JP2002033527A - Thermoelectric material and manufacturing method thereof - Google Patents
Thermoelectric material and manufacturing method thereofInfo
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- JP2002033527A JP2002033527A JP2000213419A JP2000213419A JP2002033527A JP 2002033527 A JP2002033527 A JP 2002033527A JP 2000213419 A JP2000213419 A JP 2000213419A JP 2000213419 A JP2000213419 A JP 2000213419A JP 2002033527 A JP2002033527 A JP 2002033527A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ペルチエ効果やゼ
ーベック効果を発現し得る熱電材料およびその製造法に
関する。The present invention relates to a thermoelectric material capable of exhibiting a Peltier effect and a Seebeck effect, and a method for producing the same.
【０００２】[0002]
【従来の技術】例えば、金属または異種の半導体を接合
して電気回路を形成し、直流電流を流すと一方の接合部
で発熱、他方の接合部で吸熱現象が生じる。この現象は
ペルチエ効果と称されている。ペルチエ効果を利用して
対象物を電子的に冷却することは熱電冷却と称され、そ
の目的で用いられる素子は熱電冷却素子またはペルチエ
素子と称されている。2. Description of the Related Art For example, when an electric circuit is formed by joining metals or different kinds of semiconductors and a direct current is applied, heat is generated at one junction and heat is absorbed at the other junction. This phenomenon is called the Peltier effect. Electronically cooling an object using the Peltier effect is called thermoelectric cooling, and the element used for that purpose is called a thermoelectric cooling element or a Peltier element.
【０００３】また、２つの接合部間に温度差を生じさせ
ると、温度差に比例した起電力が発生する。この現象は
ゼーベック効果と称されている。ゼーベック効果で生じ
た起電力を利用して行う発電は熱電発電と称され、その
目的に使用される素子は熱電発電素子と称されている。
以上のような異種の金属または半導体を接合した基本構
造を持つ素子は熱電素子と総称され、熱電素子に使用さ
れる熱電性能の高い金属あるいは半導体は熱電材料と称
されている。When a temperature difference is generated between two junctions, an electromotive force is generated in proportion to the temperature difference. This phenomenon is called the Seebeck effect. Power generation using electromotive force generated by the Seebeck effect is called thermoelectric power generation, and an element used for that purpose is called a thermoelectric power generation element.
An element having a basic structure in which different kinds of metals or semiconductors are joined as described above is generally called a thermoelectric element, and a metal or semiconductor having high thermoelectric performance used for the thermoelectric element is called a thermoelectric material.
【０００４】熱電冷却は、固体素子による冷却であるた
め、有害な冷媒ガスを用いる必要が無く、騒音発生も無
く、局部冷却も可能であるという特徴を有する。さら
に、熱電冷却素子は、電流方向を切り換えればペルチエ
効果による加熱が行えるため、精密な温度調節ができ
る。このような特徴を生かした熱電冷却素子の用途とし
ては、電子部品の冷却や精密な温度調節が挙げられる。
また、熱電冷却素子を使用することによって、フロンな
どの有害ガスを用いない冷蔵庫や冷凍冷蔵庫も実現でき
る。[0004] Since thermoelectric cooling is cooling by a solid-state element, there is no need to use harmful refrigerant gas, no noise is generated, and local cooling is possible. Furthermore, since the thermoelectric cooling element can be heated by the Peltier effect by switching the current direction, precise temperature control can be performed. Applications of the thermoelectric cooling element utilizing such features include cooling of electronic components and precise temperature control.
Further, by using a thermoelectric cooling element, a refrigerator or a refrigerator free of harmful gases such as chlorofluorocarbon can be realized.
【０００５】熱電発電は、発電所、自動車などの熱機関
の廃熱利用による発電、豊富な太陽エネルギーを利用し
た発電など、エネルギーの有効利用を可能にする。熱電
素子の性能は、通常、ゼーベック係数（α）、電気伝導
率（σ）、出力因子（ＰＦ）、性能指数（Ｚ）、無次元
性能指数（ＺＴ）、熱伝導率（κ）、電気抵抗率（ρ）
で表される。これらの熱電素子の性能は、各種熱電性能
と称されている。ここで、ゼーベック係数（α）、電気
伝導率（σ）、出力因子（ＰＦ）、性能指数（Ｚ）、無
次元性能指数（ＺＴ）については、その値が大きい程、
熱電素子の性能が高い。熱伝導率（κ）および電気抵抗
率（ρ）については、その値が小さい程、熱電素子の性
能が高い。[0005] Thermoelectric power generation enables effective use of energy, such as power generation using waste heat from heat engines such as power plants and automobiles, and power generation using abundant solar energy. Generally, the performance of a thermoelectric element is expressed by Seebeck coefficient (α), electrical conductivity (σ), power factor (PF), figure of merit (Z), dimensionless figure of merit (ZT), thermal conductivity (κ), and electrical resistance. Rate (ρ)
It is represented by The performance of these thermoelectric elements is called various thermoelectric performances. Here, as for the Seebeck coefficient (α), electric conductivity (σ), power factor (PF), figure of merit (Z), and dimensionless figure of merit (ZT), the larger the value is,
High performance of thermoelectric element. Regarding the thermal conductivity (κ) and the electrical resistivity (ρ), the smaller the value, the higher the performance of the thermoelectric element.
【０００６】特に、無次元性能指数（ＺＴ）は「ＺＴ＝
α2 σＴ／κ（ここに、Ｔは絶対温度である）」で表さ
れ、熱電冷却における成績係数、熱電発電における変換
効率等の熱電変換エネルギー効率を決定する重要な要素
である。そのため、性能指数（Ｚ＝α2 σ／κ）の値が
大きい熱電材料を用いて熱電素子を作製することによ
り、冷却および発電の効率を高めることが可能となる。
即ち、熱電材料としては、ゼーベック係数（α）と電気
伝導率（σ）が高く、且つ熱伝導率（κ）の低い材料が
好ましい。In particular, the dimensionless figure of merit (ZT) is expressed as “ZT =
α 2 σT / κ (where T is an absolute temperature) ”, and is an important factor that determines thermoelectric conversion energy efficiency such as coefficient of performance in thermoelectric cooling and conversion efficiency in thermoelectric power generation. Therefore, by manufacturing a thermoelectric element using a thermoelectric material having a large figure of merit (Z = α 2 σ / κ), the efficiency of cooling and power generation can be increased.
That is, as the thermoelectric material, a material having a high Seebeck coefficient (α) and a high electrical conductivity (σ) and a low thermal conductivity (κ) is preferable.
【０００７】熱電発電素子は高温側と低温側の温度差を
利用して発電し、熱電冷却素子は電流により低温側から
高温側へ熱量を移動することによって機能を果たすた
め、これらの素子は温度の異なった部分に挿入されるこ
とになる。従って、低温側と高温側で熱膨張差が生じ、
素子内に熱せん断応力が発生する。そのため、熱電材料
には、熱電性能に加えて、機械的強度および加工特性等
も要求される。A thermoelectric power generation element generates electricity by utilizing a temperature difference between a high temperature side and a low temperature side, and a thermoelectric cooling element performs a function by moving heat from a low temperature side to a high temperature side by an electric current. Will be inserted into different parts. Therefore, a difference in thermal expansion occurs between the low temperature side and the high temperature side,
Thermal shear stress occurs in the element. Therefore, in addition to thermoelectric performance, thermoelectric materials are required to have mechanical strength, processing characteristics, and the like.
【０００８】従来の熱電材料としては、Ｂｉ−Ｔｅ系合
金（Ｂｉ2 Ｔｅ3 組成を基とし、Ｓｂ2 Ｔｅ3 および／
またはＢｉ2 Ｓｅ3 との擬二元系あるいは擬三元系の固
溶体）が挙げられる。この合金は、一方向性凝固法など
で作製することによって、Ｂｉ2 Ｔｅ3 の結晶構造がｃ
方向に長い菱面体であってこのｃ方向にＢｉとＴｅが層
状に並んだ構造となっているため、熱電性能が高い反
面、ｃ面で劈開され易い。したがって、Ｂｉ−Ｔｅ系合
金からなる熱電材料は、熱せん断応力に弱く、機械的強
度が低いという問題点がある。[0008] Conventional thermoelectric materials include Bi-Te alloys (based on Bi 2 Te 3 composition, Sb 2 Te 3 and / or
Or a pseudo-binary or pseudo-ternary solid solution with Bi 2 Se 3 ). This alloy is made by a unidirectional solidification method or the like so that the crystal structure of Bi 2 Te 3 is c
Since it is a rhombohedron long in the direction and has a structure in which Bi and Te are arranged in a layer in the c direction, the thermoelectric performance is high, but it is easily cleaved on the c plane. Therefore, a thermoelectric material made of a Bi-Te alloy has a problem that it is weak to thermal shear stress and has low mechanical strength.
【０００９】この問題点を解決するために、Ｂｉ−Ｔｅ
系合金を粉末焼結法で成形することによって、熱電性能
を犠牲にしてせん断応力に強い熱電素子を得ることも提
案されている。しかし、この方法では、４６０〜５００
℃程度の温度領域で加圧成形する必要があるため、製造
コストが高くなる。最近では、室温〜６００℃程度の中
温領域での熱電特性が高いことから、ＣｏＳｂ3 を代表
とするスクッテルダイト系材料とハーフホイスラー合金
材料の実用化が期待されている。ただし、これらの材料
は、熱伝導度が高いため性能指数が低く、現時点では実
用化段階に至っていない。また、スクッテルダイト系材
料については、機械的強度も良好ではない。In order to solve this problem, Bi-Te
It has also been proposed to obtain a thermoelectric element resistant to shear stress at the expense of thermoelectric performance by molding a system alloy by a powder sintering method. However, in this method, 460-500
Since it is necessary to perform pressure molding in a temperature range of about ° C, the production cost is increased. Recently, the practical use of a skutterudite-based material represented by CoSb 3 and a half-Heusler alloy material has been expected because of its high thermoelectric properties in a medium temperature range of room temperature to 600 ° C. However, these materials have a low thermal index due to their high thermal conductivity, and have not yet reached the stage of practical use. Further, the mechanical strength of the skutterudite-based material is not good.
【００１０】スクッテルダイト系材料に十分な機械的強
度と熱電特性を付与するためには、例えば、特開平１０
−１０２１６０号公報に記載されているように１ＧＰａ
以上の圧力で加圧成形するか、特開平１１−４０８６２
号公報に記載されているように１μｍ以下に粉砕した後
に５００〜６００℃で加圧熱処理する必要がある。In order to impart sufficient mechanical strength and thermoelectric properties to a skutterudite-based material, for example, Japanese Patent Application Laid-Open No.
1 GPa as described in
Pressure molding at the above pressure or JP-A-11-40862
As described in Japanese Patent Application Laid-Open No. H10-260, it is necessary to perform pressure heat treatment at 500 to 600 ° C. after pulverization to 1 μm or less.
【００１１】[0011]
【発明が解決しようとする課題】本発明は、このような
従来技術の問題点に着目してなされたものであり、熱電
性能が高いだけでなく、機械的強度および加工特性にも
優れた熱電材料を提供することを課題とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and is not only high in thermoelectric performance but also excellent in mechanical strength and processing characteristics. It is an object to provide materials.
【００１２】[0012]
【課題を解決するための手段】上記課題を解決するため
に、本発明は、Ｓｂ、Ａｓ、Ｔｅ、およびＳｅから選択
された１種以上の半金属元素を含む組成の結晶からなる
Ａ相と、Ａ相を構成する半金属元素と融点が１００℃以
上１０００℃以下である低融点元素とを含む組成のｂ相
とを有し、Ａ相の存在率が５０．０体積％以上９９．９
体積％以下であり、ｂ相の存在率が０．１体積％以上５
０．０体積％以下である物質の成形体からなる熱電材料
を提供する。Means for Solving the Problems To solve the above problems, the present invention provides an A phase comprising a crystal having a composition containing one or more metalloid elements selected from Sb, As, Te, and Se. And a b phase having a composition including a metalloid element constituting the A phase and a low melting point element having a melting point of 100 ° C. or more and 1000 ° C. or less, and the abundance of the A phase is 50.0 vol% or more and 99.9.
% By volume or less, and the b phase abundance is 0.1% by volume or more and 5% by volume or more.
Provided is a thermoelectric material comprising a molded article of a substance having a content of 0.0% by volume or less.
【００１３】Ａ相としては、例えば、以下に示す材料
〜からなる結晶相が挙げられる。Ａ相は、これらの材
料のうちの一つの結晶相で構成されていてもよいし、２
種以上の結晶相で形成されていてもよい。これらの材料
は熱電特性の高い材料である。 Ｂｉ−Ｔｅ系合金に、３Ｂ族、４Ｂ族、５Ｂ族、６Ｂ
族、または７Ｂ族に属する各種元素がドープされた多元
系材料。Ｂｉ−Ｔｅ系合金の具体例としては、ＢｉとＴ
ｅとの二元系固溶体、（Ｂｉ2 Ｔｅ3 ）と（Ｓｂ2 Ｔｅ
3 ）との擬二元系固溶体、（Ｂｉ2 Ｔｅ3 ）と（Ｂｉ2
Ｓｅ3 ）との擬二元系固溶体、（Ｂｉ2Ｔｅ3 ）と（Ｓ
ｂ2 Ｔｅ3 ）と（Ｓｂ2 Ｓｅ3 ）との擬三元系固溶体等
が挙げられる。Examples of the A phase include a crystal phase composed of the following materials. The A phase may be composed of one crystal phase of these materials,
It may be formed of more than one kind of crystal phase. These materials have high thermoelectric properties. Bi-Te alloys include 3B, 4B, 5B, 6B
A multi-element material doped with various elements belonging to Group 7B or Group 7B. Specific examples of Bi-Te alloys include Bi and T
e, a binary solid solution of (Bi 2 Te 3 ) and (Sb 2 Te
3) a pseudo-binary solid solution of the (Bi 2 Te 3) (Bi 2
Pseudo-binary solid solution with (Se 3 ), (Bi 2 Te 3 ) and (S
pseudo-ternary solid solution of (b 2 Te 3 ) and (Sb 2 Se 3 ).
【００１４】Ｐｂ−Ｔｅ、Ｐｂ−Ｓｎ−Ｔｅ、Ｐｂ−
Ｇｅ−ＴｅなどのＰｂＴｅ系材料、（ＡｇＳｂＴ
ｅ2 ）1-x （ＧｅＴｅ）x などのＴＡＧＳ系材料、Ｇ
ｄＴｅ1. 49、ＬａＴｅ1.46などの希土類−カルコゲン系
材料、Ａｇ−Ｓｂ−ＴｅなどのＳｂ−Ｔｅ系材料、
Ｂｉ0.85Ｓｂ0.1 5 などのＢｉ−Ｓｂ系材料、Ｚｎ4
Ｓｂ3 などのＺｎ−Ｓｂ系材料、ＣｏＳｂ3 を代表と
するスクッテルダイト系材料、ＸＮｉＳｎ1-y Ｓｂy
（Ｘ＝Ｚｒ，Ｈｆ，Ｔｉ、０＜ｙ＜１）、ＰｔＭｎＳ
ｂ、ＹＮｉＳｂ等のハーフホイスラー合金系材料。Pb-Te, Pb-Sn-Te, Pb-
PbTe-based materials such as Ge-Te, (AgSbT
e 2 ) TAGS-based materials such as 1-x (GeTe) x , G
rare earth such as dTe 1. 49, LaTe 1.46 - chalcogen based material, Sb-Te-based material such as Ag-Sb-Te,
Bi-Sb based material such as Bi 0.85 Sb 0.15 , Zn 4
Zn-Sb-based material, such as Sb 3, skutterudite material typified by CoSb 3, XNiSn 1-y Sb y
(X = Zr, Hf, Ti, 0 <y <1), PtMnS
b, half-Heusler alloy-based materials such as YNiSb.
【００１５】スクッテルダイト系材料は、８族元素Ｍと
５Ｂ族元素（プニコゲン）ＰｎによりＭＰｎ3 で表され
る組成の立方晶系の固溶体である。ＭとしてはＣｏ、Ｒ
ｈ、Ｉｒなどが挙げられ、ＰｎとしてはＳｂ、Ａｓ、Ｐ
が挙げられる。また、ＭをＦｅ、Ｎｉ、Ｐｔ、Ｐｄ、Ｒ
ｕ、Ｏｓなどで置換したもの、ＰｎをＴｅ、Ｓｎ、Ｂ
ｉ、Ｇｅ、Ｓｅ、Ｓｉなどで置換したものも、スクッテ
ルダイト系材料に含まれる。The skutterudite-based material is a cubic solid solution having a composition represented by MPn 3 by a Group 8 element M and a Group 5B element (punicogen) Pn. M is Co, R
h, Ir and the like, and Pn is Sb, As, P
Is mentioned. Further, M is Fe, Ni, Pt, Pd, R
u, Os, etc., Pn is Te, Sn, B
Those substituted with i, Ge, Se, Si, etc. are also included in the skutterudite-based material.
【００１６】また、スクッテルダイト系材料の結晶格子
には、Ｍ4 Ｐｎ12当たり１個の割合で空格子が存在する
が、この空格子の全部或いは一部に、Ｌａ、Ｃｅ、Ｙｂ
などの希土類元素、Ｂａ、Ｃａなどのアルカリ土類元
素、またはＴｌやＳｎなどが導入されたフィルドスクッ
テルダイトＬｘＭ4 Ｐｎ12材料（０＜ｘ≦１）も、スク
ッテルダイト系材料に含まれる。In the crystal lattice of the skutterudite-based material, one vacancy exists per M 4 Pn 12 , and La, Ce, Yb
Skutterudite-based materials also include filled skutterudite LxM 4 Pn 12 materials (0 <x ≦ 1) into which rare earth elements such as Ba, Ca or the like, or Tl or Sn or the like are introduced. .
【００１７】ハーフホイスラー合金系材料は、α（Ｙを
含む希土類元素、Ｔｉ、Ｚｒ、Ｈｆ、アルカリ土類金
属、Ｐｔ等の８族元素）、β（Ｎｉ、Ｍｎ、Ａｇ、Ｃｕ
などの遷移金属）、γ（５Ｂ族元素、６Ｂ族元素、Ａ
ｌ、Ｓｎ）の３つの元素によりαβγで表される組成の
立方晶岩塩型構造の金属間化合物である。ハーフホイス
ラー合金系材料の結晶構造の一例として、岩塩型立方晶
の単位格子である単純立方格子の頂点に、最近接元素が
他元素となるようにα原子とβ原子が配置され、半数の
単純立方格子の体心位置にγ原子が配置されている結晶
構造がある。Half Heusler alloy materials include α (a rare earth element including Y, a group 8 element such as Ti, Zr, Hf, alkaline earth metal, and Pt), and β (Ni, Mn, Ag, Cu).
Γ (group 5B element, group 6B element, A
l, Sn) are intermetallic compounds having a cubic rock salt type structure having a composition represented by αβγ by three elements. As an example of the crystal structure of a half-Heusler alloy material, α and β atoms are arranged at the top of a simple cubic lattice, which is a unit cell of a rock salt type cubic, so that the nearest element is another element, and half of the simple crystals are There is a crystal structure in which γ atoms are arranged at the body center position of a cubic lattice.
【００１８】ｂ相の組成は、Ａ相を構成する半金属元素
と、融点が１００℃以上１０００℃以下である低融点元
素とを含む組成である。なお、ｂ相には、これらの元素
以外の元素が、ｂ相全体の５０原子％以下の割合で含ま
れていてもよい。ｂ相用の低融点元素（融点が１００℃
以上１０００℃以下である元素）としては、Ｂｉ、Ｚ
ｎ、Ａｌ、Ｉｎ、Ｃｄ、Ｐｂ、Ｔｌ、Ｓｎ等が挙げられ
る。但し、Ｓｂ、Ａｓ、Ｔｅ、Ｓｅはｂ相用の低融点元
素に含まれない。ｂ相に２種類以上の元素を含む場合に
は、全ての元素の融点が１００℃以上１０００℃以下で
あるか、これらの元素の合金または化合物の融点がこの
範囲にある必要がある。The composition of the b-phase is a composition containing a metalloid element constituting the A-phase and a low-melting element having a melting point of 100 ° C. or more and 1000 ° C. or less. The b phase may contain elements other than these elements at a ratio of 50 atomic% or less of the entire b phase. Low melting point element for phase b (melting point is 100 ° C
Bi or Z)
n, Al, In, Cd, Pb, Tl, Sn and the like. However, Sb, As, Te, and Se are not included in the low melting point element for the b phase. When two or more elements are contained in the b-phase, it is necessary that the melting points of all the elements are 100 ° C. or more and 1000 ° C. or less, or the melting points of alloys or compounds of these elements are within this range.
【００１９】ｂ相の例としては、以下に示す相が挙げら
れる。ｂ相はＡ相とは異なる相である。ｂ相はこれらの
相のうちの一つの相で構成されていてもよいし、２種以
上の相で形成されていてもよい。これらの相は、半導体
あるいは半金属的な性質を有する。Ｂｉ0.85Ｓｂ0.1 5
などの組成のＳｂ−Ｂｉ相、Ｂｉ2 Ｓｅ3 などの組成の
Ｓｅ−Ｂｉ相、Ｂｉ2 Ｔｅ3 、ＢｉＴｅＩなどの組成の
Ｔｅ−Ｂｉ相。ＺｎＳｂ、Ｚｎ4 Ｓｂ3 、Ｚｎ3 Ｓｂ2
などの組成のＳｂ−Ｚｎ相、Ｚｎ3 Ａｓ2 などの組成の
Ａｓ−Ｚｎ相、ＺｎＴｅなどの組成のＴｅ−Ｚｎ相、Ｚ
ｎＳｅなどの組成のＳｅ−Ｚｎ相。Examples of the b phase include the following phases. The b phase is a different phase from the A phase. The b phase may be composed of one of these phases, or may be composed of two or more phases. These phases have semiconducting or semimetallic properties. Bi 0.85 Sb 0.1 5
Sb-Bi-phase composition, such as, Se-Bi phase composition, such as Bi 2 Se 3, Bi 2 Te 3, BiTeI Te-Bi phase composition, such as. ZnSb, Zn 4 Sb 3, Zn 3 Sb 2
, An As-Zn phase such as Zn 3 As 2, a Te—Zn phase such as ZnTe, Z
Se-Zn phase having a composition such as nSe.
【００２０】ＡｌＳｂなどの組成のＳｂ−Ａｌ相、Ａｌ
Ａｓなどの組成のＡｓ−Ａｌ相、ＩｎＳｂなどの組成の
Ｓｂ−Ｉｎ相、ＩｎＡｓなどの組成のＡｓ−Ｉｎ相、Ｃ
ｕＩｎＴｅ2 などの組成のＴｅ−Ｉｎ相、ＴｌＩｎＳｅ
2 などの組成のＳｅ−Ｉｎ相。ＣｄＴｅなどの組成のＴ
ｅ−Ｃｄ相、ＰｂＴｅなどの組成のＴｅ−Ｐｂ相、Ｐｂ
Ｓｅなどの組成のＳｅ−Ｐｂ相、ＴｌＩｎＴｅ2 などの
組成のＴｅ−Ｔｌ相、ＴｌＩｎＳｅ2 などの組成のＳｅ
−Ｔｌ相。Sb-Al phase having a composition such as AlSb, Al
As-Al phase having a composition such as As, Sb-In phase having a composition such as InSb, As-In phase having a composition such as InAs, C
Te-In phase of composition such as uInTe 2 , TlInSe
Se-In phase having a composition such as 2 . T of composition such as CdTe
e-Cd phase, Te-Pb phase having composition such as PbTe, Pb
Se-Pb phase of the composition, such as Se, Te-Tl-phase composition, such as TlInTe 2, Se composition such TlInSe 2
-Tl phase.
【００２１】以上のように、本発明の熱電材料は、熱電
特性の高い材料からなるＡ相と、半導体あるいは半金属
的な性質の材料からなるｂ相とで構成されている。ま
た、ｂ相は低融点で延展性のある元素を含む。したがっ
て、この熱電材料は、Ａ相の有する高い出力因子を保持
しながら、ｂ相によって熱伝導度が低減されるか電気伝
導度が増大されるため、全体の性能指数が高くなる。こ
れに加えて、ｂ相に含まれる低融点元素による延展性に
起因して、機械的強度および加工特性にも優れた熱電材
料となる。このような特性を得るために、Ａ相の存在率
を５０．０体積％以上９９．９体積％以下とし、ｂ相の
存在率を０．１体積％以上５０．０体積％以下とする必
要がある。As described above, the thermoelectric material of the present invention is composed of the A phase made of a material having high thermoelectric properties and the b phase made of a material having semiconductor or semimetallic properties. The b-phase contains a low melting point and spreadable element. Therefore, the thermoelectric material has a high figure of merit because the thermal conductivity is reduced or the electrical conductivity is increased by the b phase while maintaining the high output factor of the A phase. In addition, a thermoelectric material having excellent mechanical strength and processing characteristics due to the spreadability due to the low melting point element contained in the b-phase. In order to obtain such characteristics, the abundance of the A phase needs to be 50.0% by volume or more and 99.9% by volume or less, and the abundance of the b phase needs to be 0.1% by volume or more and 50.0% by volume or less. There is.
【００２２】本発明の熱電材料において、Ａ相を構成す
る半金属元素としてＳｂを含むことが好ましい。これに
より、各種熱電性能のうち特にゼーベック係数が大きい
熱電材料が得られる。本発明の熱電材料において、ｂ相
を構成する低融点元素としてＢｉを含むことが好まし
い。これにより、成形加工性が特に良好になり、電気伝
導度の増大効果が大きくなる。また、ｂ相がＳｂ−Ｂｉ
相であると、性能指数がより高い熱電材料が得られる。In the thermoelectric material of the present invention, it is preferable that Sb is contained as a metalloid element constituting the A phase. Thereby, a thermoelectric material having a particularly large Seebeck coefficient among various thermoelectric performances can be obtained. In the thermoelectric material of the present invention, Bi is preferably contained as a low-melting element constituting the b-phase. Thereby, the moldability is particularly good, and the effect of increasing the electric conductivity is increased. Also, the b phase is Sb-Bi
A phase results in a thermoelectric material with a higher figure of merit.
【００２３】本発明の熱電材料でＡ相がスクッテルダイ
ト系材料からなる場合には、ｂ相を共存させることによ
って得られる効果が高い。すなわち、スクッテルダイト
系材料からなるＡ相にｂ相を共存させることによって、
スクッテルダイト系材料からなる熱電性能の高い熱電材
料を、低温で成形可能にすることができる。本発明の熱
電材料において、ｂ相が、熱電性能の高いＳｂ−Ｂｉ相
である場合には、ｂ相がＡ相の表面を囲むような構造で
あることが好ましい。このような構造であると、Ａ相と
ｂ相の界面におけるフォノンの散乱効果が高いため、熱
伝導度の低減効果が高くなる。ただし、このような構造
ではなく、Ａ相の粒界に微細なｂ相の結晶が分散してい
るような構造であっても、ｂ相の微結晶がフォノンの散
乱源となるため、熱伝導度の低減効果はある程度得られ
る。When the A phase is made of a skutterudite-based material in the thermoelectric material of the present invention, the effect obtained by coexisting the b phase is high. That is, by allowing the b-phase to coexist with the A-phase made of skutterudite-based material,
A thermoelectric material having a high thermoelectric performance made of a skutterudite-based material can be formed at a low temperature. In the thermoelectric material of the present invention, when the b phase is an Sb-Bi phase having high thermoelectric performance, it is preferable that the b phase surrounds the surface of the A phase. With such a structure, the effect of scattering phonons at the interface between the A phase and the b phase is high, so that the effect of reducing the thermal conductivity is high. However, even in a structure in which fine b-phase crystals are dispersed in the grain boundaries of the A-phase instead of such a structure, the fine crystals of the b-phase serve as phonon scattering sources, so that heat conduction is suppressed. The effect of reducing the degree is obtained to some extent.
【００２４】本発明の熱電材料において、隣合うＡ相間
に存在するｂ相をなす結晶の大きさ（厚さあるいは粒
径）は例えば１ｎｍ〜５０μｍとする。ｂ相の結晶がこ
の程度の大きさであればｂ相の機能が十分に発揮され
る。ｂ相をなす材料の電気伝導度がＡ相をなす材料より
も低い場合は、ｂ相の結晶の大きさは小さい（薄い）方
が好ましい。電気伝導度の低下量を少なくし、熱伝導度
の低下量を大きくするために、ｂ相の結晶の大きさは例
えば１〜１０００ｎｍであることが好ましい。In the thermoelectric material of the present invention, the size (thickness or particle size) of the crystal forming the b phase existing between the adjacent A phases is, for example, 1 nm to 50 μm. If the b-phase crystal has such a size, the function of the b-phase is sufficiently exhibited. When the electrical conductivity of the material forming the b-phase is lower than that of the material forming the A-phase, the crystal size of the b-phase is preferably smaller (thinner). In order to reduce the amount of decrease in electric conductivity and increase the amount of decrease in thermal conductivity, the size of the b-phase crystal is preferably, for example, 1 to 1000 nm.
【００２５】ｂ相には、金属相であるｂ’相が含まれて
いてもよい。その場合、個々のｂ’相は十分に小さく、
ｂ相内に拡散された状態となっている必要がある。非常
に少量の小さいｂ’相が、ｂ相に分散状態で存在してい
る場合であれば、ゼーベック係数と熱伝導度の性能を大
きく損なうことなく、電気伝導度を大きくすることもで
きる。The b phase may include a b 'phase which is a metal phase. In that case, the individual b 'phases are small enough,
It must be in a state of being diffused in the b-phase. If a very small amount of the small b 'phase is present in a dispersed state in the b phase, the electrical conductivity can be increased without significantly impairing the Seebeck coefficient and the thermal conductivity.
【００２６】また、このｂ’相がｎｍオーダーの大きさ
の結晶であれば、熱伝導度の低減作用を得ることができ
る場合もある。成形加工性の観点からは、ｂ’相の存在
が望ましい場合もある。このｂ’相のｂ相中での存在率
は１０体積％以下とする。本発明はまた、本発明の熱電
材料の製造方法として、Ｓｂ、Ａｓ、Ｔｅ、およびＳｅ
から選択された１種以上の半金属元素を含む組成の結晶
からなる材料（第１の材料）と、融点が１００℃以上１
０００℃以下（好ましくは１００℃以上６５０℃以下、
より好ましくは１００℃以上４５０℃以下）である低融
点元素を含む組成の材料（第２の材料）とを用い、粉末
焼結法で所定形状の成形体を得ることを特徴とする熱電
材料の製造方法を提供する。If the b ′ phase is a crystal having a size on the order of nm, the effect of reducing the thermal conductivity may be obtained in some cases. From the viewpoint of moldability, the presence of the b 'phase may be desirable in some cases. The proportion of the b ′ phase in the b phase is 10% by volume or less. The present invention also provides a method for producing the thermoelectric material of the present invention, which includes Sb, As, Te, and Se.
(A first material) composed of a crystal having a composition containing at least one metalloid element selected from the group consisting of:
000 ° C or less (preferably 100 ° C or more and 650 ° C or less,
A material having a composition including a low melting point element (more preferably 100 ° C. or more and 450 ° C. or less) (a second material), and obtaining a molded body having a predetermined shape by a powder sintering method. A manufacturing method is provided.
【００２７】この方法で熱電材料を製造すると、焼結の
際に、第１の材料の半金属元素と第２の材料の低融点元
素とが反応し、第１の材料（Ａ相をなす結晶）の粒界
に、半金属元素と低融点元素とを含む組成であって、半
導体あるいは半金属的な性質の相（ｂ相）が生じる。第
２の材料の低融点元素（ｂ相をなす低融点元素）として
融点が１００℃未満の元素を使用すると、半金属元素と
低融点元素との反応が十分に進まないうちに、低融点元
素が溶けてＡ相の結晶粒界に存在しない状態となる。こ
れにより、特に粉末焼結法で成形加工する場合は、加圧
成形法では型から成形体が抜けなくなったり、常圧成形
法では成形体の形が崩れたりする。When a thermoelectric material is manufactured by this method, the metalloid element of the first material and the low-melting element of the second material react during sintering, and the first material (the crystal forming the A phase) A phase (b phase) having a composition containing a metalloid element and a low melting point element and having semiconductor-like or metalloid properties is generated at the grain boundary of (a). When an element having a melting point of less than 100 ° C. is used as the low-melting element (low-melting element forming the b phase) of the second material, the low-melting element is not sufficiently reacted with the metalloid element before the low-melting element progresses. Dissolves into a state where it does not exist at the crystal grain boundary of phase A. As a result, in particular, when molding is performed by the powder sintering method, the molded article cannot be removed from the mold by the pressure molding method, or the molded article loses its shape by the normal pressure molding method.
【００２８】低融点元素の代わりに融点が１０００℃を
越える元素を用いると、Ａ相をなす結晶粒の周りにこの
元素が拡散しないうちに焼結が終了して、Ａ相をなす結
晶の粒界にｂ相が形成されない恐れがある。また、Ａ相
をなす結晶粒が成長して大きくなるため、ｂ相の機能が
十分に発揮されない。第２の材料として使用する低融点
元素の融点は、１００℃以上４５０℃以下であることが
特に好ましい。４５０℃以下の低温で熱電材料の成形加
工が可能となるため、成形加工性が特に良好になって、
低コストで製造できるようになる。また、４５０℃以下
ではＡ相をなす結晶の粒成長が起こらないため、ｂ相の
機能が十分に発揮されて、得られる熱電材料の熱伝導度
が特に低くなる。If an element having a melting point exceeding 1000 ° C. is used in place of the low melting point element, sintering is completed before the element diffuses around the crystal grains forming the A phase, and the crystal grains forming the A phase are formed. The b phase may not be formed in the field. Further, since the crystal grains forming the A phase grow and become large, the function of the b phase is not sufficiently exhibited. The melting point of the low-melting element used as the second material is particularly preferably from 100 ° C to 450 ° C. Because it is possible to form the thermoelectric material at a low temperature of 450 ° C. or less, the formability is particularly good.
It can be manufactured at low cost. At 450 ° C. or lower, since the crystal growth of the A phase does not occur, the function of the b phase is sufficiently exhibited, and the thermal conductivity of the obtained thermoelectric material is particularly low.
【００２９】特に、融点が２７１℃であるＢｉを使用す
ることが好ましい。ｂ相の低融点元素としてＢｉを使用
することによって、得られる熱電材料の成形加工性が特
に良好となるとともに、熱電性能も良好となる。Ａ相の
融点は、ｂ相をなす低融点元素の融点以上であることが
好ましい。この場合、熱処理条件によっては、粒界にｂ
相をなす低融点元素の拡散状態が良好となって、得られ
る熱電材料の各種熱電性能が向上する。好ましい組合せ
は、Ａ相の融点が６５０℃を超えていて、ｂ相をなす低
融点元素の融点が６５０℃以下である組合せである。さ
らに好ましい組合せは、Ａ相の融点が４５０℃を超えて
いて、ｂ相をなす低融点元素の融点が４５０℃以下であ
る組合せである。In particular, it is preferable to use Bi having a melting point of 271 ° C. By using Bi as the low-melting element of the b-phase, the formability of the obtained thermoelectric material is particularly improved, and the thermoelectric performance is also improved. The melting point of the A phase is preferably equal to or higher than the melting point of the low melting point element forming the b phase. In this case, depending on the heat treatment conditions, b
The diffusion state of the low-melting element forming a phase is improved, and the thermoelectric performance of the obtained thermoelectric material is improved. A preferred combination is a combination in which the melting point of the A phase exceeds 650 ° C. and the melting point of the low-melting element forming the b phase is 650 ° C. or less. A more preferable combination is a combination in which the melting point of the phase A exceeds 450 ° C. and the melting point of the low-melting element forming the phase b is 450 ° C. or less.
【００３０】本発明の熱電材料を本発明の方法で製造し
た場合、ｂ相をなす半金属元素は、(a) Ａ相の主相を構
成していた半金属元素か、(b) Ａ相の副相Ａ’相を構成
していた半金属元素に由来するものである。なお、 (a)
の場合には、前記半金属元素以外のＡ相に含まれていた
元素が、ｂ相に混在することが多い。この混在する元素
のｂ相での存在比が原子比で５０％を超えない限り、本
発明の方法で製造された熱電材料の各種熱電性能は良好
なものとなる。When the thermoelectric material of the present invention is manufactured by the method of the present invention, the b-phase semimetal element is (a) the semimetal element constituting the main phase of the A phase, or (b) the A metal phase. Is derived from the metalloid element constituting the sub-phase A ′. (A)
In the case of the above, the elements contained in the A phase other than the metalloid element are often mixed in the b phase. As long as the abundance ratio of the mixed elements in the b phase does not exceed 50% in atomic ratio, various thermoelectric performances of the thermoelectric material manufactured by the method of the present invention become good.
【００３１】(a)の場合であって、Ｓｂ、Ａｓ、Ｔｅ、
およびＳｅから選択された１種以上の半金属元素を含む
組成の材料（Ａ相用の材料）として、ＡｇやＳｎ等の金
属元素を含む材料を使用して製造された熱電材料は、ｂ
相に前記金属元素が混在され易いが、例えばＳｂ−Ｚｎ
系材料からなるｂ相に、ＡｇやＳｎが０．１〜２０体積
％程度含まれていても問題はない。これらの金属元素が
適切な組成で含まれていることによって、得られる熱電
材料の各種熱電性能が向上することもある。In the case of (a), Sb, As, Te,
And a thermoelectric material manufactured using a material containing a metal element such as Ag or Sn as a material having a composition containing one or more metalloid elements selected from Se and Se (material for the A phase) is b
It is easy for the metal element to be mixed in the phase, for example, Sb-Zn
There is no problem even if about 0.1 to 20% by volume of Ag or Sn is contained in the b phase made of the system material. By including these metal elements in an appropriate composition, various thermoelectric performances of the obtained thermoelectric material may be improved.
【００３２】また、本発明の熱電材料を本発明の方法で
製造する際に、Ａ相とｂ相との界面によるフォノンの散
乱効果を高める目的で、通常、公知の方法で粉砕された
粉体をＡ相材料として使用することが好ましい。この場
合、Ａ相材料は粒子の表面が乱れた状態となっているた
め、粒子の内部より表面の結晶性が悪く、表面の熱電性
能が劣った状態にある。このＡ相の粒子の表面にｂ相が
形成される際に、Ａ相の粒子の表面がｂ相形成用に添加
された低融点元素でクリーニングされる。これと同時
に、Ａ相とｂ相との界面におけるフォノンの散乱効果が
得られるため、この方法で得られた熱電材料は各種熱電
性能が高いものとなる。Further, when the thermoelectric material of the present invention is produced by the method of the present invention, a powder crushed by a known method is usually used for the purpose of enhancing the phonon scattering effect at the interface between the A phase and the b phase. Is preferably used as the A-phase material. In this case, since the surface of the particle of the phase A material is in a disordered state, the crystallinity of the surface is lower than that of the inside of the particle, and the thermoelectric performance of the surface is inferior. When the b-phase is formed on the surface of the A-phase particles, the surfaces of the A-phase particles are cleaned with the low-melting element added for the b-phase formation. At the same time, a phonon scattering effect at the interface between the A-phase and the b-phase is obtained, so that the thermoelectric material obtained by this method has various thermoelectric properties.
【００３３】(b)の場合には、主相であるＡ相より副相
であるＡ’相の方が通常は熱電性能が劣るため、Ａ相に
Ａ’相が存在する熱電材料はＡ’相が存在しないＡ相か
らなる熱電材料よりも熱電性能が低い。特にＡ’相が金
属相である場合は、ゼーベック係数が低下し、熱伝導度
が増加する傾向がある。この熱電材料に低融点元素を添
加して、Ａ’相全体又はその粒界を半導体化することに
より、Ａ相の熱電性能の低下を抑えることができる。こ
れを副相のクリーニング効果と呼ぶ。In the case of (b), the thermoelectric material in which the A 'phase exists in the A phase is generally inferior in the thermoelectric performance of the A' phase which is the sub phase than the A phase which is the main phase. It has lower thermoelectric performance than the thermoelectric material composed of the A phase having no phase. In particular, when the A 'phase is a metal phase, the Seebeck coefficient tends to decrease and the thermal conductivity tends to increase. By adding a low-melting element to this thermoelectric material and converting the entire A ′ phase or its grain boundaries into a semiconductor, a decrease in the thermoelectric performance of the A phase can be suppressed. This is called a sub-phase cleaning effect.
【００３４】このクリーニングが十分に行われず、Ａ相
にＡ’相が存在する熱電材料であっても、Ａ’相の存在
率が全体の１０体積％以下であり、個々のＡ’相が分散
された状態となっていれば、熱電性能の低下を小さく抑
えることができる。また、Ａ相に添加する低融点元素の
種類によっては、Ａ相にＡ’相が存在する熱電材料の熱
電性能が、Ａ’相が存在しないＡ相からなる熱電材料よ
りも高くできることもある。Even if the cleaning is not sufficiently performed and the thermoelectric material has the A ′ phase in the A phase, the A ′ phase abundance is 10% by volume or less and the individual A ′ phases are dispersed. In this state, a decrease in thermoelectric performance can be suppressed. Further, depending on the type of the low-melting element added to the A phase, the thermoelectric performance of the thermoelectric material in which the A ′ phase exists in the A phase may be higher than that of the A phase in which the A ′ phase does not exist.
【００３５】以上のように、Ａ相とｂ相とからなる熱電
材料がＡ相のみからなる熱電材料よりも熱伝導度が低く
なるメカニズムとしては、主に、Ａ相の結晶粒子表面の
クリーニング効果と副相のクリーニング効果（半導体
化）が挙げられる。また、Ａ相の粒界に分散状態で存在
するｂ相の微結晶によるフォノンの散乱効果も挙げられ
る。As described above, the mechanism by which the thermoelectric material composed of the A phase and the b phase has lower thermal conductivity than the thermoelectric material composed of only the A phase mainly has a cleaning effect on the surface of the crystal grains of the A phase. And a cleaning effect (semiconductor conversion) of the subphase. Further, there is also a phonon scattering effect due to microcrystals of the b phase existing in a dispersed state at the grain boundaries of the A phase.
【００３６】例えば、Ｌａ−Ｆｅ−Ｃｏ−Ｓｂ系材料か
らなるＡ相と、Ｓｂ−Ｚｎ系材料からなるｂ相で構成さ
れた熱電材料として、ＳｂよりもＺｎの比率が多い組成
であって、大きさが０．３〜１００ｎｍであるＳｂ−Ｚ
ｎ結晶が、ｂ相内に存在しているものが確認されてい
る。この熱電材料の熱伝導度が特に小さい理由は、この
微細なＳｂ−Ｚｎ結晶の存在によるものと推測される。For example, as a thermoelectric material composed of an A phase composed of a La—Fe—Co—Sb-based material and a b phase composed of an Sb—Zn-based material, the composition is such that the ratio of Zn is larger than that of Sb. Sb-Z having a size of 0.3 to 100 nm
It has been confirmed that the n crystal exists in the b phase. The reason why the thermal conductivity of the thermoelectric material is particularly low is presumed to be due to the presence of the fine Sb-Zn crystals.
【００３７】本発明の熱電材料は、例えば、粉末焼結法
によって製造することができる。その場合には先ず、第
１の材料（Ａ相をなす結晶）と第２の材料（ｂ相を構成
する低融点元素を含む材料）とを粉体状で混合する。第
１の材料として粒径が０．１μｍ未満の粉体を使用する
と、Ａ相をなす結晶の表面が酸化されやすくなるため、
得られる熱電材料の電気伝導度が低下する。また、Ａ相
をなす結晶粒が凝集し易くなるため、熱電材料のＡ相の
粒界にｂ相が十分に形成され難くなる。第１の材料とし
て粒径が１００μｍより大きいものを使用すると、熱電
材料のＡ相の粒界でのｂ相によるフォノンの散乱効果が
十分に得られなくなるため、熱伝導度の低減効果が低く
なる。The thermoelectric material of the present invention can be manufactured by, for example, a powder sintering method. In that case, first, the first material (crystal constituting the A phase) and the second material (material containing the low melting point element constituting the b phase) are mixed in powder form. When a powder having a particle size of less than 0.1 μm is used as the first material, the surface of the crystal forming the A phase is easily oxidized.
The resulting thermoelectric material has reduced electrical conductivity. In addition, since the crystal grains forming the A phase are easily aggregated, it is difficult to sufficiently form the b phase at the grain boundary of the A phase of the thermoelectric material. If the first material has a particle size larger than 100 μm, the effect of phonon scattering by the b phase at the grain boundary of the A phase of the thermoelectric material cannot be sufficiently obtained, and the effect of reducing the thermal conductivity is reduced. .
【００３８】したがって、第１の材料として粒径が０．
１〜１００μｍであるものを使用することが好ましい。
第１の材料として粒径が０．５〜１０μｍであるものを
使用すると、得られる熱電材料の各種熱電性能が向上す
るため特に好ましい。第１の材料をこのような好ましい
粒径にするために、通常、第１の材料は粉砕工程によっ
て粉砕された後に、第２の材料と混合される。この粉砕
は、例えば、粉砕機として、ジョークラッシャー、スタ
ンプミル、ロータミル、ピンミル、コーヒーミル、ボー
ルミル、ジェットミル、アトライター等を用いて行われ
る。Therefore, the first material has a particle size of 0.1.
It is preferable to use one having a thickness of 1 to 100 μm.
It is particularly preferable to use a first material having a particle size of 0.5 to 10 μm because various thermoelectric performances of the obtained thermoelectric material are improved. In order to bring the first material to such a preferred particle size, the first material is usually mixed with the second material after being ground by a grinding step. This pulverization is performed using, for example, a jaw crusher, a stamp mill, a rotor mill, a pin mill, a coffee mill, a ball mill, a jet mill, an attritor, or the like as a pulverizer.
【００３９】なお、第１の材料は、ガスアトマイズ法、
固相反応法、Ｒ／Ｄ法（還元拡散法）、メカニカルアロ
イング法などで製造することにより、粉体状で得ること
もできる。この方法で得られた粉体の粒径が前述の好ま
しい範囲にあれば、粉砕工程を行う必要はない。第２の
材料も粉体状のものを使用することが好ましい。第１の
材料と第２の材料との混合工程は、自動乳鉢、Ｖ型ミキ
サ、タンブラ、リボンミキサ、ロータリミキサなど、通
常用いられる混合機を使用して行うことができる。第１
の材料および／または第２の材料の粉砕とこの混合工程
とを同時に行ってもよい。The first material is a gas atomizing method,
It can also be obtained in powder form by producing by a solid phase reaction method, an R / D method (reduction diffusion method), a mechanical alloying method, or the like. If the particle size of the powder obtained by this method is in the above-mentioned preferable range, it is not necessary to perform the pulverizing step. It is preferable to use the second material in powder form. The step of mixing the first material and the second material can be performed using a commonly used mixer such as an automatic mortar, a V-shaped mixer, a tumbler, a ribbon mixer, and a rotary mixer. First
The pulverization of the material and / or the second material and the mixing step may be performed simultaneously.
【００４０】次に、第１の材料と第２の材料との粉体状
の混合物を型に入れて成形し、１００℃以上の温度で焼
結する。熱処理雰囲気は非酸化性雰囲気であることが好
ましく、アルゴンやヘリウムなどの希ガス、窒素ガス中
などの不活性ガス中で、或いは水素ガスを含む還元ガス
中で熱処理を行うことが好ましい。また、焼結時の圧力
は、常圧、加圧下、あるいは真空中のいずれであっても
構わない。Next, a powdery mixture of the first material and the second material is put into a mold, molded, and sintered at a temperature of 100 ° C. or more. The heat treatment atmosphere is preferably a non-oxidizing atmosphere, and the heat treatment is preferably performed in a rare gas such as argon or helium, an inert gas such as a nitrogen gas, or a reducing gas containing a hydrogen gas. The pressure during sintering may be any of normal pressure, under pressure, or in vacuum.
【００４１】この熱処理によって、第１の材料の半金属
元素と第２の材料の低融点元素とが反応して、第１の材
料（Ａ相をなす結晶）の粒界に、半金属元素と低融点元
素とを含む組成の結晶からなる、半導体あるいは半金属
的な性質の相（ｂ相）が生じる。この熱処理は成形と同
時に行うこともでき、ホットプレス法、ＨＩＰ法、ＳＰ
Ｓ法（放電プラズマ焼結法）などのような加圧熱処理法
が採用できる。これらの方法のうち、ＳＰＳ法を採用す
ると熱処理時間を短くすることができる。By this heat treatment, the metalloid element of the first material and the low-melting element of the second material react with each other, and the metalloid element and the metalloid element are formed at the grain boundaries of the first material (the crystals forming the A phase). A semiconductor- or semi-metallic phase (b phase) composed of crystals having a composition containing a low-melting element is generated. This heat treatment can be performed simultaneously with the molding, and can be performed by hot pressing, HIP, SP
A pressure heat treatment method such as the S method (discharge plasma sintering method) can be employed. When the SPS method is employed among these methods, the heat treatment time can be shortened.
【００４２】また、この方法では、第２の材料として、
融点が１００℃以上１０００℃以下の低融点元素を使用
することによって、低融点元素が蒸散などで大量に失わ
れることがないため、成形体に変形が生じたり、加圧熱
処理の際に型から抜けなくなったりすることが避けられ
る。混合物の成形を冷間プレスで行った後に熱処理を行
う場合には、熱処理後の成形体が十分な機械的強度を有
するように、第２の材料の添加量、熱処理条件（温度お
よび時間）、熱処理後の冷却速度などを工夫する必要が
ある。例えば、Ａ相の粒界が微細な結晶相またはアモル
ファス相になるように、材料組成、熱処理条件などを制
御する。このような制御を行うことにより、ｂ相による
フォノンの散乱効果が特に高くなるため、得られる熱電
材料の機械的強度が高くなるだけでなく、得られる熱電
材料の熱伝導度を低くすることができる。In this method, as the second material,
By using a low-melting element having a melting point of 100 ° C. or more and 1000 ° C. or less, a large amount of the low-melting element is not lost due to evaporation, etc. It is possible to avoid getting stuck. When the heat treatment is performed after the mixture is formed by a cold press, the amount of the second material added, the heat treatment conditions (temperature and time), and the heat treatment are adjusted so that the formed body after the heat treatment has sufficient mechanical strength. It is necessary to devise the cooling rate after the heat treatment. For example, the material composition, heat treatment conditions, and the like are controlled so that the grain boundary of the A phase becomes a fine crystalline phase or an amorphous phase. By performing such control, the phonon scattering effect by the b-phase is particularly increased, so that not only the mechanical strength of the obtained thermoelectric material is increased, but also the thermal conductivity of the obtained thermoelectric material is reduced. it can.
【００４３】[0043]
【発明の実施の形態】以下、本発明の実施形態について
説明する。本発明の実施形態に相当する熱電材料を以下
のようにして作製した。先ず、純度９９．９％のＬａ、
純度９９．５％のＦｅ、純度９９．９％のＣｏを、原子
比で１：３：１となるようにアーク溶解を行った後、純
度９９．９９％のＳｂを、原子比で（Ｌａ＋Ｃｏ＋Ｆ
ｅ）：Ｓｂ＝５：１４となるように添加して、さらにア
ーク溶解を行った。このようにして得られたインゴット
に対して、Ａｒ雰囲気中、６００℃で４０時間の条件
で、均質化焼鈍処理を行った。Embodiments of the present invention will be described below. A thermoelectric material corresponding to the embodiment of the present invention was produced as follows. First, La having a purity of 99.9%,
After arc melting of 99.5% pure Fe and 99.9% pure Co at an atomic ratio of 1: 3: 1, Sb of 99.99% pure was dissolved in an atomic ratio of (La + Co + F).
e): Sb was added so as to be 5:14, and arc melting was further performed. The ingot thus obtained was subjected to a homogenization annealing treatment in an Ar atmosphere at 600 ° C. for 40 hours.
【００４４】次に、このインゴットの組成をＩＣＰ発光
分析法で調べた。その結果、このインゴットの組成はＬ
ａ5.4 Ｆｅ16.1Ｃｏ5.4 Ｓｂ73.1であった。また、この
インゴットをＸ線回折装置にかけて、ＣｕＫα線による
Ｘ線回折スペクトルを得た。この結果から、このインゴ
ットは、ＬａＦｅ3 ＣｏＳｂ12を主相（Ａ相）とする結
晶であり、副相としてＳｂ相と微量の（Ｆｅ、Ｃｏ）Ｓ
ｂ2 相を含むことが分かった。Next, the composition of this ingot was examined by ICP emission spectrometry. As a result, the composition of this ingot is L
a 5.4 Fe 16.1 Co 5.4 Sb 73.1 . The ingot was applied to an X-ray diffractometer to obtain an X-ray diffraction spectrum by CuKα radiation. From this result, this ingot is a crystal having LaFe 3 CoSb 12 as a main phase (A phase), and an Sb phase and a small amount of (Fe, Co) S
It was found to contain b 2 phase.
【００４５】次に、このインゴットをコーヒーミルで粗
粉砕することにより、粒径を１０６μｍ以下にした。次
に、この粗粉体を、Ａｒ雰囲気中で回転ボールミルで微
粉砕することにより、平均粒径２μｍの微粉体（第１の
材料）を得た。次に、この微粉体に、平均粒径１〜２μ
ｍのＢｉ（純度９９％）粉体（第２の材料）を、８重量
％の割合で添加し、ヘキサンで湿潤させた状態で乳鉢に
より混合した。この混合粉体をグラファイト製の型に入
れ、４１５℃、４５ＭＰａ、５分間の条件でＳＰＳ法に
よる焼結を行うことにより成形体を得た。Next, the ingot was coarsely pulverized with a coffee mill to reduce the particle size to 106 μm or less. Next, the coarse powder was finely pulverized by a rotary ball mill in an Ar atmosphere to obtain a fine powder (first material) having an average particle diameter of 2 μm. Next, an average particle diameter of 1 to 2 μm was added to this fine powder.
m Bi (purity 99%) powder (second material) was added at a ratio of 8% by weight, and mixed with a mortar while wetted with hexane. This mixed powder was placed in a graphite mold, and sintered by the SPS method under the conditions of 415 ° C., 45 MPa, and 5 minutes to obtain a molded body.
【００４６】この成形体の組成をＩＣＰ発光分析法で調
べたところ、Ｌａ5.1 Ｆｅ15.4Ｃｏ 5.1 Ｓｂ70.1Ｂｉ
4.3 であった。また、この成形体をＸ線回折装置にかけ
て、ＣｕＫα線による回折Ｘ線スペクトルを得た。この
結果から、この成形体は、ＬａＦｅ3 ＣｏＳｂ12からな
るＡ相と、Ｓｂ−Ｂｉ相からなるｂ相とで構成されるこ
とが分かった。The composition of this compact was adjusted by ICP emission spectrometry.
Everywhere, La5.1Fe15.4Co 5.1Sb70.1Bi
4.3Met. In addition, this molded product is subjected to an X-ray diffractometer.
Thus, a diffraction X-ray spectrum by CuKα ray was obtained. this
From the results, it was found that this compact was LaFeThreeCoSb12From
A phase and a b phase composed of Sb-Bi phase
I understood.
【００４７】また、この成形体の断面の微構造を透過型
電子顕微鏡（ＴＥＭ）で観察し、ＥＤＸによる各相の同
定を行ったところ、ｂ相がＡ相を取り囲んでいるような
微構造であることが分かった。また、この成形体は、Ｌ
ａＦｅ3 ＣｏＳｂ12からなるＡ相と、Ｓｂ66Ｂｉ34から
なるｂ相とで構成され、Ａ相の存在率が８１体積％（原
子比で８７％）でありｂ相の存在率が１９体積％であっ
た。この成形体を実施例１とする。Further, the microstructure of the cross section of this molded body was observed with a transmission electron microscope (TEM), and each phase was identified by EDX. As a result, the microstructure was found to have a microstructure in which the b phase surrounded the A phase. I found it. Also, this molded product is L
and A phase consisting aFe 3 CoSb 12, is composed of a b-phase consisting of Sb 66 Bi 34, abundance of A phase 81 vol% (87% in atomic ratio), and the presence ratio of b phase 19 vol% Met. This compact is referred to as Example 1.
【００４８】実施例２として、ＣｅＣｏ4 Ｓｂ12（微量
のＢｉを含む）からなるＡ相（フィルドスクッテルダイ
ト構造）と、微量のＣｅ等を含みＳｂ：Ｂｉ＝２：８
（原子比）であるＳｂ−Ｂｉ相からなるｂ相とで構成さ
れ、Ａ相の存在率が８７体積％（原子比で９３％）であ
りｂ相の存在率が１３体積％である物質からなる成形体
を得た。成形体の組成はＣｅ5.4 Ｃｏ21.8Ｓｂ66.8Ｂｉ
6.0 であった。As Example 2, an A phase (filled skutterudite structure) composed of CeCo 4 Sb 12 (containing a small amount of Bi) and Sb: Bi = 2: 8 containing a small amount of Ce etc.
A b phase composed of Sb-Bi phase (atomic ratio), and a substance having an A phase abundance of 87% by volume (93% by atomic ratio) and a b phase abundance of 13% by volume A molded article was obtained. The composition of the compact was Ce 5.4 Co 21.8 Sb 66.8 Bi
6.0 .
【００４９】この実施例２の成形体は以下のようにして
作製した。先ず、純度９９．９％のＣｅ、純度９９．９
％のＣｏを原子比で１：４となるようにアーク溶解を行
った後、純度９９．９９％のＳｂ及びＢｉを原子比で
（Ｃｅ＋Ｃｏ）：Ｓｂ：Ｂｉ＝５：１３：１．３となる
ように添加して、さらにアーク溶解を行った。このよう
にして得られたインゴットに対して、Ａｒ雰囲気中、６
００℃で４０時間の条件で、均質化焼鈍処理を行った。The molded body of Example 2 was produced as follows. First, Ce with a purity of 99.9%, purity of 99.9%
% Of Co at an atomic ratio of 1: 4, and then Sb and Bi having a purity of 99.99% were converted to an atomic ratio of (Ce + Co): Sb: Bi = 5: 13: 1.3. And further arc melting was performed. The ingot thus obtained was placed in an Ar atmosphere at 6
The homogenizing annealing treatment was performed at 00 ° C. for 40 hours.
【００５０】次に、このインゴットの組成をＩＣＰ発光
分析法で調べた。その結果、このインゴットの組成はＣ
ｅ5.4 Ｃｏ21.8Ｓｂ66.8Ｂｉ6.0 であった。また、この
インゴットをＸ線回折装置にかけて、ＣｕＫα線による
Ｘ線回折スペクトルを得た。さらに、この成形体の断面
の微構造を透過型電子顕微鏡（ＴＥＭ）で観察し、ＥＤ
Ｘによる各相の同定を行った。この結果から、このイン
ゴットは、ＣｅＣｏ4Ｓｂ12（微量のＢｉを含む）を主
相（Ａ相）とする結晶であり、副相として、微量のＣｅ
等を含みＳｂ：Ｂｉ＝２：８（原子比）であるＳｂ−Ｂ
ｉ相を含むことが分かった。Next, the composition of this ingot was examined by ICP emission spectrometry. As a result, the composition of this ingot is C
e 5.4 Co 21.8 Sb 66.8 Bi 6.0 . The ingot was applied to an X-ray diffractometer to obtain an X-ray diffraction spectrum by CuKα radiation. Further, the microstructure of the cross section of the molded body was observed with a transmission electron microscope (TEM),
Each phase was identified by X. From these results, this ingot is a crystal having CeCo 4 Sb 12 (including a small amount of Bi) as a main phase (A phase), and a small amount of Ce as a subphase.
And Sb: Bi = 2: 8 (atomic ratio)
It was found to contain i-phase.
【００５１】次に、このインゴットをコーヒーミルで粗
粉砕することにより、粒径を１０６μｍ以下にした。次
に、この粗粉体を、Ａｒ雰囲気中で回転ボールミルで微
粉砕することにより、平均粒径２μｍの微粉体を得た。
次に、この微粉体をグラファイト製の型に入れ、４１５
℃、４５ＭＰａ、５分間の条件でＳＰＳ法による焼結を
行うことにより成形体を得た。Next, the ingot was coarsely pulverized with a coffee mill to reduce the particle size to 106 μm or less. Next, this coarse powder was finely pulverized by a rotary ball mill in an Ar atmosphere to obtain a fine powder having an average particle diameter of 2 μm.
Next, this fine powder is put into a graphite mold, and 415
A compact was obtained by sintering at 45 ° C. for 5 minutes at 5 ° C. by the SPS method.
【００５２】実施例３として、Ｌａ0.9 Ｆｅ3 ＣｏＳｂ
12からなるＡ相と、Ｓｂ55Ｂｉ45からなるｂ相とで構成
され、Ａ相の存在率が９２体積％（原子比で９５％）で
ありｂ相の存在率が８体積％である物質からなる成形体
を得た。成形体の組成はＬａ 5.1 Ｆｅ16.9Ｃｏ5.6 Ｓｂ
70.4Ｂｉ2.0 であった。この成形体は、組成がＬａ5. 2
Ｆｅ17.3Ｃｏ5.8 Ｓｂ71.7であるインゴットを用い、Ｂ
ｉの添加量を４重量％とした点以外は、実施例１と同じ
方法で作製した。As a third embodiment, La0.9FeThreeCoSb
12A phase consisting of55Bi45Consists of b phase consisting of
And the abundance of phase A is 92% by volume (95% by atomic ratio).
A molded body made of a substance having a b phase abundance of 8% by volume
I got The composition of the compact is La 5.1Fe16.9Co5.6Sb
70.4Bi2.0Met. This molded product has a composition of LaFive. Two
Fe17.3Co5.8Sb71.7Using an ingot of
Same as Example 1 except that the amount of i added was 4% by weight
Fabricated by method.
【００５３】比較例１として、ＬａＦｅ3 ＣｏＳｂ12か
らなるＡ相の粒界相のほとんどがＳｂ相である物質から
なる成形体を得た。この成形体は、Ｂｉの添加を行なわ
ず、焼結温度を４９０℃とした点以外は、実施例１と同
じ方法で作製した。この成形体の組成は、実施例１のイ
ンゴットと同じＬａ5.4 Ｆｅ16.1Ｃｏ5.4 Ｓｂ73.1であ
った。なお、焼結温度を実施例１と同じ４１５℃として
作製しようとしたが、この場合にはグラファイト型から
取り出した時に成形体が砕けてしまい、成形体の機械的
強度が不十分であった。As Comparative Example 1, a compact was obtained which was made of a material in which most of the grain boundary phase of A phase made of LaFe 3 CoSb 12 was an Sb phase. This molded body was produced in the same manner as in Example 1 except that Bi was not added and the sintering temperature was 490 ° C. The composition of this compact was La 5.4 Fe 16.1 Co 5.4 Sb 73.1 which was the same as that of the ingot of Example 1. The sintering temperature was set to 415 ° C., which is the same as in Example 1. However, in this case, the molded body was broken when taken out of the graphite mold, and the mechanical strength of the molded body was insufficient.
【００５４】比較例２として、Ｌａ0.9 Ｆｅ3 ＣｏＳｂ
12からなるＡ相の粒界相のほとんどがＳｂ相である物質
からなる成形体を得た。この成形体は、組成がＬａ5.2
Ｆｅ 17.3Ｃｏ5.8 Ｓｂ71.7であるインゴットを用いた点
以外は、比較例１と同じ方法で作製した。このようにし
て得られた実施例１〜３および比較例１，２の成形体に
ついて、室温でのゼーベック係数（α）、電気伝導度
（σ）、熱伝導率（κ）を測定した。これらの測定結果
を表１に示す。また、これらの値から計算される性能指
数（Ｚ）の値も表１に併せて示す。As Comparative Example 2, La0.9FeThreeCoSb
12Most of the grain boundary phase of A phase consisting of Sb phase
A molded article consisting of This molded product has a composition of La5.2
Fe 17.3Co5.8Sb71.7Using ingots that are
Except for the above, it was produced in the same manner as in Comparative Example 1. Like this
Molded articles of Examples 1 to 3 and Comparative Examples 1 and 2 obtained by
About the Seebeck coefficient (α) and electrical conductivity at room temperature
(Σ) and thermal conductivity (κ) were measured. These measurement results
Are shown in Table 1. Also, the performance index calculated from these values
The value of the number (Z) is also shown in Table 1.
【００５５】[0055]
【表１】 [Table 1]
【００５６】これらの結果から、実施例１〜３の成形体
は、比較例１，２の成形体と比較して電気伝導度が著し
く高く、ゼーベック係数および熱伝導度の点でも良好で
あって、高い性能指数を有することが分かる。実施例２
の成形体では、特に低い熱伝導率が得られた。また、実
施例１〜３の成形体は、回転速度１５００ｒｐｍのダイ
ヤモンドカッタにより１ｍｍ以下の大きさに切削して
も、成形体に割れが生じなかった。ただし、実施例２の
成形体で僅かなチッピングが生じる場合があった。これ
に対して比較例１，２の成形体は、プラスチックの裏打
ちをした場合でも、回転速度１００ｒｐｍのダイヤモン
ドカッタによる切削で、成形体に亀裂が生じることがあ
った。すなわち、実施例１〜３の成形体は比較例１，２
の成形体よりも、著しく高い機械強度および加工特性を
有することが分かった。From these results, the molded articles of Examples 1 to 3 have remarkably higher electric conductivity than the molded articles of Comparative Examples 1 and 2, and also have good Seebeck coefficient and thermal conductivity. It has a high figure of merit. Example 2
In the molded article of the above, a particularly low thermal conductivity was obtained. In addition, the compacts of Examples 1 to 3 did not crack even when cut into a size of 1 mm or less using a diamond cutter having a rotation speed of 1500 rpm. However, slight chipping sometimes occurred in the molded product of Example 2. On the other hand, in the molded products of Comparative Examples 1 and 2, even when the plastic was backed, cracks were sometimes generated in the molded products by cutting with a diamond cutter at a rotation speed of 100 rpm. That is, the molded articles of Examples 1 to 3 are Comparative Examples 1 and 2.
It was found to have significantly higher mechanical strength and processing characteristics than the molded article of No. 1.
【００５７】[0057]
【発明の効果】以上説明したように、本発明によれば、
熱電性能が高いだけでなく、機械的強度および加工特性
にも優れた熱電材料が得られる。As described above, according to the present invention,
A thermoelectric material having not only high thermoelectric performance but also excellent mechanical strength and processing characteristics can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山中 章三 静岡県富士市鮫島２番地の１ 旭化成工業 株式会社内 Ｆターム(参考） 4K018 AA40 EA22 KA32 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Shozo Yamanaka 2-1, Samejima, Fuji City, Shizuoka Prefecture
Claims (5)
された１種以上の半金属元素を含む組成の結晶からなる
Ａ相と、Ａ相を構成する半金属元素と融点が１００℃以
上１０００℃以下である低融点元素とを含む組成のｂ相
とを有し、Ａ相の存在率が５０．０体積％以上９９．９
体積％以下であり、ｂ相の存在率が０．１体積％以上５
０．０体積％以下である物質の成形体からなる熱電材
料。1. An A phase comprising a crystal having a composition containing at least one metalloid element selected from Sb, As, Te, and Se, and a metalloid element constituting the A phase having a melting point of 100 ° C. or more and 1000 ° C. or more. And a b phase having a composition containing a low melting point element having a melting point of not higher than 5 ° C.
% By volume or less, and the b phase abundance is 0.1% by volume or more and 5% by volume or more.
A thermoelectric material comprising a compact of a substance having a content of not more than 0.0% by volume.
含む請求項１記載の熱電材料。2. The thermoelectric material according to claim 1, wherein Sb is contained as a metalloid element constituting the A phase.
請求項１または２記載の熱電材料。3. The thermoelectric material according to claim 1, wherein the phase A is made of a skutterudite-based material.
含む請求項１乃至３のいずれか１項に記載の熱電材料。4. The thermoelectric material according to claim 1, wherein Bi is contained as a low-melting element constituting the b-phase.
熱電材料の製造方法において、 Ｓｂ、Ａｓ、Ｔｅ、およびＳｅから選択された１種以上
の半金属元素を含む組成の結晶からなる材料と、融点が
１００℃以上１０００℃以下である低融点元素を含む組
成の材料とを用い、粉末焼結法で所定形状の成形体を得
ることを特徴とする熱電材料の製造方法。5. The method for producing a thermoelectric material according to claim 1, wherein a crystal having a composition containing one or more metalloid elements selected from Sb, As, Te, and Se. A method for producing a thermoelectric material, comprising using a material having a composition containing a low-melting element having a melting point of 100 ° C. or more and 1000 ° C. or less, and obtaining a molded body having a predetermined shape by a powder sintering method.
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