JP2020167265A - Thermoelectric conversion material and manufacturing method thereof - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 238000007731 hot pressing Methods 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 3
- 238000005259 measurement Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
Description
本発明は、新規な熱電変換材料、及びその製造方法に関する。 The present invention relates to a novel thermoelectric conversion material and a method for producing the same.
熱電変換材料とは温度差をつけることによって電力を取り出せる材料をいう。可動部分がなく故障しにくいため、メンテナンスフリーの排熱回収技術として注目されている。熱電変換材料の性能は以下の無次元性能指数ＺＴで表すことができ、この値が高いものが優れた特性を示すものとされる。
ＺＴ＝Ｓ2Ｔ／ρκ
［Ｓ：ゼーベック係数（Ｖ／Ｋ）、Ｔ：温度（Ｋ）、ρ：電気抵抗率（Ω・ｍ）、κ：熱伝導率（ｗ/ｍ・Ｋ）］
A thermoelectric conversion material is a material that can extract electric power by making a temperature difference. Since there are no moving parts and it is hard to break down, it is attracting attention as a maintenance-free waste heat recovery technology. The performance of the thermoelectric conversion material can be represented by the following dimensionless performance index ZT, and those having a high value are considered to exhibit excellent characteristics.
ZT = S 2 T / ρκ
[S: Seebeck coefficient (V / K), T: Temperature (K), ρ: Electrical resistivity (Ω · m), κ: Thermal conductivity (w / m · K)]
これまでに実用化された熱電変換材料としては、ビスマス・テルル系材料、鉛・テルル系材料、シリコン・ゲルマニウム系材料などが挙げられる。
また、このような熱電変換材料の一つとして、Ｍｇ3Ｓｂ2を基本構造とするものが研究されている。例えば、Ｍｇ3Ｓｂ2のＳｂサイトにＴｅを置換することによってＭｇ3Ｓｂ2に電子ドープすることで、熱電変換性能の高い、ｎ型の熱電変換材料が得られる。しかしながら、この材料では、ＳｂはＭｇと共有結合しており、Ｓｂ原子をＴｅにより原子置換することによって電子の移動が妨げられるため、より高い熱電変換性能を得るには、共有結合に乱れを導入することなくキャリアーを注入することが求められる。
これについて、最近、Ｍｇ3Ｓｂ2のＳｂサイトにＴｅを置換するのではなく、ＭｇサイトにＹをドープすることにより、ｎ型の熱電変換材料を得ることが報告された（非特許文献１）。
Examples of thermoelectric conversion materials that have been put into practical use so far include bismuth-tellurium-based materials, lead-tellurium-based materials, and silicon-germanium-based materials.
Further, as one of such thermoelectric conversion materials, a material having Mg 3 Sb 2 as a basic structure has been studied. For example, by electron doped Mg 3 Sb 2 by replacing Te to Sb site Mg 3 Sb 2, high thermoelectric conversion performance, n-type thermoelectric conversion material is obtained. However, in this material, Sb is covalently bonded to Mg, and electron transfer is hindered by substituting the Sb atom with Te. Therefore, in order to obtain higher thermoelectric conversion performance, a disorder is introduced into the covalent bond. It is required to inject the carrier without doing it.
Regarding this, it has recently been reported that an n-type thermoelectric conversion material can be obtained by doping the Mg site with Y instead of substituting Te at the Sb site of Mg 3 Sb 2 (Non-Patent Document 1). ..
上述のように多くの材料が開発されているにも関わらず、熱電変換材料が広く世の中に普及するには至っていない。その理由の一つとして、従来の材料では性能がまだ不十分であることが挙げられる。そのため、従来の熱電変換材料以上の性能が期待できる新規な熱電変換材料が求められている。
本発明は、上述のような従来技術やその問題点を背景としたものであり、従来以上の熱電変換性能が期待できる熱電変換材料を提供することを課題とする。
Despite the fact that many materials have been developed as described above, thermoelectric conversion materials have not yet become widespread in the world. One of the reasons is that the performance of conventional materials is still insufficient. Therefore, there is a demand for a new thermoelectric conversion material that can be expected to have higher performance than the conventional thermoelectric conversion material.
The present invention is based on the above-mentioned prior art and its problems, and an object of the present invention is to provide a thermoelectric conversion material that can be expected to have thermoelectric conversion performance higher than that of the prior art.
本発明者らは、上述の従来の熱電変換材料のうち、Ｍｇ3Ｓｂ2を基本構造とするものについて、従来から研究を行ってきており、その中で、Ｍｇ3Ｓｂ2の共有結合サイトであるＳｂサイトにＴｅを置換するのではなく、イオン結合サイトの原子を置換することによってキャリアーを注入すること、具体的にはＭｇイオンをＹイオンで置換することによって電子をドープすることにより、良好な熱電変換性能を有する熱電変換材料が得られることを、見出した。 The present inventors have been conducting research on the above-mentioned conventional thermoelectric conversion materials having Mg 3 Sb 2 as a basic structure, and among them, at the covalent bond site of Mg 3 Sb 2. Good by injecting carriers by substituting atoms at ionic bond sites, rather than substituting Te for certain Sb sites, specifically by doping electrons by substituting Mg ions with Y ions. It has been found that a thermoelectric conversion material having excellent thermoelectric conversion performance can be obtained.
本発明者らによる上記研究は、非特許文献１の研究とは別個に、独自になされたものであり、例えば、非特許文献１においては、上記熱電変換材料を、各金属成分をボールミルにより粉砕し、得られた粉末をホットプレスすることにより製造しているのに対し、本発明においては、各金属成分を加熱溶融し、これを粉砕した後、ホットプレスすることにより製造する。また、非特許文献１においては、グレインサイズが５００ｎｍ〜１μｍ程度の熱電変換材料が得られているのに対し、本発明においては、数十ミクロンオーダーのグレインサイズの熱電変換材料が得られる。
そして、本発明によれば、このようにして得られた熱電変換材料については、図１に示すようなＺＴ値と温度との関係が得られるところ、これを非特許文献１において得られているＺＴ値と温度との関係（非特許文献中のＦｉｇ.４（ｄ）及びＦｉｇ.５（ｆ））と対比すると明らかなとおり、７００〜８００Ｋ（４２７〜５２７℃）の高温領域では、多くの場合、非特許文献１の方が高いＺＴ値を示しているものの、より低温の３００〜４００または４５０Ｋ（２７〜１２７または１７７℃）の領域では、本発明の方が、ＺＴ値が高い。
The above-mentioned research by the present inventors was independently performed separately from the research of Non-Patent Document 1. For example, in Non-Patent Document 1, the above-mentioned thermoelectric conversion material is pulverized by a ball mill for each metal component. Then, while the obtained powder is produced by hot-pressing, in the present invention, each metal component is heated and melted, pulverized, and then hot-pressed. Further, in Non-Patent Document 1, a thermoelectric conversion material having a grain size of about 500 nm to 1 μm is obtained, whereas in the present invention, a thermoelectric conversion material having a grain size on the order of several tens of microns can be obtained.
According to the present invention, the thermoelectric conversion material thus obtained has a relationship between the ZT value and the temperature as shown in FIG. 1, which is obtained in Non-Patent Document 1. In the high temperature region of 700 to 800 K (427 to 527 ° C.), many In this case, although Non-Patent Document 1 shows a higher ZT value, the present invention has a higher ZT value in the lower temperature region of 300 to 400 or 450 K (27 to 127 or 177 ° C.).
本発明は、上記のような試験、研究過程で得られた知見に基づいて完成するに至ったものであり、本件では以下のような発明が提供される。
＜１＞次の一般式で表される熱電変換材料であって、
Ｍｇ3-x+dＹxＳｂ2-yＢｉy
（式中、０＜ｘ≦０.１、０≦ｙ≦１、−０.１≦ｄ≦１である）
グレイン径が数十ミクロンのオーダーであることを特徴とする、熱電変換材料。
＜２＞次の一般式で表される、グレイン径が数十ミクロンのオーダーである熱電変換材料の製造方法であって、
Ｍｇ3-x+dＹxＳｂ2-yＢｉy
（式中、０＜ｘ≦０.１、０≦ｙ≦１、−０.１≦ｄ≦１である）
それぞれ上記一般式で規定する組成となるように秤量したＭｇ、Ｙ、Ｓｂ及びＢｉを混合し、加熱して、溶融させた後、冷却し、得られた溶融体を粉砕し、ホットプレスにより焼結することによって、緻密な焼結体として得ることを特徴とする、熱電変換材料の製造方法。
＜３＞＜１＞に記載の熱電変換材料を含む熱電変換素子。
The present invention has been completed based on the findings obtained in the above-mentioned tests and research processes, and the following inventions are provided in this case.
<1> A thermoelectric conversion material represented by the following general formula.
Mg 3-x + d Y x Sb 2-y By y
(In the formula, 0 <x ≦ 0.1, 0 ≦ y ≦ 1, −0.1 ≦ d ≦ 1)
A thermoelectric conversion material characterized by a grain diameter on the order of several tens of microns.
<2> A method for producing a thermoelectric conversion material having a grain diameter on the order of several tens of microns, which is represented by the following general formula.
Mg 3-x + d Y x Sb 2-y By y
(In the formula, 0 <x ≦ 0.1, 0 ≦ y ≦ 1, −0.1 ≦ d ≦ 1)
Mg, Y, Sb and Bi weighed so as to have the compositions specified by the above general formulas are mixed, heated and melted, then cooled, the obtained melt is crushed and baked by hot pressing. A method for producing a thermoelectric conversion material, which comprises obtaining a dense sintered body by binding.
<3> A thermoelectric conversion element containing the thermoelectric conversion material according to <1>.
本発明の製造方法により、従来技術による同様の組成の焼結体よりもグレインサイズが大きい焼結体からなる熱電変換材料が得られる。本発明の熱電変換材料は、１５０℃程度以下の比較的低い温度領域において、当該従来技術の熱電変換材料よりも、より高いＺＴ値を有し、当該温度領域において、熱電変換材料として、より優れた特性を有するものであり、特に環境からの排熱や人体の体温などの日常的な熱から電力を回収し、有効利用する上で、優れた効果を有するものである。 According to the production method of the present invention, a thermoelectric conversion material made of a sintered body having a larger grain size than a sintered body having a similar composition according to the prior art can be obtained. The thermoelectric conversion material of the present invention has a higher ZT value than the thermoelectric conversion material of the prior art in a relatively low temperature region of about 150 ° C. or less, and is more excellent as a thermoelectric conversion material in the temperature region. It has the above-mentioned characteristics, and in particular, it has an excellent effect in recovering electric power from daily heat such as exhaust heat from the environment and body temperature of the human body and effectively using it.
本発明の熱電変換材料は、従来のＭｇ3Ｓｂ2を基本構造とする熱電変換材料におけるＭｇイオンサイトの一部をＹイオンで置換することによって電子をドープすることにより得られる、グレイン径が数十ミクロンのオーダーの焼結体からなるものであり、その組成は、次の一般式で表される。
Ｍｇ3-x+dＹxＳｂ2-yＢｉy
（式中、０＜ｘ≦０.１、０≦ｙ≦１、−０.１≦ｄ≦１である)
The thermoelectric conversion material of the present invention has a number of grain diameters, which is obtained by doping electrons by substituting a part of Mg ion sites with Y ions in a conventional thermoelectric conversion material having a basic structure of Mg 3 Sb 2. It is composed of sintered bodies on the order of 10 microns, and its composition is expressed by the following general formula.
Mg 3-x + d Y x Sb 2-y By y
(In the formula, 0 <x ≦ 0.1, 0 ≦ y ≦ 1, −0.1 ≦ d ≦ 1)
本発明の熱電変換材料は、出発原料として各構成元素の単体金属を前記の化学組成となるように混合した混合物を加熱溶融して、溶融体を得、これを粉砕後、得られた粉体を焼結して製造することができる。 The thermoelectric conversion material of the present invention is obtained by heating and melting a mixture of elemental metals of each constituent element as a starting material so as to have the above chemical composition to obtain a melt, which is pulverized, and then the obtained powder. Can be produced by sintering.
具体的には、前記化学組成となるように混合された混合粉末を高温に加熱して、溶融体を得る。得られた溶融体を粉砕し、再度ホットプレス装置などを用いて焼結体とする。
前記混合粉末の加熱温度は、混合粉末が溶融し、溶融体が得られる温度であり、各単体金属の混合比率によって変化するが、６００℃以上、例えば１０００℃〜１４００℃程度の温度であることが適切である。
また、前記ホットプレスの条件は、３０ＭＰａ以上、例えば３０ＭＰａ〜９０ＭＰａ程度の圧力、４００〜７００℃程度の温度で、２０分以上、例えば１〜４時間程度の時間、行うことが好ましい。
Specifically, the mixed powder mixed so as to have the above chemical composition is heated to a high temperature to obtain a melt. The obtained melt is crushed and again used in a hot press or the like to obtain a sintered body.
The heating temperature of the mixed powder is a temperature at which the mixed powder is melted to obtain a melt, and varies depending on the mixing ratio of each elemental metal, but is 600 ° C. or higher, for example, about 1000 ° C. to 1400 ° C. Is appropriate.
The hot press conditions are preferably 30 MPa or more, for example, a pressure of about 30 MPa to 90 MPa, a temperature of about 400 to 700 ° C., and 20 minutes or more, for example, about 1 to 4 hours.
次に、実施例により本発明を更に詳細に説明するが、本発明はこれらの実施例により何ら限定されない。 Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
＜実施例１＞熱電変換材料Ｍｇ3-x+dＹxＳｂ2-yＢｉyの製造
本実施例では、熱電変換材料の合成の出発原料としてアルカリ土類金属を取り扱うため、基本的なハンドリングは全てアルゴン雰囲気のグローブボックス内で行った。
<Example 1> Manufacture of thermoelectric conversion material Mg 3-x + d Y x Sb 2-y Biy In this example, alkaline earth metals are used as a starting material for the synthesis of thermoelectric conversion materials, so the basic handling is All went in a glove box with an argon atmosphere.
（Ｍｇ3-x+dＹxＳｂ2-yＢｉyの合成）
本実施例では、出発原料として、純度９９.９％のＭｇ（粒径３−７ｍｍ）、純度９９.９９９９％のＳｂ(ショット)、純度９９.９９９９％のＢｉ（ショット）及び純度９９.９％のＹ（−２０ｍｅｓｈ）を使用した。これらを後述の表１に示す各仕込み組成となるように秤量して、各秤量物を調製した。Ｍｇのみアルミナタンマン管への充填密度の向上を目的に軽く粉砕を行っている。各秤量物をアルミナタンマン管の中に入れ、それをＳＵＳ３１６Ｌのステンレス鋼パイプ中に密封した。パイプ中に密封した出発原料をマッフル炉に入れ、９００℃で５時間熱処理を行なった後、１１８０℃まで温度を上げ１０分保持後、１０℃／Ｈｒの降温レートにて室温まで温度を下げた。
得られた溶融体をそれぞれ粉末状に粉砕した後、７０ＭＰａ、６００℃、１時間保持の条件でホットプレスして緻密な焼結体を得た。
図１に、得られた焼結体の光学顕微鏡写真像を示す。図１から、当該焼結体が、平均２０〜４０ミクロン程度の、数十ミクロンオーダーのグレイン径を有する粒子が焼結してなるものであることが観察される。
(Synthesis of Mg 3-x + d Y x Sb 2-y Biy)
In this example, as starting materials, Mg with a purity of 99.9% (particle size 3-7 mm), Sb (shot) with a purity of 99.99999%, Bi (shot) with a purity of 99.99999%, and purity 99.9 % Y (-20 mesh) was used. These were weighed so as to have each of the charged compositions shown in Table 1 described later, and each weighed product was prepared. Only Mg is lightly pulverized for the purpose of improving the filling density of the alumina tanman tube. Each weighing material was placed in an alumina tanman tube and sealed in a SUS316L stainless steel pipe. The starting material sealed in the pipe was placed in a muffle furnace, heat-treated at 900 ° C. for 5 hours, then raised to 1180 ° C. and held for 10 minutes, and then lowered to room temperature at a temperature lowering rate of 10 ° C./Hr. ..
The obtained melts were pulverized into powders and then hot-pressed under the conditions of holding at 70 MPa, 600 ° C. for 1 hour to obtain a dense sintered body.
FIG. 1 shows an optical micrograph image of the obtained sintered body. From FIG. 1, it is observed that the sintered body is obtained by sintering particles having a grain diameter on the order of several tens of microns, which is about 20 to 40 microns on average.
＜実施例２＞熱電変換材料Ｍｇ3-x+dＹxＳｂ2-yＢｉyの熱電特性の測定
得られた各焼結体について熱電特性を測定した。
電気抵抗及びゼーベック係数はアドバンス理工（株）のＺＥＭ-３を用いて測定した。測定温度範囲は室温から５００℃、測定中のガス雰囲気はアルゴンガス雰囲気、電流５０ｍＡ、試料両端にかかる温度差は約５℃とした。測定試料の形状はおよそ１.５ｍｍ×２.０ｍｍ×８.０ｍｍである。
熱伝導率はＮＥＴＺＳＣＨのＬＦＡ４５７を用いてレーザーフラッシュ法により測定した。測定温度範囲は室温から７００℃、ガス雰囲気はアルゴンガスとした。測定試料の形状は直径１０ｍｍ、厚さ２.０ｍｍである。
各焼結体について得られた電気抵抗、ゼーベック係数及び熱伝導率からＺＴを導出した。
表１に、本発明の方法により得られた各焼結体における各金属成分の仕込み組成、及び得られた焼結体のＺＴの最大値を示す。
<Example 2> Measurement of thermoelectric characteristics of thermoelectric conversion material Mg 3-x + d Y x Sb 2-y Biy The thermoelectric characteristics of each of the obtained sintered bodies were measured.
The electrical resistance and Seebeck coefficient were measured using ZEM-3 of Advance Riko Co., Ltd. The measurement temperature range was room temperature to 500 ° C., the gas atmosphere during measurement was an argon gas atmosphere, the current was 50 mA, and the temperature difference between both ends of the sample was about 5 ° C. The shape of the measurement sample is approximately 1.5 mm × 2.0 mm × 8.0 mm.
The thermal conductivity was measured by the laser flash method using LFA457 of NETZSCH. The measurement temperature range was room temperature to 700 ° C., and the gas atmosphere was argon gas. The shape of the measurement sample is 10 mm in diameter and 2.0 mm in thickness.
ZT was derived from the electrical resistance, Seebeck coefficient and thermal conductivity obtained for each sintered body.
Table 1 shows the charged composition of each metal component in each sintered body obtained by the method of the present invention, and the maximum value of ZT of the obtained sintered body.
また、図２に、表１において最大のＺＴ値が得られた仕込み組成Ｍｇ3.5Ｙ0.02Ｓｂ1.5Ｂｉ0.5の焼結体における、各測定温度に対するＺＴ値の変化の様子を示す。 Further, FIG. 2 shows the change in the ZT value with respect to each measurement temperature in the sintered body having the charged composition Mg 3.5 Y 0.02 Sb 1.5 Bi 0.5 in which the maximum ZT value was obtained in Table 1.
Claims (3)
Ｍｇ3-x+dＹxＳｂ2-yＢｉy
（式中、０＜ｘ≦０.１、０≦ｙ≦１、−０.１≦ｄ≦１である）
グレイン径が数十ミクロンのオーダーであることを特徴とする、熱電変換材料。 It is a thermoelectric conversion material represented by the following general formula.
Mg 3-x + d Y x Sb 2-y By y
(In the formula, 0 <x ≦ 0.1, 0 ≦ y ≦ 1, −0.1 ≦ d ≦ 1)
A thermoelectric conversion material characterized by a grain diameter on the order of several tens of microns.
Ｍｇ3-x+dＹxＳｂ2-yＢｉy
（式中、０＜ｘ≦０.１、０≦ｙ≦１、−０.１≦ｄ≦１である)
それぞれ上記一般式で規定する組成となるように秤量したＭｇ、Ｙ、Ｓｂ及びＢｉを混合し、加熱して、溶融させた後、冷却し、得られた溶融体を粉砕し、ホットプレスにより焼結することによって、緻密な焼結体として得ることを特徴とする、上記熱電変換材料の製造方法。 A method for producing a thermoelectric conversion material having a grain diameter on the order of several tens of microns, which is expressed by the following general formula.
Mg 3-x + d Y x Sb 2-y By y
(In the formula, 0 <x ≦ 0.1, 0 ≦ y ≦ 1, −0.1 ≦ d ≦ 1)
Mg, Y, Sb and Bi weighed so as to have the compositions specified by the above general formulas are mixed, heated and melted, then cooled, the obtained melt is crushed and baked by hot pressing. The method for producing a thermoelectric conversion material, which comprises obtaining a dense sintered body by binding.
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| CN112921205A (en) * | 2021-01-26 | 2021-06-08 | 广西大学 | Rapid preparation of high thermoelectric property n-type Mg3Sb2Method for producing base material |
| CN113121234A (en) * | 2021-04-09 | 2021-07-16 | 中国科学院电工研究所 | Mg3Sb 2-based thermoelectric material with high-temperature stability and preparation method thereof |
| CN113488578A (en) * | 2021-06-29 | 2021-10-08 | 同济大学 | Low-grade waste heat recovery antimonide thermoelectric module with high conversion efficiency and preparation method thereof |
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