JP2011216568A - Thermoelectric conversion material comprising magnesium, tin, and silicon, and method of manufacturing the same - Google Patents
Thermoelectric conversion material comprising magnesium, tin, and silicon, and method of manufacturing the same Download PDFInfo
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本発明は熱を直接電気に変換する熱電変換材料に関するものである。熱電変換材料を用いて製造される熱電モジュールは、特に自動車や各種製造プラント、発電プラント、ゴミ焼却施設などで発生する排熱などの未利用のエネルギーを効率良く電気に変換するものであり、本発明によれば、省エネルギーに寄与するとともに作今問題となっている二酸化炭素の排出を抑制する効果が奏される。本発明は、このような熱電変換材料として用いられるマグネシウム、錫及び珪素からなる金属間化合物の焼結体、及びその製造方法の技術分野に属するものである。 The present invention relates to a thermoelectric conversion material that directly converts heat into electricity. Thermoelectric modules manufactured using thermoelectric conversion materials efficiently convert unused energy such as exhaust heat generated in automobiles, various manufacturing plants, power plants, garbage incineration facilities, etc. into electricity. According to the invention, the effect of suppressing the emission of carbon dioxide, which contributes to energy saving and is a problem at present, is exhibited. The present invention belongs to the technical field of a sintered body of an intermetallic compound composed of magnesium, tin and silicon used as such a thermoelectric conversion material, and a method for producing the same.
熱電変換材料は、その材料の両端に温度差をつけることにより、熱エネルギーを直接電気エネルギーに変換（ゼーベック効果）して取り出せる性質を持つ材料で、その性能の高さの指標として、下式で示される性能指数(Figure of merit) Ｚが用いられ、この値が大きいほど高性能であることを意味する。
Ｚ＝α2 σ／κ（Ｋ-1） （１）
ここで、α：ゼーベック係数（Ｖ／Ｋ）、σ：電気伝導度（Ｓ／ｍ）、κ：熱伝導率（Ｗ／ｍＫ）である。
また、熱電変換材料の性能の目安として、上記性能指数Ｚに絶対温度をかけて無次元量として表現した、無次元性能指数ＺＴを用いることも多い。
マグネシウム（Ｍｇ）と錫（Ｓｎ）と珪素（Ｓｉ）からなる金属間化合物においてＭｇ２ Ｓｎ１−ｘ Ｓｉｘ が知られており、該金属間化合物の焼結体でｘ＝０．４〜０．６の範囲のものが熱電特性に優れていることが報告されている（特許文献１及び特許文献２参照）。
A thermoelectric conversion material is a material that has the property of converting thermal energy directly into electrical energy (Seebeck effect) by creating a temperature difference at both ends of the material. As an indicator of its high performance, The figure of merit Z shown is used, and a larger value means higher performance.
Z = α 2 σ / κ (K −1 ) (1)
Here, α: Seebeck coefficient (V / K), σ: electrical conductivity (S / m), and κ: thermal conductivity (W / mK).
Further, as a measure of the performance of the thermoelectric conversion material, a dimensionless figure of merit ZT expressed as a dimensionless quantity by multiplying the above figure of merit Z by absolute temperature is often used.
Mg 2 Sn 1-x Si x is known in an intermetallic compound composed of magnesium (Mg), tin (Sn), and silicon (Si), and x = 0.4 to 0 in a sintered body of the intermetallic compound. .6 range is reported to have excellent thermoelectric properties (see
上記の公知の金属間化合物Ｍｇ２ Ｓｎ１−ｘ Ｓｉｘ の焼結体は、Ｍｇの蒸発のため単相をつくることが難しいという欠点があった。また、熱電特性が未だ十分に満足し得るものではなく、さらに熱電特性を向上させることが要求されている。
本発明は、これらの課題を解決するものであり、熱電特性に優れた、特に高温領域において熱電特性に優れたＭｇＳｎＳｉ系熱電変換材料及びその製造方法を提供することを目的とするものである。
The known sintered body of the intermetallic compound Mg 2 Sn 1-x Si x has a drawback that it is difficult to form a single phase due to evaporation of Mg. In addition, the thermoelectric characteristics are not sufficiently satisfactory, and it is required to further improve the thermoelectric characteristics.
The present invention solves these problems, and an object of the present invention is to provide an MgSnSi-based thermoelectric conversion material excellent in thermoelectric characteristics, particularly in a high temperature region, and a method for producing the same.
本発明は、下記の熱電変換材料及びその製造方法を提供することにより、上記課題を解決したものである。
「マグネシウム、錫及び珪素からなる金属間化合物Ｍｇｘ Ｓｎ１−ｙ Ｓｉｙ の焼結体からなり、焼結体組成において２．０２＜ｘ≦２．１０であることを特徴とする熱電変換材料。」
「原料の秤量工程、秤量した原料を溶解し、溶製材を得る工程、溶製材を粉砕し、分級して焼結原料を得る工程、焼結原料を焼結して焼結体を得る工程を含む、マグネシウム、錫及び珪素からなる熱電変換材料の製造方法であって、上記原料の秤量工程において、マグネシウムを、金属間化合物Ｍｇｘ Ｓｎ１−ｙ Ｓｉｙ の焼結体組成において２．０２＜ｘ≦２．１０となるように秤量することを特徴とする熱電変換材料の製造方法。」
This invention solves the said subject by providing the following thermoelectric conversion material and its manufacturing method.
“Thermoelectric conversion material comprising a sintered body of an intermetallic compound Mg x Sn 1-y Si y composed of magnesium, tin and silicon, wherein the sintered body composition is 2.02 <x ≦ 2.10 . "
"The raw material weighing step, the step of melting the weighed raw material to obtain a molten material, the step of pulverizing and classifying the molten material to obtain the sintered raw material, the step of sintering the sintered raw material and obtaining the sintered body A method for producing a thermoelectric conversion material comprising magnesium, tin and silicon, wherein, in the raw material weighing step, magnesium is contained in a sintered body composition of an intermetallic compound Mg x Sn 1-y Si y at 2.02 < A method for producing a thermoelectric conversion material, characterized by weighing so as to satisfy x ≦ 2.10. ”
本発明の熱電変換材料は、Ｍｇが化学量論量よりも多いため、Ｍｇの格子間に入り込むことによってＮ型のキャリアとして働き、キャリア濃度が向上し、その結果、電気伝導率の向上と、格子間に入り込むことによるフォノンの散乱による熱伝導率の低下が有効に起こり特性が向上する。特に、４００℃〜５００℃の範囲においての特性の低下が起こらない。 Since the thermoelectric conversion material of the present invention has a larger amount of Mg than the stoichiometric amount, it works as an N-type carrier by entering between the lattices of Mg, the carrier concentration is improved, and as a result, the electrical conductivity is improved, A decrease in thermal conductivity due to phonon scattering due to entering between the lattices effectively occurs and the characteristics are improved. In particular, the characteristics do not deteriorate in the range of 400 ° C to 500 ° C.
本発明の熱電変換材料を、その好ましい製造方法に基づいて説明する。
本発明の熱電変換材料は、マグネシウム（Ｍｇ）、錫（Ｓｎ）及び珪素（Ｓｉ）からなる金属間化合物の焼結体であって、Ｍｇｘ Ｓｎ１−ｙ Ｓｉｙ で表される焼結体組成（モル比）において２．０２＜ｘ≦２．１０、好ましくは２．０５≦ｘ≦２．１０になるように、Ｍｇを化学量論量よりも多く原料仕込み時に秤量し作製されたものである。
Ｍｇｘ Ｓｎ１−ｙ Ｓｉｙ で表される焼結体組成（モル比）において２．０２＜ｘ≦２．１０とすることにより、熱電特性に優れた、特に高温領域において熱電特性に優れた熱電変換材料が得られる。ｘが上記範囲より小さくても、また大きくても、熱電特性が低下する。
The thermoelectric conversion material of this invention is demonstrated based on the preferable manufacturing method.
The thermoelectric conversion material of the present invention is a sintered body of an intermetallic compound composed of magnesium (Mg), tin (Sn), and silicon (Si), and is a sintered body represented by Mg x Sn 1-y Si y Made by weighing Mg more than the stoichiometric amount when raw materials are charged so that 2.02 <x ≦ 2.10, preferably 2.05 ≦ x ≦ 2.10 in composition (molar ratio) It is.
By setting 2.02 <x ≦ 2.10 in the sintered body composition (molar ratio) represented by Mg x Sn 1-y Si y , the thermoelectric characteristics are excellent, particularly in the high temperature region. A thermoelectric conversion material is obtained. Even if x is smaller or larger than the above range, the thermoelectric characteristics are deteriorated.
本発明の熱電変換材料は、金属間化合物Ｍｇｘ Ｓｎ１−ｙ Ｓｉｙ における原料仕込み組成（モル比）において０．２≦ｙ≦０．６であるものが好ましく、０．２≦ｙ≦０．４であるものがより好ましい。ｙが０．２未満であると、熱伝導率が大きくなり無次元性能指数が低下する、またｙが０．６超であると、熱伝導率が大きくなり無次元性能指数が低下する。 The thermoelectric conversion material of the present invention preferably has 0.2 ≦ y ≦ 0.6 in the raw material charge composition (molar ratio) in the intermetallic compound Mg x Sn 1-y Si y , and 0.2 ≦ y ≦ 0. .4 is more preferable. If y is less than 0.2, the thermal conductivity increases and the dimensionless figure of merit decreases, and if y exceeds 0.6, the thermal conductivity increases and the dimensionless figure of merit decreases.
また、本発明の熱電変換材料には、Ｎ型キャリア濃度の制御がしやすい観点から、ドー パントとしてＳｂを添加することが好ましい。
Ｓｂの添加量は、金属間化合物Ｍｇｘ Ｓｎ１−ｙ−ｚ Ｓｉｙ Ｓｂｚ における原料仕込み組成（モル比）において、好ましくは０．００５≦ｚ≦０．０２となる量であり、より好ましくは０．００７５≦ｚ≦０．０１となる量である。
In addition, it is preferable to add Sb as a dopant to the thermoelectric conversion material of the present invention from the viewpoint of easy control of the N-type carrier concentration.
The amount of Sb added is preferably such that 0.005 ≦ z ≦ 0.02, in the raw material charge composition (molar ratio) in the intermetallic compound Mg x Sn 1-yz Si y Sb z . Is an amount such that 0.0075 ≦ z ≦ 0.01.
本発明の熱電変換材料を製造するには、まず、原料であるＭｇ、Ｓｎ及びＳｉを所定量秤量する。Ｍｇ及びＳｎは１ｍｍ〜５ｍｍ程度の大きさの塊状物を使用するのが好ましく、Ｓｉは粉末を使用する。
これらの原料の秤量は、マグネシウムを、金属間化合物Ｍｇｘ Ｓｎ１−ｙ Ｓｉｙ の焼結体組成において２．０２＜ｘ≦２．１０、好ましくは２．０５≦ｘ≦２．１０となるように秤量する。
具体的には、金属間化合物Ｍｇｘ Ｓｎ１−ｙ Ｓｉｙ における原料仕込み組成（モル比）において、２．０５＜ｘ＜２．４０、０．２≦ｙ≦０．６となるように秤量するのが好ましく、２．１０≦ｘ≦２．３０、０．２≦ｙ≦０．４となるように秤量するのがより好ましい。
ドーパントとしてＳｂを添加する場合には、金属間化合物Ｍｇｘ Ｓｎ１−ｙ−ｚ Ｓｉｙ Ｓｂｚ における原料仕込み組成において、２．０５＜ｘ＜２．４０、０．２≦ｙ≦０．６、０．００５≦ｚ≦０．０２となるように秤量するのが好ましく、２．１０≦ｘ≦２．３０、０．２≦ｙ≦０．４、０．００７５≦ｚ≦０．０１となるように秤量するのがより好ましい。
In order to manufacture the thermoelectric conversion material of the present invention, first, Mg, Sn and Si as raw materials are weighed in predetermined amounts. It is preferable to use a lump of about 1 mm to 5 mm for Mg and Sn, and Si uses a powder.
These raw materials are weighed such that magnesium is 2.02 <x ≦ 2.10, preferably 2.05 ≦ x ≦ 2.10 in the sintered body composition of the intermetallic compound Mg x Sn 1-y Si y. Weigh as follows.
Specifically, the raw material charge composition (molar ratio) in the intermetallic compound Mg x Sn 1-y Si y is weighed so that 2.05 <x <2.40 and 0.2 ≦ y ≦ 0.6. It is preferable to weigh so that 2.10 ≦ x ≦ 2.30 and 0.2 ≦ y ≦ 0.4.
When adding Sb as a dopant, in the raw material charge composition in the intermetallic compound Mg x Sn 1-yz Si y Sb z , 2.05 <x <2.40, 0.2 ≦ y ≦ 0.6 , 0.005 ≦ z ≦ 0.02, preferably 2.10 ≦ x ≦ 2.30, 0.2 ≦ y ≦ 0.4, 0.0075 ≦ z ≦ 0.01 It is more preferable to weigh so that
次に、秤量した原料を溶解法により溶解し、焼結原料となる溶製材を得る。この時、原料の溶解は、Ｍｇの蒸発を抑制するため、密封系内で行うことが好ましく、例えば、溶解用ルツボをステンレス管に封管したカプセル化溶解法を採用することが好ましい。これにより焼結体のＭｇの組成を容易に制御できる。
溶解条件は、通常のＭｇＳｎＳｉ系熱電変換材料の場合と同様であり、例えば、温度が好ましくは９００℃以上、より好ましくは９５０〜１１４０℃、保持時間が好ましくは５時間以上、より好ましくは１０〜２０時間である。
Next, the weighed raw materials are melted by a melting method to obtain a melted material to be a sintered raw material. At this time, the raw material is preferably dissolved in a sealed system in order to suppress the evaporation of Mg. For example, it is preferable to employ an encapsulation dissolution method in which a melting crucible is sealed in a stainless steel tube. Thereby, the Mg composition of the sintered body can be easily controlled.
The dissolution conditions are the same as in the case of a normal MgSnSi thermoelectric conversion material. For example, the temperature is preferably 900 ° C. or higher, more preferably 950 to 1140 ° C., the holding time is preferably 5 hours or longer, more preferably 10 to 10 ° C. 20 hours.
次いで、上記溶製材を粉砕し、分級して焼結原料を得る。分級は、ふるいにより１００μｍ以下となるように行うことが好ましい。
この焼結原料を、例えば放電プラズマ焼結法（ＳＰＳ）を用いて焼結し、焼結体を作製する。この時の焼結条件は、好ましくは、焼結圧力３０〜８０ＭＰａ、焼結温度６００〜７５０℃、焼結時間１０〜６０分、より好ましくは、焼結圧力３０〜５０ＭＰａ、焼結温度６５０〜７００℃、焼結時間３０〜６０分である。
このようにして得られる焼結体は、Ｍｇｘ Ｓｎ１−ｙ Ｓｉｙ 単相である。
Next, the melted material is pulverized and classified to obtain a sintered raw material. The classification is preferably performed so as to be 100 μm or less by sieving.
This sintered raw material is sintered using, for example, a discharge plasma sintering method (SPS) to produce a sintered body. The sintering conditions at this time are preferably a sintering pressure of 30 to 80 MPa, a sintering temperature of 600 to 750 ° C., a sintering time of 10 to 60 minutes, and more preferably a sintering pressure of 30 to 50 MPa and a sintering temperature of 650 to 650. 700 ° C., sintering
The sintered body obtained in this way is a Mg x Sn 1-y Si y single phase.
以下、本発明の実施例を示す。 Examples of the present invention will be described below.
実施例
粒状Ｍｇ（山石金属製 純度９９．９％、粒径１〜２ｍｍ）、粒状Ｓｎ（レアメタリック製 純度９９．９９％、粒径１〜２ｍｍ）、Ｓｉ粉末（高純度化学製 純度９９．９％）及びＳｂ粉末（高純度化学製 純度９９．９％）を用意し、これらの配合比をＭｇｘ Ｓｎ１−ｙ−ｚ Ｓｉｙ Ｓｂｚ で表されるモル比で、Ｍｇ量：ｘ＝２．００、２．０２、２．０５、２．１０、２．２０又は２．３０、Ｓｎ量：ｙ＝０．４、ドーパントであるＳｂ量：ｚ＝０．０１になるように秤量し、これらの合計が２５ｇになるようにする。次いで、秤量した原料をＡｒ雰囲気中グローブボックス内で蓋付きＢＮルツボに充填した後、Ａｒ雰囲気中でステンレスの管の中に入れ、両端をステンレス蓋で溶接しカプセル化を行う。このカプセルを電気炉内に挿入し、Ａｒ気流中で１１４０℃で１０時間溶解させて、溶製材を得る。その後、この溶製材を粉砕、分級して、焼結原料とする。この焼結原料を黒鉛型に充填し、３０ＭＰａ，７００℃×３０min の条件で放電プラズマ焼結（ＳＰＳ）を行い、目的のＭｇｘ Ｓｎ１−ｙ−ｚ Ｓｉｙ Ｓｂｚ 焼結体をそれぞれ得た。
Examples Granular Mg (purity 99.9%, manufactured by Yamaishi Metal, particle size 1-2 mm), granular Sn (purity 99.99%, rare metal particle purity 1-2 mm), Si powder (purity 99.000 purity, high purity chemical) 9%) and Sb powder (purity 99.9%, manufactured by High-Purity Chemical Co., Ltd.), and these compounding ratios are expressed as Mg x Sn 1-yz Si y Sb z in a molar ratio, Mg amount: x = 2.00, 2.02, 2.05, 2.10, 2.20 or 2.30, Sn amount: y = 0.4, dopant Sb amount: z = 0.01 The total of these is 25 g. Next, the weighed raw materials are filled in a BN crucible with a lid in a glove box in an Ar atmosphere, and then placed in a stainless steel tube in an Ar atmosphere, and both ends are welded with a stainless steel lid and encapsulated. The capsule is inserted into an electric furnace and melted at 1140 ° C. for 10 hours in an Ar stream to obtain a melted material. Thereafter, the melted material is pulverized and classified to obtain a sintered raw material. This sintering raw material is filled into a graphite mold, and discharge plasma sintering (SPS) is performed under the conditions of 30 MPa and 700 ° C. × 30 min to obtain the target Mg x Sn 1-yz Si y Sb z sintered bodies, respectively. It was.
これらの焼結体の組成分析をＩＣＰ（誘導結合プラズマ：Inductively Coupled Plasuma)により測定した結果を表１に示す。原料仕込み組成においてｘ＝２．００、２．０２、２．０５、２．１０、２．２０、２．３０で、それぞれ、焼結体組成においてｘ＝１．９８（比較例）、２．００（比較例）、２．０２（比較例）、２．０５、２．０８、２．１０であった。 Table 1 shows the results of composition analysis of these sintered bodies measured by ICP (Inductively Coupled Plasuma). In the raw material charging composition, x = 2.00, 2.02, 2.05, 2.10, 2.20, 2.30, and in the sintered body composition, x = 1.98 (comparative example). 00 (comparative example), 2.02 (comparative example), 2.05, 2.08, and 2.10.
得られた焼結体を粉砕し、粉末Ｘ線回折測定を行った。その結果、図１に示すように、Ｍｇ２ Ｓｎ０．６ Ｓｉ０．４ 単相であり、遊離Ｍｇの存在は観測されなかった。
上述の焼結体から３Ｗ×１．５ｔ×２０Ｌ（ｍｍ）の試験片を切り出し、ゼーベック係数及び電気伝導度を測定した。この結果を図２及び図３に示す。ゼーベック係数は、負の値を示し、Ｎ型伝導を示した。焼結体組成においてｘが１．９８から上昇するに伴い、焼結体の電気伝導率は向上し、ｘ＝２．０８のときに最も良い電気伝導率を示した。
The obtained sintered body was pulverized and subjected to powder X-ray diffraction measurement. As a result, as shown in FIG. 1, it was an Mg 2 Sn 0.6 Si 0.4 single phase, and the presence of free Mg was not observed.
A test piece of 3 W × 1.5 t × 20 L (mm) was cut out from the above sintered body, and the Seebeck coefficient and electrical conductivity were measured. The results are shown in FIGS. The Seebeck coefficient showed a negative value and showed N-type conduction. As x increased from 1.98 in the sintered body composition, the electrical conductivity of the sintered body was improved, and the best electrical conductivity was shown when x = 2.08.
また、上述の焼結体からφ１０×１．５ｔ（ｍｍ）の試験片を切り出し、レーザーフラッシュ法により熱拡散率を求め、示差熱分析法により比熱を求め、得られた熱伝導率を図４に示した。これより、焼結体組成においてｘ＝２．０５の焼結体は、比較的低い熱伝導率を有していることがわかる。次に、ヴィーデマン−フランツ則より、キャリアによる熱伝導率を算出した。この結果を図５に示した。このキャリアによる熱伝導率を、上述の測定した熱伝導率から差し引くことにより、格子熱伝導率を算出した。この結果を図６に示した。格子熱伝導率は、焼結体組成においてｘ＝２．０５の焼結体では、ｘ＝２．０２の焼結体（比較例）と比較すると、特に３００℃以上の高温側での上昇が少ないことが判った。これは、過剰のＭｇがＭｇ格子間にはいり欠陥を生じさせたためフォノンの散乱が起こり格子熱伝導率が低下したと考えられる。キャリアによる熱伝導率は、ｘ＝２．０５の焼結体では、大きな値を示した。実際にホール測定によりキャリア密度を測定した結果、ｘ＝２．０２の焼結体（比較例）でｎ＝５ｘ１０19／ｃｍ3 、ｘ＝２．０５の焼結体でｎ＝２ｘ１０20／ｃｍ3 となっており、これより、過剰のＭｇがＭｇ格子間にはいりドナー欠陥を生じさせたためキャリア密度の上昇がなされたと考えられる。 Further, a test piece of φ10 × 1.5 t (mm) was cut out from the above sintered body, the thermal diffusivity was determined by the laser flash method, the specific heat was determined by the differential thermal analysis method, and the obtained thermal conductivity was shown in FIG. It was shown to. From this, it can be seen that the sintered body having a sintered body composition of x = 2.05 has a relatively low thermal conductivity. Next, the thermal conductivity by the carrier was calculated from the Wiedemann-Franz rule. The results are shown in FIG. The lattice thermal conductivity was calculated by subtracting the thermal conductivity due to this carrier from the above measured thermal conductivity. The results are shown in FIG. The lattice thermal conductivity of the sintered body with x = 2.05 in the sintered body composition is increased on the high temperature side of 300 ° C. or higher, particularly when compared with the sintered body with x = 2.02 (comparative example). It turns out that there are few. This is presumably because excess Mg caused a crack in the Mg lattice, resulting in phonon scattering and a decrease in lattice thermal conductivity. The thermal conductivity by the carrier showed a large value in the sintered body with x = 2.05. As a result of actually measuring the carrier density by hole measurement, n = 5 × 10 19 / cm 3 in the sintered body of x = 2.02 (comparative example) and n = 2 × 10 20 / cm in the sintered body of x = 2.05. From this, it is considered that the carrier density was increased because excess Mg was inserted between Mg lattices to cause donor defects.
以上のように、過剰のＭｇはキャリア密度をＳｂ添加で生じるドナー密度よりもさらに多くすることができるため、ゼーベック係数が低下する真性領域になる温度が高くなる効果が生じる。また熱伝導率が３００℃以上の高温側での上昇が少ない。そのため図７に示した無次元性能指数の高温側、特に４００〜５００℃の特性が低下しない特徴がある。図７に示すように、焼結体組成においてｘ＝２．０２以下の焼結体（比較例）では、この効果が少なく、４００〜５００℃での特性の低下がある。 As described above, excess Mg can make the carrier density even higher than the donor density generated by the addition of Sb, so that there is an effect of increasing the temperature at which the Seebeck coefficient decreases and becomes an intrinsic region. Moreover, there is little rise in the high temperature side whose heat conductivity is 300 degreeC or more. Therefore, there is a feature that the characteristics at the high temperature side of the dimensionless figure of merit shown in FIG. As shown in FIG. 7, in a sintered body (comparative example) with x = 2.02 or less in the sintered body composition, this effect is small and there is a decrease in characteristics at 400 to 500 ° C.
本発明の熱電変換材料及びその製造方法は、自動車や各種製造プラント、発電プラント、ゴミ焼却施設などで発生する排熱などの未利用のエネルギーを効率良く電気に変換する用途に用いられる熱電変換材料及びその製造方法である。 The thermoelectric conversion material of the present invention and the production method thereof are thermoelectric conversion materials used for the purpose of efficiently converting unused energy such as exhaust heat generated in automobiles, various production plants, power generation plants, garbage incineration facilities, etc. into electricity. And its manufacturing method.
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| JP2017175122A (en) * | 2016-03-17 | 2017-09-28 | 三菱マテリアル株式会社 | Magnesium-based thermoelectric conversion material, magnesium-based thermoelectric conversion element, thermoelectric conversion device, and method for manufacturing magnesium-based thermoelectric conversion material |
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| JP2018182087A (en) * | 2017-04-14 | 2018-11-15 | トヨタ紡織株式会社 | METHOD OF PRODUCING Mg-BASED THERMOELECTRIC MATERIAL, AND METHOD OF RECOVERING PERFORMANCE OF Mg-BASED THERMOELECTRIC MATERIAL |
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