JPH1060563A - Cobalt triantimonide series composite material - Google Patents
Cobalt triantimonide series composite materialInfo
- Publication number
- JPH1060563A JPH1060563A JP8237160A JP23716096A JPH1060563A JP H1060563 A JPH1060563 A JP H1060563A JP 8237160 A JP8237160 A JP 8237160A JP 23716096 A JP23716096 A JP 23716096A JP H1060563 A JPH1060563 A JP H1060563A
- Authority
- JP
- Japan
- Prior art keywords
- cobalt
- powder
- atoms
- triantimonide
- antimony
- 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
Abstract
Description
【０００１】[0001]
【発明が属する技術分野】本発明は、ゼーベック効果や
ペルチェ効果による熱電変換機能を有する複合材料に関
する。[0001] The present invention relates to a composite material having a thermoelectric conversion function based on the Seebeck effect or the Peltier effect.
【０００２】[0002]
【従来技術とその問題点】ペルチェ効果を利用して熱電
冷却やゼーベック効果を利用して熱電発電を行うために
用いられる熱電変換材料は、一般に材料組成固有の熱電
特性を有するものであるが、この熱電特性は、また強い
温度依存性を示すものでもあった。このため使用に際し
ては、例えば低温領域用としてはＢｉ2Ｔｅ3系、中温領
域用としてはＰｂＴｅ系、高温領域用としてはＳｉＧｅ
系の熱電材料が用いられているように、使用温度領域に
よって有用な熱電特性を示す熱電材料を選択する必要が
あった。また、用途によっては広範囲な使用温度を要さ
れることもある。例えば熱電冷却では熱電材料からなる
素子の吸熱側と放熱側で温度差が生じ、更に熱電発電で
もかなりの温度差を利用することから素子の発熱側とそ
れ以外の部分では大きな温度差が生じる。有用な熱電特
性を発現できる温度領域が狭い熱電材料では、このよう
な用途には十分対応できない。2. Description of the Related Art Thermoelectric conversion materials used for thermoelectric cooling utilizing the Peltier effect and thermoelectric generation utilizing the Seebeck effect generally have thermoelectric characteristics inherent to the material composition. The thermoelectric properties also exhibited strong temperature dependence. Therefore, when used, for example, a Bi 2 Te 3 system for the low temperature region, a PbTe system for the medium temperature region, and SiGe for the high temperature region
It is necessary to select a thermoelectric material exhibiting useful thermoelectric characteristics depending on the operating temperature range, as in the case of using a thermoelectric material of the system. Also, depending on the application, a wide range of operating temperatures may be required. For example, in thermoelectric cooling, a temperature difference occurs between the heat absorbing side and the heat radiating side of an element made of a thermoelectric material, and a considerable temperature difference is used in thermoelectric power generation, so that a large temperature difference occurs between the heat generating side of the element and other parts. A thermoelectric material having a narrow temperature range in which useful thermoelectric properties can be exhibited cannot be sufficiently used for such an application.
【０００３】このため、例えばＢｉ2Ｔｅ3系熱電材料で
は、各温度で優れた熱電特性を示すようにＢｉ2Ｔｅ3の
正孔又は自由電子のキャリア濃度を変えて最高の熱電特
性を示す温度を変化させた幾種かの材料を、例えばキャ
リア濃度の昇降順に組み合わせて一体化させ、有用な熱
電特性を示す温度領域を拡大させた傾斜構造型熱電材料
が知られている。また、低温から高温までの大きな温度
差から効率良く発電するために、ＳｉＧｅ系、ＰｂＴｅ
系、Ｂｉ2Ｔｅ3系の各材料を組み合わせて一体化させた
いわゆるカスケード型素子も提案されている。しかし、
何れも異組成物間の接合部で抵抗率が増大し、エネルギ
ー損失が大きく期待通りの特性を得るには至っていな
い。For this reason, for example, in a Bi 2 Te 3 -based thermoelectric material, the carrier concentration of the holes or free electrons of Bi 2 Te 3 is changed so that the thermoelectric material exhibits the best thermoelectric characteristics at each temperature. For example, there is known an inclined structure-type thermoelectric material in which several materials having different values are combined and integrated, for example, in ascending and descending order of carrier concentration, and a temperature region showing useful thermoelectric characteristics is expanded. Further, in order to efficiently generate power from a large temperature difference from a low temperature to a high temperature, a SiGe-based, PbTe
System, so-called cascade elements are integrated by combining the materials of Bi 2 Te 3 system have also been proposed. But,
In any case, the resistivity increases at the junction between the different compositions, the energy loss is large, and the expected characteristics have not been obtained.
【０００４】また、温度依存性が比較的小さく、低温領
域から中温領域の幅広い温度域において安定した熱電特
性を示す材料として、Ｃｏの一部をＮｉ，Ｆｅ等で置換
した、或いは、Ｓｂの一部をＳｎやＴｅ等で置換したス
クッテルダイト型構造のＣｏＳｂ3系半導体材料も知ら
れている。一方、ペルチェ効果やゼーベック効果を示す
熱電材料の熱電特性の優劣は、一般に性能指数Ｚ
（Ｋ-1）で表され、Ｚが大きいほど熱電材料としての特
性が優れている。（Ｚ＝α2／（ρ・κ） 但し、αは
熱電能、ρは電気抵抗率、κは熱伝導率。）前記のＣｏ
Ｓｂ3系半導体材料では、キャリアとなる自由電子や正
孔の濃度を変化させて電気抵抗率（ρ）を下げることが
できるが、その場合熱伝導率の上昇をもたらすことがあ
り、性能指数の向上には必ずしも結びつくものではなか
った。Further, as a material having relatively small temperature dependence and exhibiting stable thermoelectric characteristics in a wide temperature range from a low temperature range to a medium temperature range, a part of Co is replaced by Ni, Fe, or the like, or one of Sb is used. A CoSb 3 -based semiconductor material having a skutterudite structure in which a portion is replaced with Sn, Te, or the like is also known. On the other hand, thermoelectric materials exhibiting the Peltier effect or the Seebeck effect are generally superior in thermoelectric properties due to the performance index Z.
It is represented by (K -1 ), and the larger the Z, the better the properties as a thermoelectric material. (Z = α 2 / (ρ · κ) where α is thermoelectric power, ρ is electrical resistivity, κ is thermal conductivity.)
In an Sb 3 -based semiconductor material, the electrical resistivity (ρ) can be lowered by changing the concentration of free electrons and holes serving as carriers, but in that case, the thermal conductivity may be increased, and the figure of merit of the performance index may be increased. It did not necessarily lead to improvement.
【０００５】[0005]
【発明が解決しようとする課題】電気抵抗率と熱伝導率
の積は金属の種類によらず与えられた温度で一定である
というウィーデマン・フランツの法則により、電気抵抗
率と熱伝導率を同時に小さくすることは非常に困難であ
る。本発明は、抵抗率を少なくとも上昇させずに熱伝導
率を下げることが可能な構造を有し、幅広い温度域に於
いて優れた熱電特性を示す複合材料を得ることを目的と
する。According to the Wiedemann-Franz law that the product of the electrical resistivity and the thermal conductivity is constant at a given temperature regardless of the type of metal, the electrical resistivity and the thermal conductivity can be simultaneously determined. It is very difficult to make it small. An object of the present invention is to obtain a composite material having a structure capable of lowering the thermal conductivity without increasing the resistivity at least, and exhibiting excellent thermoelectric properties in a wide temperature range.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、熱電特性
の温度依存性が小さいスクッテルダイト型構造の三アン
チモン化コバルトに於いて、該三アンチモン化コバルト
の結晶格子の中心に大きな空孔があることに注目し、そ
の空孔を原子で充填させたものは、空孔侵入原子の熱振
動によりフォノンが散乱され、電気抵抗を殆ど上昇させ
ることなく熱伝導率が減少すること、また更に、キャリ
アとしての正孔および自由電子の濃度を調整するために
アンチモン又はコバルトの一部をアンチモン及びコバル
ト以外の原子で置換したものでは電気抵抗の低減もでき
る上に熱伝導率も低いものとなり、その結果、このよう
な結晶構造を有する三アンチモン化コバルト系複合材料
は幅広い温度域に於いて優れた熱電特性を示すことがで
きる複合材料となることを見出した。Means for Solving the Problems The present inventors have found that in a skutterudite-type cobalt triantimonide having a small temperature dependence of thermoelectric characteristics, a large space is formed at the center of the crystal lattice of the cobalt triantimonide. Focusing on the presence of holes, the vacancies filled with atoms are scattered by phonons due to the thermal oscillations of the vacant atoms, and the thermal conductivity decreases with almost no increase in electrical resistance. Furthermore, in the case where antimony or cobalt is partially replaced by atoms other than antimony and cobalt in order to adjust the concentration of holes and free electrons as carriers, the electric resistance can be reduced and the thermal conductivity is low. As a result, a cobalt triantimonide-based composite material having such a crystal structure becomes a composite material that can exhibit excellent thermoelectric properties over a wide temperature range. It was found that.
【０００７】即ち本発明は、スクッテルダイト型構造の
三アンチモン化コバルトの空孔に原子半径１．４オング
ストローム以上の原子が充填されていることを特徴とす
る三アンチモン化コバルト系複合材料である。That is, the present invention is a cobalt triantimonide-based composite material, characterized in that the vacancy of a skutterudite-type structure is filled with atoms having an atomic radius of 1.4 Å or more. .
【０００８】また本発明は、スクッテルダイト型構造の
三アンチモン化コバルトのコバルトサイトのＣｏの一部
またはアンチモンサイトのＳｂの一部をＣｏ及びＳｂ以
外の金属原子で置換したものであることを特徴とする前
記の三アンチモン化コバルト系複合材料である。Further, the present invention relates to a skutterudite type cobalt triantimonide in which a part of Co in the cobalt site or a part of Sb in the antimony site is substituted with a metal atom other than Co and Sb. A cobalt triantimonide-based composite material as described above.
【０００９】[0009]
【発明の実施の形態】本発明に於ける三アンチモン化コ
バルト系複合材料は、スクッテルダイト型構造の三アン
チモン化コバルト（ＣｏＳｂ3）内の空孔に原子半径
１．４オングストローム以上の任意の原子が侵入した構
造を有するものである。スクッテルダイト型構造の三ア
ンチモン化コバルト内の空孔の大きさは、原子半径１．
４オングストロームの原子がほぼ過不足無く収納可能な
大きさであるので原子半径１．４オングストローム以上
の原子で該空孔を充填すると、格子定数が増大して原結
晶構造からの歪みが生じ、この歪みが侵入原子の熱振動
によるフォノンの散乱を更に増大させることになり、熱
伝導率をより減少させることが可能になる。尚、原子半
径１．４オングストローム未満の原子も該空孔に侵入す
ることができ侵入原子の熱振動によるフォノンの散乱に
よって熱伝導率の減少も見られるものの、原結晶構造か
らの歪みが殆ど生じない為、熱伝導率の顕著な減少は起
こり難い。BEST MODE FOR CARRYING OUT THE INVENTION The cobalt triantimonide-based composite material according to the present invention has a structure in which vacancies in a skutterudite type cobalt triantimonide (CoSb 3 ) have an atomic radius of 1.4 Å or more. It has a structure in which atoms have penetrated. The size of the vacancies in the skutterudite-type cobalt triantimonide has an atomic radius of 1.
Since atoms of 4 Å are of a size that can be accommodated without any excess or shortage, filling the vacancies with atoms having an atomic radius of 1.4 Å or more increases the lattice constant and causes distortion from the original crystal structure. The strain further increases the scattering of phonons due to the thermal oscillations of the interstitial atoms, which can further reduce the thermal conductivity. Although atoms having an atomic radius of less than 1.4 angstroms can penetrate into the vacancies and the thermal conductivity decreases due to phonon scattering due to thermal vibration of the penetrating atoms, distortion from the original crystal structure almost occurs. Therefore, a significant decrease in thermal conductivity is unlikely to occur.
【００１０】また、好ましくは、前記スクッテルダイト
型構造の空孔を原子で充填した三アンチモン化コバルト
のコバルトサイトのＣｏ又はアンチモンサイトのＳｂの
一部をＣｏ及びＳｂ以外の金属原子で置換、望ましくは
Ｃｕ、Ｚｎ、Ａｌ、Ｔｉ、Ｆｅ、Ｎｉ、Ｔｅ、Ｓｅ、Ｓ
ｎ等の何れかの金属原子で置換し、ｐ型又はｎ型半導性
を付与するためにキャリアとしての正孔または自由電子
の濃度を調整した三アンチモン化コバルト系複合材料と
する。この場合、スクッテルダイト型構造の空孔を原子
で充填したことによる熱伝導率の低減化とキャリア濃度
調整による電気抵抗率の低減化を同時に成し得た材料と
なる。Preferably, Co of the cobalt site of cobalt triantimonide or Sb of the antimony site in which the vacancy of the skutterudite structure is filled with atoms is replaced with a metal atom other than Co and Sb. Desirably, Cu, Zn, Al, Ti, Fe, Ni, Te, Se, S
A cobalt triantimonide-based composite material in which the concentration of holes or free electrons as carriers is adjusted in order to impart p-type or n-type semiconductivity by substitution with any metal atom such as n. In this case, the material is a material that can simultaneously reduce the thermal conductivity by filling the holes of the skutterudite structure with atoms and reduce the electrical resistivity by adjusting the carrier concentration.
【００１１】このような三アンチモン化コバルト系複合
材料は、例えば以下のような方法により製造することが
できる。即ち、等モル比の高純度コバルト粉末と高純度
アンチモン粉末からなる混合粉末を用いて溶融法により
合金塊を作製し、この合金塊を粉砕して粉末にする。次
いでコバルトが４、空孔を埋める原子が１、追加するア
ンチモンが１２のモル比となるように前記コバルト含有
の粉末合金及び充填用原子の粉末及びアンチモン粉末か
らなる混合粉末を調整し、必要に応じ該混合粉末を所望
の形状に成形し、これを非酸化性性雰囲気、望ましくは
不活性ガス中で焼結を行うことによりスクッテルダイト
構造内の空孔が原子半径１．４オングストローム以上の
原子で充填された三アンチモン化コバルト系複合材料を
作製することができる。[0011] Such a cobalt triantimonide composite material can be produced, for example, by the following method. That is, an alloy lump is produced by a melting method using a mixed powder composed of an equimolar ratio of high-purity cobalt powder and high-purity antimony powder, and the alloy lump is pulverized into powder. Next, a mixed powder composed of the cobalt-containing powder alloy, the filling atom powder, and the antimony powder was adjusted so that the molar ratio of cobalt was 4, the number of atoms filling the vacancies was 1, and the amount of added antimony was 12. Accordingly, the mixed powder is formed into a desired shape, and this is sintered in a non-oxidizing atmosphere, preferably an inert gas, so that pores in the skutterudite structure have an atomic radius of 1.4 angstroms or more. A cobalt triantimonide-based composite material filled with atoms can be produced.
【００１２】また、コバルトサイトのＣｏの一部をＣｏ
及びＳｂ以外の金属原子で置換、又はアンチモンサイト
のＳｂの一部をＣｏ及びＳｂ以外の金属原子で置換さ
れ、空孔が原子で充填された三アンチモン化コバルト系
複合材料の製造方法としては、例えば、所望の置換金属
原子Ｍによる置換割合をＸ（但し、０＜Ｘ＜１）とする
と、Ｃｏの一部をＭで置換する場合は、Ｃｏ1-XＭXＳｂ
組成となる量の高純度コバルト粉末と高純度アンチモン
粉末及び高純度Ｍ粉末を秤量（Ｃｏ：Ｍ：Ｓｂ＝（１−
Ｘ）モル：Ｘモル：１モル）混合し、該混合粉末を用い
て溶融法により合金塊を作製し、この合金塊を粉砕して
粉末にする。次いでＣｏ1-XＭXが４、空孔を埋める原子
が１、追加するアンチモンが１２のモル比となるよう
に、前記Ｍ含有コバルト−アンチモンの合金粉末及び充
填用原子Ｍの粉末及びアンチモン粉末からなる混合粉末
を調整し、必要に応じ該混合粉末を所望の形状に成形
し、これを非酸化性雰囲気、望ましくは不活性ガス中で
焼結することによりスクッテルダイト構造内の空孔が原
子半径１．４オングストローム以上の原子で充填された
ｎ型半導体の三アンチモン化コバルト系複合材料を作製
することができる。Further, a part of Co of the cobalt site is replaced with Co.
And a metal atom other than Sb, or a part of Sb of antimony site is replaced with a metal atom other than Co and Sb, and the method for producing a cobalt triantimonide-based composite material in which holes are filled with atoms includes: For example, assuming that the substitution ratio by a desired substitution metal atom M is X (where 0 <X <1), when a part of Co is substituted by M, Co 1−X M X Sb
The amounts of the high-purity cobalt powder, high-purity antimony powder, and high-purity M powder in the composition were weighed (Co: M: Sb = (1-
X) mol: X mol: 1 mol), and an alloy lump is produced by a melting method using the mixed powder, and the alloy lump is pulverized to a powder. Then Co 1-X M X is 4, 1 atom to fill the vacancies, as antimony to add a molar ratio of 12, the M-containing cobalt - alloy powder and filling atom M antimony powder and antimony powder The mixed powder consisting of is formed, if necessary, the mixed powder is formed into a desired shape, and this is sintered in a non-oxidizing atmosphere, desirably an inert gas, so that pores in the skutterudite structure are formed. An n-type semiconductor cobalt triantimonide-based composite material filled with atoms having an atomic radius of 1.4 angstroms or more can be manufactured.
【００１３】また、Ｓｂの一部をＭで置換する場合は、
ＣｏＭXＳｂ1-X組成となる量の高純度コバルト粉末と高
純度アンチモン粉末及び高純度Ｍ粉末を秤量（Ｃｏ：
Ｍ：Ｓｂ＝１モル：Ｘモル：（１−Ｘ）モル）混合し、
該混合粉末を用いて溶融法により合金塊を作製し、この
合金塊を粉砕して粉末にする。次いでコバルトが４、空
孔を埋める原子が１、追加するＭXＳｂ1-Xが１２のモル
比となるように、前記Ｍ含有コバルト−アンチモンの合
金粉末及び充填用原子Ｍの粉末及びアンチモン粉末から
なる混合粉末を調整し、必要に応じ該混合粉末を所望の
形状に成形し、これを不活性ガス中で焼結を行うことに
よりスクッテルダイト構造内の空孔が原子で充填された
ｐ型半導体の三アンチモン化コバルト系複合材料を作製
することができる。When a part of Sb is replaced by M,
A high purity cobalt powder, a high purity antimony powder and a high purity M powder are weighed in amounts such that a CoM X Sb 1-X composition is obtained (Co:
M: Sb = 1 mol: X mol: (1-X) mol)
Using the mixed powder, an alloy lump is produced by a melting method, and the alloy lump is pulverized into a powder. Then, the M-containing cobalt-antimony alloy powder, the filling atom M powder, and the antimony powder are mixed such that the molar ratio of cobalt is 4, the number of atoms filling the vacancies is 1, and the added M x Sb 1-x is 12. The mixed powder consisting of was formed, and if necessary, the mixed powder was formed into a desired shape, and this was sintered in an inert gas, whereby p in the skutterudite structure was filled with atoms. It is possible to produce a cobalt triantimonide-based composite material of a type semiconductor.
【００１４】[0014]
［実施例１］ コバルトとアンチモンのモル比が１：１
になるようにコバルト粉末（（株）高純度化学研究所、
純度９９．９％）とアンチモン粉末（住友金属鉱山
（株）、純度９９．９９９％）を混合したものをアルゴ
ンガスを充填させた石英管内に封入した。この石英管を
電気炉にて約１２５０℃で２４時間加熱処理し、炉内放
冷後の石英管内の合金塊を取り出し、これを粉砕して合
金粉末を得た。該合金粉末及び錫粉末及びアンチモン粉
末を用い、コバルトと錫とアンチモンのモル比が４：
１：１２になる混合粉末を作製した。次いで該混合粉末
をアルゴンガスを充填させた石英管内に封入した。この
石英管を電気炉にて約６００℃で２時間加熱処理し、炉
内放冷後の石英管内には塊状の生成物が存在した。該生
成物は粉末Ｘ線回折により錫が空孔に侵入したスクッテ
ルダイト型構造の三アンチモン化コバルトであることを
確認し、その格子定数は９．０４オングストロームであ
った。また、この三アンチモン化コバルト系材料の熱伝
導率は静的比較法による測定の結果、３．２Ｗ／ｍＫで
あった。[Example 1] The molar ratio of cobalt to antimony was 1: 1.
Become a cobalt powder (High Purity Chemical Laboratory, Inc.)
A mixture of 99.9% purity and antimony powder (Sumitomo Metal Mining Co., Ltd., 99.999% purity) was sealed in a quartz tube filled with argon gas. The quartz tube was heated in an electric furnace at about 1250 ° C. for 24 hours, and after cooling in the furnace, an alloy lump in the quartz tube was taken out and pulverized to obtain an alloy powder. Using the alloy powder, tin powder and antimony powder, the molar ratio of cobalt, tin and antimony was 4:
A mixed powder of 1:12 was prepared. Next, the mixed powder was sealed in a quartz tube filled with argon gas. This quartz tube was heated in an electric furnace at about 600 ° C. for 2 hours, and after cooling in the furnace, a lump product was present in the quartz tube. The product was confirmed by powder X-ray diffraction to be cobalt triantimonide having a skutterudite structure in which tin had penetrated holes, and its lattice constant was 9.04 Å. The thermal conductivity of this cobalt triantimonide-based material was 3.2 W / mK as a result of measurement by a static comparison method.
【００１５】［実施例２］ 前記実施例１に於いて、錫
粉末の代わりに珪素粉末又はゲルマニウム粉末又は鉛粉
末を用いる以外は全て実施例１と同様の方法で、コバル
トと珪素とアンチモンのモル比、又はコバルトとゲルマ
ニウムとアンチモンのモル比、又はコバルトと鉛とアン
チモンのモル比が、何れも４：１：１２になる混合粉末
をそれぞれ作製した。該混合粉末をアルゴンガスを充填
させた石英管内にそれぞれ封入した。各石英管を電気炉
にて約６００℃で２時間加熱処理し、炉内放冷後の石英
管内から得た各合成物はＸ線回折により、珪素又はゲル
マニウム又は鉛がそれぞれ空孔に侵入したスクッテルダ
イト型構造の三アンチモン化コバルトであることを確認
し、その格子定数とにより測定した熱伝導率は、珪素侵
入型では格子定数９．０３オングストローム、熱伝導率
５．５Ｗ／ｍＫ、ゲルマニウム侵入型では格子定数９．
０３オングストローム、熱伝導率５．６Ｗ／ｍＫ、鉛侵
入型では格子定数９．０４オングストロームで熱伝導率
３．５Ｗ／ｍＫであった。Example 2 The procedure of Example 1 was repeated except that silicon powder, germanium powder, or lead powder was used instead of tin powder. A mixed powder was prepared in which the ratio, or the molar ratio of cobalt, germanium, and antimony, or the molar ratio of cobalt, lead, and antimony was 4: 1: 12. The mixed powder was sealed in quartz tubes filled with argon gas. Each quartz tube was heat-treated in an electric furnace at about 600 ° C. for 2 hours, and silicon, germanium, or lead respectively penetrated the pores by X-ray diffraction in each of the composites obtained from the inside of the quartz tube after cooling in the furnace. It was confirmed that it was a skutterudite-type cobalt triantimonide, and the thermal conductivity measured by its lattice constant was found to be 9.03 angstroms, a thermal conductivity of 5.5 W / mK, and a germanium of silicon intrusion type. In the interstitial type, the lattice constant is 9.
It had a thermal conductivity of 3.5 W / mK with a lattice constant of 9.04 angstroms for the lead penetration type.
【００１６】［実施例３］ 実施例１と同様のコバルト
とアンチモンとニッケルの各粉末を用い、ニッケルで２
モル％のコバルトを置換してＣｏ0.98Ｎｉ0.02Ｓｂの組
成になるように秤量した混合粉末をアルゴンガスを充填
させた石英管内に封入し、この石英管を電気炉にて約１
２５０℃で２４時間加熱処理し、炉内放冷後の石英管内
の合金塊を取り出し、これを粉砕して合金粉末を得た。
該合金粉末及び錫粉末及びアンチモン粉末を用い、Ｃｏ
0.98Ｎｉ0.02と錫とアンチモンのモル比が４：１：１２
になる混合粉末を作製した。次いで該混合粉末をアルゴ
ンガスを充填させた石英管内に封入した。この石英管を
電気炉にて約６００℃で２時間加熱処理し、炉内放冷後
の石英管内には塊状の生成物が存在した。該生成物は粉
末Ｘ線回折により錫が空孔に侵入したスクッテルダイト
型構造のＣｏの一部がＮｉで置換されたｎ型の三アンチ
モン化コバルトであることを確認し、その格子定数は
９．０４オングストロームであり、また熱伝導率を静的
比較法により測定した結果、３．５Ｗ／ｍＫであった。Example 3 The same powder of cobalt, antimony and nickel as used in Example 1 was used.
A mixed powder weighed so as to have a composition of Co 0.98 Ni 0.02 Sb by substituting mol% of cobalt was sealed in a quartz tube filled with argon gas, and this quartz tube was placed in an electric furnace for about 1 hour.
Heat treatment was performed at 250 ° C. for 24 hours, and after cooling in the furnace, an alloy lump in the quartz tube was taken out and pulverized to obtain an alloy powder.
Using the alloy powder, tin powder and antimony powder, Co
0.98 Ni 0.02 , tin: antimony molar ratio of 4: 1: 12
Was prepared. Next, the mixed powder was sealed in a quartz tube filled with argon gas. This quartz tube was heated in an electric furnace at about 600 ° C. for 2 hours, and after cooling in the furnace, a lump product was present in the quartz tube. The product was confirmed by powder X-ray diffraction to be an n-type cobalt triantimonide in which part of Co having a skutterudite structure in which tin had penetrated the pores was replaced with Ni, and the lattice constant was As a result of measuring the thermal conductivity by a static comparison method, it was 3.5 W / mK.
【００１７】［実施例４］ 実施例１と同様のコバルト
とアンチモンと錫の各粉末を用い、錫で０．１５モル％
のアンチモンを置換して ＣｏＳｂ0.9985Ｓｎ0.0015に
なるように秤量した混合粉末をアルゴンガスを充填させ
た石英管内に封入し、この石英管を電気炉にて約１２５
０℃で２４時間加熱処理し、炉内放冷後の石英管内の合
金塊を取り出し、これを粉砕して合金粉末を得た。該合
金粉末及び錫粉末及びアンチモン粉末を用い、コバルト
と錫とＳｂ0.9985Ｓｎ0.0015のモル比が４：１：１２に
なる混合粉末を作製した。次いで該混合粉末をアルゴン
ガスを充填させた石英管内に封入した。この石英管を電
気炉にて約６００℃で２時間加熱処理し、炉内放冷後の
石英管内には塊状の生成物が存在した。該生成物は粉末
Ｘ線回折により錫が空孔に侵入したスクッテルダイト型
構造のＳｂの一部がＳｎで置換されたｐ型の三アンチモ
ン化コバルトであることを確認し、その格子定数は９．
０４オングストロームであり、また熱伝導率を静的比較
法により測定した結果、３．５Ｗ／ｍＫであった。Example 4 The same powder of cobalt, antimony and tin as in Example 1 was used, and 0.15 mol% of tin was used.
The mixed powder weighed so that the antimony is replaced with CoSb 0.9985 Sn 0.0015 is sealed in a quartz tube filled with argon gas, and this quartz tube is placed in an electric furnace at about 125 ° C.
Heat treatment was performed at 0 ° C. for 24 hours, and an alloy lump in the quartz tube after cooling in the furnace was taken out and pulverized to obtain an alloy powder. Using the alloy powder, tin powder and antimony powder, a mixed powder having a molar ratio of cobalt: tin: Sb 0.9985 Sn 0.0015 of 4: 1: 12 was prepared. Next, the mixed powder was sealed in a quartz tube filled with argon gas. This quartz tube was heated in an electric furnace at about 600 ° C. for 2 hours, and after cooling in the furnace, a lump product was present in the quartz tube. The product was confirmed by powder X-ray diffraction to be p-type cobalt triantimonide in which a part of Sb of the skutterudite structure in which tin had penetrated the pores was replaced with Sn, and the lattice constant was 9.
As a result of measuring the thermal conductivity by a static comparison method, it was 3.5 W / mK.
【００１８】［比較例１］ コバルトとアンチモンのモ
ル比が１：３になるようにコバルト粉末（（株）高純度
化学研究所、純度９９．９％）とアンチモン粉末（住友
金属鉱山（株）、純度９９．９９９％）を混合したもの
をアルゴンガスを充填させた石英管内に封入した。この
石英管を電気炉にて約１２５０℃で２４時間加熱処理
し、炉内放冷後の石英管内の合金塊を取り出した。該合
金塊は粉末Ｘ線回折による定性分析から空孔内に原子を
含まないスクッテルダイト型構造の三アンチモン化コバ
ルト（ＣｏＳｂ3）であることを確認した。また、この
三アンチモン化コバルトの熱伝導率を静的比較法で測定
したところ、５．８Ｗ／ｍＫであった。Comparative Example 1 Cobalt powder (high purity chemical laboratory, purity 99.9%) and antimony powder (Sumitomo Metal Mining Co., Ltd.) so that the molar ratio of cobalt to antimony was 1: 3. , Purity 99.999%) was sealed in a quartz tube filled with argon gas. This quartz tube was subjected to heat treatment in an electric furnace at about 1250 ° C. for 24 hours, and an alloy lump in the quartz tube after cooling in the furnace was taken out. Qualitative analysis by powder X-ray diffraction confirmed that the alloy mass was cobalt triantimonide (CoSb 3 ) having a skutterudite-type structure containing no atoms in the pores. The thermal conductivity of the cobalt triantimonide measured by a static comparison method was 5.8 W / mK.
【００１９】［比較例２］ コバルトとアンチモンのモ
ル比が１：１になるようにコバルト粉末（（株）高純度
化学研究所、純度９９．９％）とアンチモン粉末（住友
金属鉱山（株）、純度９９．９９９％）を混合したもの
をアルゴンガスを充填させた石英管内に封入した。この
石英管を電気炉にて約１２５０℃で２４時間加熱処理
し、炉内放冷後の石英管内の合金塊を取り出し、これを
粉砕して、アンチモン化コバルト粉末を得た。この粉末
及びチタン粉末及びアンチモン粉末を用い、コバルトと
チタンとアンチモンのモル比が４：１：１２になる混合
粉末を作製した。次いで該混合粉末をアルゴンガスを充
填させた石英管内に封入した。この石英管を電気炉にて
約６００℃で２時間加熱処理し、炉内放冷後の石英管内
には塊状の合成物が存在した。該合成物は粉末Ｘ線回折
による定性分析からチタンが空孔に侵入したスクッテル
ダイト型構造の三アンチモン化コバルトであることを確
認した。また、得られた合成物の熱伝導率は静的比較法
による測定の結果、３．７Ｗ／ｍＫであった。Comparative Example 2 Cobalt powder (High Purity Chemical Laboratory Co., Ltd., purity 99.9%) and antimony powder (Sumitomo Metal Mining Co., Ltd.) so that the molar ratio of cobalt to antimony was 1: 1. , Purity 99.999%) was sealed in a quartz tube filled with argon gas. The quartz tube was heated in an electric furnace at about 1250 ° C. for 24 hours, and after cooling in the furnace, an alloy lump in the quartz tube was taken out and pulverized to obtain a cobalt antimonide powder. Using this powder, titanium powder and antimony powder, a mixed powder having a molar ratio of cobalt, titanium and antimony of 4: 1: 12 was prepared. Next, the mixed powder was sealed in a quartz tube filled with argon gas. The quartz tube was heat-treated at about 600 ° C. for 2 hours in an electric furnace, and after cooling in the furnace, there was a massive compound in the quartz tube. Qualitative analysis by powder X-ray diffraction confirmed that the synthesized product was cobalt triantimonide having a skutterudite structure in which titanium had entered pores. The thermal conductivity of the obtained composite was 3.7 W / mK as a result of measurement by a static comparison method.
【００２０】[0020]
【発明の効果】本発明による、三アンチモン化コバルト
系複合材料は、接合界面を有しないので界面で発生する
電気抵抗の増加も無く、かつスクッテルダイト型構造か
らの格子を歪ませた構造を有すことによって電気抵抗が
上昇することなく熱伝導率を大幅に下げることができる
為、更には低減化された熱伝導率に加えてｐ型若しくは
ｎ型半導体としてキャリア濃度の調整を施すことにより
電気抵抗を下げることもできる為、何れの場合も少なく
とも低温〜概ね５００℃迄の幅広い温度範囲で高い性能
指数、即ち優れた熱電特性を発現できる。このため本複
合材料は熱電冷却或いは熱電発電等の用途に対し優れた
適用性を有する可能性が高いものである。The cobalt triantimonide-based composite material according to the present invention does not have a junction interface, so there is no increase in electric resistance generated at the interface, and the lattice distorted structure from the skutterudite structure is obtained. By having this, the thermal conductivity can be greatly reduced without increasing the electrical resistance, and further by adjusting the carrier concentration as a p-type or n-type semiconductor in addition to the reduced thermal conductivity. Since the electrical resistance can be reduced, a high figure of merit, that is, excellent thermoelectric properties can be exhibited in any case at least in a wide temperature range from low temperature to about 500 ° C. Therefore, the composite material is highly likely to have excellent applicability to applications such as thermoelectric cooling or thermoelectric power generation.
フロントページの続き (72)発明者 滝沢 博胤 宮城県仙台市太白区富沢４丁目８番50号 コ−ポしらかば102Continuation of front page (72) Inventor Hirotane Takizawa 4-80, Tomizawa, Tashiro-ku, Sendai-shi, Miyagi Prefecture
Claims (2)
化コバルトの空孔に原子半径１．４オングストローム以
上の原子が充填されていることを特徴とする三アンチモ
ン化コバルト系複合材料。1. A cobalt triantimonide-based composite material, characterized in that vacancy of a skutterudite-type cobalt triantimonide is filled with atoms having an atomic radius of 1.4 angstroms or more.
化コバルトのコバルトサイトのＣｏの一部またはアンチ
モンサイトのＳｂの一部をＣｏ及びＳｂ以外の金属原子
で置換したものであることを特徴とする請求項１記載の
三アンチモン化コバルト系複合材料。2. Cobalt triantimonide having a skutterudite structure in which a part of Co of cobalt site or a part of Sb of antimony site is substituted with a metal atom other than Co and Sb. The cobalt triantimonide composite material according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8237160A JPH1060563A (en) | 1996-08-20 | 1996-08-20 | Cobalt triantimonide series composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8237160A JPH1060563A (en) | 1996-08-20 | 1996-08-20 | Cobalt triantimonide series composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1060563A true JPH1060563A (en) | 1998-03-03 |
Family
ID=17011291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8237160A Pending JPH1060563A (en) | 1996-08-20 | 1996-08-20 | Cobalt triantimonide series composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1060563A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348755C (en) * | 2003-12-25 | 2007-11-14 | 同济大学 | Method for synthesizing tin white cobalt series thermoelectric material |
| WO2008150026A1 (en) | 2007-06-05 | 2008-12-11 | Toyota Jidosha Kabushiki Kaisha | Thermoelectric conversion element and process for producing the thermoelectric conversion element |
| KR100910158B1 (en) | 2007-09-10 | 2009-07-30 | 충주대학교 산학협력단 | Sn-FILLED AND Te-DOPED SKUTTERUDITE THERMOELECTRIC MATERIAL AND METHOD FOR MANUFACTURING THE SAME |
| US8394284B2 (en) | 2007-06-06 | 2013-03-12 | Toyota Jidosha Kabushiki Kaisha | Thermoelectric converter and method of manufacturing same |
| US8828277B2 (en) | 2009-06-18 | 2014-09-09 | Toyota Jidosha Kabushiki Kaisha | Nanocomposite thermoelectric conversion material and method of producing the same |
| JP2016066795A (en) * | 2014-09-22 | 2016-04-28 | 国立研究開発法人物質・材料研究機構 | Silicon- and tellurium-doped skutterudite thermoelectric conversion semiconductor, method for manufacturing the same, and thermoelectric power-generation element arranged by use thereof |
-
1996
- 1996-08-20 JP JP8237160A patent/JPH1060563A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348755C (en) * | 2003-12-25 | 2007-11-14 | 同济大学 | Method for synthesizing tin white cobalt series thermoelectric material |
| WO2008150026A1 (en) | 2007-06-05 | 2008-12-11 | Toyota Jidosha Kabushiki Kaisha | Thermoelectric conversion element and process for producing the thermoelectric conversion element |
| US8617918B2 (en) | 2007-06-05 | 2013-12-31 | Toyota Jidosha Kabushiki Kaisha | Thermoelectric converter and method thereof |
| US8394284B2 (en) | 2007-06-06 | 2013-03-12 | Toyota Jidosha Kabushiki Kaisha | Thermoelectric converter and method of manufacturing same |
| KR100910158B1 (en) | 2007-09-10 | 2009-07-30 | 충주대학교 산학협력단 | Sn-FILLED AND Te-DOPED SKUTTERUDITE THERMOELECTRIC MATERIAL AND METHOD FOR MANUFACTURING THE SAME |
| US8828277B2 (en) | 2009-06-18 | 2014-09-09 | Toyota Jidosha Kabushiki Kaisha | Nanocomposite thermoelectric conversion material and method of producing the same |
| JP2016066795A (en) * | 2014-09-22 | 2016-04-28 | 国立研究開発法人物質・材料研究機構 | Silicon- and tellurium-doped skutterudite thermoelectric conversion semiconductor, method for manufacturing the same, and thermoelectric power-generation element arranged by use thereof |
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