２７】又、本実施形態においては、Ｎ型熱電素子
としての合金材料を、Ｂｉ2 Ｔｅ3とＢｉ2 Ｓｅ3 、Ｐ
型熱電素子としての合金材料をＳｂ2 Ｔｅ3 とＢｉ2 Ｔ
ｅ3として示したが、これに限定されることはなく、例
えばＮ型熱電素子としての合金材料を，ＰｂＴｅとＧｅ
Ｔｅ、Ｐ型熱電素子としての合金材料をＰｂＴｅとＰｂ
Ｓｅ、として、本実施形態と同様の組織構造とすること
により、同様の効果が得られる。In this embodiment, the alloy material for the N-type thermoelectric element is Bi 2 Te 3 and Bi 2 Se 3 , P.
Type alloy materials for thermoelectric elements are Sb 2 Te 3 and Bi 2 T
Although shown as e 3, it is not limited thereto, for example, an alloy material as a N-type thermoelectric element, PbTe and Ge
The alloy materials for Te and P-type thermoelectric elements are PbTe and Pb.
The same effect can be obtained by using Se as a tissue structure similar to that of the present embodiment.
【００２８】[0028]
【発明の効果】請求項１の発明は、以下の如く効果を有
する。The invention of claim 1 has the following effects.
【００２９】相対的に電気伝導度の大きい合金の粒界
に、相対的にゼーベック係数の大きい合金を配置した熱
電素子とした。これにより、電気伝導度、ゼーベック係
数共に向上し、性能指数を飛躍的に向上させることがで
きる。A thermoelectric element was prepared by arranging an alloy having a relatively large Seebeck coefficient at a grain boundary of an alloy having a relatively large electrical conductivity. Thereby, both the electric conductivity and the Seebeck coefficient can be improved, and the figure of merit can be dramatically improved.
【００３０】請求項２の発明は、以下の如く効果を有す
る。The invention of claim 2 has the following effects.
【００３１】相対的に電気伝導度の大きいＢｉ2 Ｔｅ3
合金粒子の粒界に、相対的にゼーベック係数の大きいＢ
ｉ2 Ｓｅ3 合金粒子を配置した熱電素子とした。これに
より、電気伝導度はＢｉ2 Ｔｅ3 合金に近くなり、ゼー
ベック係数はＢｉ2 Ｓｅ3 に近くなる。この両者の長所
を兼ね備えたＮ型熱電素子とするため、性能指数が飛躍
的に向上する。Bi 2 Te 3 having a relatively high electric conductivity
B having a relatively large Seebeck coefficient at the grain boundary of the alloy particles
The thermoelectric element was arranged with i 2 Se 3 alloy particles. Thereby, the electric conductivity is close to that of Bi 2 Te 3 alloy, and the Seebeck coefficient is close to that of Bi 2 Se 3 . Since the N-type thermoelectric element has both advantages, the figure of merit is dramatically improved.
【００３２】請求項３の発明は、以下の如く効果を有す
る。The invention of claim 3 has the following effects.
【００３３】相対的に電気伝導度の大きいＳｂ2 Ｔｅ3
合金粒子の粒界に、相対的にゼーベック係数の大きいＢ
ｉ2 Ｔｅ3 合金粒子を配置した熱電素子とした。これに
より、電気伝導度はＳｂ2 Ｔｅ3 合金に近くなり、ゼー
ベック係数はＢｉ2 Ｔｅ3 に近くなる。この両者の長所
を兼ね備えたＰ型熱電素子とするため、性能指数が飛躍
的に向上する。Sb 2 Te 3 having a relatively high electric conductivity
B having a relatively large Seebeck coefficient at the grain boundary of the alloy particles
The thermoelectric element was arranged with i 2 Te 3 alloy particles. As a result, the electric conductivity is close to that of the Sb 2 Te 3 alloy, and the Seebeck coefficient is close to that of Bi 2 Te 3 . Since the P-type thermoelectric element has both advantages, the figure of merit is dramatically improved.
【００３４】[0034]
１ Ｎ型熱電素子 ２ ｎ−Ｂｉ2 Ｔｅ3 合金粒子 ３ Ｂｉ2 Ｓｅ3 合金粒子 ４ Ｐ型熱電素子 ５ Ｓｂ2 Ｔｅ3 合金粒子 ６ ｐ−Ｂｉ2 Ｔｅ3 合金1 N-type thermoelectric element 2 n-Bi 2 Te 3 alloy particle 3 Bi 2 Se 3 alloy particle 4 P-type thermoelectric element 5 Sb 2 Te 3 alloy particle 6 p-Bi 2 Te 3 alloy
【図１】本実施形態における、Ｎ型熱電素子の内部の組
織構造を示す図である。FIG. 1 is a diagram showing an internal structure of an N-type thermoelectric element in the present embodiment.
【図２】本実施形態における、Ｐ型熱電素子の断面図で
ある。FIG. 2 is a cross-sectional view of a P-type thermoelectric element according to this embodiment.
Claims (3)
粉末焼結体であり、相対的に電気伝導度の大きい合金の
粒界に、相対的にゼーベック係数の大きい合金が配置さ
れた、熱電素子。1. A thermoelectric powder sintered body formed by combining two or more kinds of alloys, wherein an alloy having a relatively large Seebeck coefficient is arranged at a grain boundary of an alloy having a relatively large electrical conductivity. element.
Ｂｉ2 Ｔｅ3 であり、前記相対的にゼーベック係数の大
きい合金はＢｉ2 Ｓｅ3 であることを特徴とする、請求
項１に記載の熱電素子。2. The alloy having a relatively high electric conductivity is Bi 2 Te 3 , and the alloy having a relatively high Seebeck coefficient is Bi 2 Se 3. Thermoelectric element.
Ｓｂ2 Ｔｅ3 であり、前記相対的にゼーベック係数の大
きい合金はＢｉ2 Ｔｅ3 であることを特徴とする、請求
項１に記載の熱電素子。3. The alloy having a relatively large electric conductivity is Sb 2 Te 3 , and the alloy having a relatively large Seebeck coefficient is Bi 2 Te 3. Thermoelectric element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7332409A JPH09172202A (en) | 1995-12-20 | 1995-12-20 | Thermoelectric element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7332409A JPH09172202A (en) | 1995-12-20 | 1995-12-20 | Thermoelectric element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09172202A true JPH09172202A (en) | 1997-06-30 |
Family
ID=18254651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7332409A Pending JPH09172202A (en) | 1995-12-20 | 1995-12-20 | Thermoelectric element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09172202A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002033527A (en) * | 2000-07-13 | 2002-01-31 | Asahi Kasei Corp | Thermoelectric material and manufacturing method thereof |
| WO2007034632A1 (en) * | 2005-09-22 | 2007-03-29 | Ube Industries, Ltd. | Thermo-electric converting material and process for producing the same |
| JP2008539600A (en) * | 2005-04-28 | 2008-11-13 | クール シールド，インコーポレーテッド | Formable Peltier heat transfer element and method for manufacturing the same |
| ITBO20110043A1 (en) * | 2011-02-02 | 2012-08-03 | Eonsudenergia Srl | CATALYST FOR WASTE THERMOLYSIS |
-
1995
- 1995-12-20 JP JP7332409A patent/JPH09172202A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002033527A (en) * | 2000-07-13 | 2002-01-31 | Asahi Kasei Corp | Thermoelectric material and manufacturing method thereof |
| JP2008539600A (en) * | 2005-04-28 | 2008-11-13 | クール シールド，インコーポレーテッド | Formable Peltier heat transfer element and method for manufacturing the same |
| WO2007034632A1 (en) * | 2005-09-22 | 2007-03-29 | Ube Industries, Ltd. | Thermo-electric converting material and process for producing the same |
| JP2007088239A (en) * | 2005-09-22 | 2007-04-05 | Ube Ind Ltd | Thermoelectric conversion material and its manufacturing method |
| ITBO20110043A1 (en) * | 2011-02-02 | 2012-08-03 | Eonsudenergia Srl | CATALYST FOR WASTE THERMOLYSIS |
| EP2484440A1 (en) * | 2011-02-02 | 2012-08-08 | Eonsudenergia S.r.l. | A catalyst for waste thermolysis |
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