WO2017072982A1 - 熱電変換材料 - Google Patents
熱電変換材料 Download PDFInfo
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Definitions
- the present invention relates to a thermoelectric conversion material.
- Non-Patent Document 2 discloses a thermoelectric conversion material represented by the chemical formula Mg 3 Sb 2-x Bi x (0 ⁇ x ⁇ 0.4).
- Non-Patent Document 3 discloses a thermoelectric conversion material represented by the chemical formula Mg 3-x Mn x Sb 2 (0 ⁇ x ⁇ 0.4).
- An object of the present invention is to provide a novel thermoelectric conversion material.
- thermoelectric conversion material represented by the following chemical formula (I). Mg 3 + m A a B b D 2-e E e (I) here, Element A represents at least one selected from the group consisting of Ca, Sr, Ba, and Yb, Element B represents at least one selected from the group consisting of Mn and Zn, The value of m is ⁇ 0.39 or more and 0.42 or less, The value of a is 0 or more and 0.12 or less, The value of b is 0 or more and 0.48 or less, Element D represents at least one selected from the group consisting of Sb and Bi, The element E represents at least one selected from the group consisting of Se and Te, The value of e is 0.001 or more and 0.06 or less,
- the thermoelectric conversion material has a La 2 O 3 type crystal structure, and the thermoelectric conversion material is n-type.
- the present invention provides a novel thermoelectric conversion material.
- FIG. 1 shows a schematic diagram of a La 2 O 3 type crystal structure.
- Figure 2A is a graph showing the diffraction spectrum analysis result of La 2 O 3 type crystal structure.
- 2B is a graph showing the results of X-ray diffraction analysis of the thermoelectric conversion material according to Example 1.
- FIG. 2C is a graph showing the results of X-ray diffraction analysis of the thermoelectric conversion material according to Example 6.
- FIG. 3 is a graph showing the relationship between the temperature and the thermoelectric conversion performance index ZT of the thermoelectric conversion materials according to Example 1, Example 6, and Comparative Example 1.
- FIG. 4 is a graph showing the relationship between the temperature and the Seebeck coefficient S of the thermoelectric conversion materials according to Example 1, Example 6, and Comparative Example 1.
- FIG. 5 is a graph showing an analysis result of energy dispersive X-ray spectroscopy in Example 1.
- 6 is a diagram showing a transmission electron microscope image of the thermoelectric conversion material according to Example 1.
- thermoelectric conversion material according to the present invention is represented by the following chemical formula (I).
- Element A represents at least one selected from the group consisting of Ca, Sr, Ba, and Yb
- Element B represents at least one selected from the group consisting of Mn and Zn
- the value of m is ⁇ 0.39 or more and 0.21 or less
- the value of a is 0 or more and 0.12 or less
- the value of b is 0 or more and 0.48 or less
- Element D represents at least one selected from the group consisting of Sb and Bi
- the element E represents at least one selected from the group consisting of Se and Te
- the value of e is 0.001 or more and 0.06 or less.
- the thermoelectric conversion material according to the present invention has a La 2 O 3 type crystal structure and is n-type.
- thermoelectric conversion material according to the present invention does not necessarily contain the element A.
- thermoelectric conversion material according to the present invention does not necessarily contain the element B.
- thermoelectric conversion material according to the present invention must contain the element Mg, the element D, and the element E.
- thermoelectric conversion material according to the present invention is characterized by both containing the element E and having a value of e of 0.001 or more and 0.06 or less.
- thermoelectric conversion materials As is well known in the technical field of thermoelectric conversion materials, the performance of thermoelectric conversion materials is represented by a thermoelectric conversion performance index ZT and Seebeck coefficient S. As demonstrated in Examples 1 to 4 and Comparative Examples 1 to 2 described later, when the value of e is 0.001 or more and 0.06 or less, the performance of the thermoelectric conversion material is dramatically improved. To improve. See Table 3. Further, such a thermoelectric conversion material is n-type. On the other hand, as demonstrated in Comparative Example 1, when the value of e is equal to 0, the thermoelectric conversion material has low performance and is p-type. When the value of e exceeds 0.06, the performance of the thermoelectric conversion material is also low. Desirably, the value of e is 0.004 or more and 0.020 or less.
- thermoelectric conversion material according to the present invention has a La 2 O 3 type crystal structure.
- FIG. 1 shows a schematic diagram of a La 2 O 3 type crystal structure.
- the thermoelectric conversion material according to the present invention may be monocrystalline or polycrystalline.
- the value of m is ⁇ 0.39 or more and 0.42 or less. See Example 26 and Example 29 below.
- the value of m can be between ⁇ 0.39 and 0.21.
- m m′ ⁇ a ⁇ b (II) here, m ′ is 0 or more and 0.42 or less.
- m ′ is 0 or more and 0.42 or less.
- thermoelectric conversion material An example of a method for producing a thermoelectric conversion material according to the present invention will be described below.
- an antimony-bismuth alloy is obtained by dissolving antimony and bismuth in an arc melting method at a temperature of 1000 degrees Celsius to 1500 degrees Celsius.
- an antimony-bismuth alloy, magnesium powder, and selenium powder are charged into the crucible.
- the crucible is heated to a temperature of 800 degrees Celsius to 1500 degrees Celsius to obtain an MgSbBiSe alloy.
- thermoelectric conversion material rarely matches the molar ratio of the starting material.
- the MgSbBiSe alloy is subjected to spark plasma sintering to obtain MgSbBiSe crystals. In this way, a thermoelectric conversion material formed from MgSbBiSe crystals is obtained.
- Example 1 (Production method)
- a thermoelectric conversion material represented by the chemical formula Mg 3.08 Sb 1.49 Bi 0.49 Se 0.02 and having a La 2 O 3 crystal structure was produced as follows.
- Example 1 magnesium powder (2.33 grams, 0.096 mole) and selenium powder (0.0474 grams, 0.0006 mole) were added to the Sb—Bi powder. These powders were thoroughly mixed.
- Sb: Bi: Se molar ratio was 0.096: 0.045: 0.0144: 0.0006, ie 3.2: 1.5: 0.48. : 0.02.
- the mixed powder was subjected to a tableting machine to obtain a tablet.
- the tablet was put into a carbon crucible.
- the carbon crucible was filled with argon gas.
- the tablet was heated for 10 seconds at a temperature of 800-1000 degrees Celsius. In this way, the tablet was melted to obtain an ingot.
- the ingot was thrown into a mortar placed in a glove box filled with argon.
- the ingot was pulverized in a glove box to obtain MgSbBiSe powder.
- Each powder had a particle size of 100 ⁇ m or less.
- the powder was sintered by the following spark plasma sintering method (hereinafter referred to as “SPS method”).
- SPS method spark plasma sintering method
- the powder was filled into a cylindrical die formed from graphite.
- the cylindrical die had an outer diameter of 50 millimeters and an inner diameter of 10 millimeters.
- Argon gas was supplied to the cylindrical die. While a pressure of 50 MPa was applied to the material filled in the cylindrical die, a pulse current was passed through the material. In this way, the temperature of the material filled in the cylindrical die was increased at a rate of approximately 20 degrees Celsius / minute. The temperature of the material was maintained at 600 degrees Celsius for 30 minutes. Subsequently, the temperature of the material was lowered to room temperature, and a dense sintered body was obtained.
- the thermoelectric conversion material according to Example 1 was obtained.
- thermoelectric conversion material according to Example 1 was analyzed by energy dispersive X-ray spectroscopy (hereinafter referred to as “EDX”). Specifically, the thermoelectric conversion material according to Example 1 was supplied to an X-ray spectrometer (manufactured by Bruker, trade name: XFlash6
- FIG. 5 is a graph showing the results of EDX in Example 1. From FIG. 5, it was revealed that the thermoelectric conversion material according to Example 1 had a composition of Mg 3.08 Sb 1.49 Bi 0.49 Se 0.02 .
- FIG. 2B shows the result.
- FIG. 2A shows a La 2 O 3 type crystal structure having an a-axis lattice constant of 0.460 nanometers, a b-axis lattice constant of 0.460 nanometers, and a c-axis lattice constant of 0.729 nanometers ( or is a graph showing the X-ray diffraction spectrum of CaAl 2 Si 2 -type structure).
- the peaks included in the diffraction spectrum in Example 1 coincide with the diffraction peaks in FIG. 2A. Therefore, FIG. 2B reveals that the thermoelectric conversion material according to Example 1 has a La 2 O 3 type crystal structure.
- thermoelectric conversion material according to Example 1 shows a transmission electron microscope image of the thermoelectric conversion material according to Example 1.
- FIG. 6 The atomic arrangement period of the crystal grains included in the La 2 O 3 type crystal structure having the above three lattice constants coincided with the atomic arrangement period defined along the orientation direction shown in FIG.
- the thermoelectric conversion material according to Example 1 was a polycrystalline body having a La 2 O 3 type structure.
- Table 1 below shows the Seebeck coefficient S and the thermoelectric conversion performance index ZT of the thermoelectric conversion material according to Example 1.
- Table 1 shows the Seebeck coefficient S and the thermoelectric conversion performance index ZT of the thermoelectric conversion material according to Example 1.
- thermoelectric conversion material according to Example 1 is n-type.
- the thermoelectric conversion material according to Example 1 has a high thermoelectric conversion performance index ZT of 0.58 even at a temperature of 331K.
- thermoelectric conversion material according to Example 1 has a high thermoelectric conversion figure of merit ZT of 1.49 at a temperature of 713K.
- Comparative Example 1 Granular antimony, granular bismuth, magnesium powder, and selenium powder each weigh 5.48 grams (ie 0.045 mole), 3.13 grams (ie 0.015 mole), 2.33 grams (ie 0.096 mol), and 0 grams (ie, 0 mol).
- the same experiment as in Example 1 was performed. Note that selenium was not used in Comparative Example 1.
- a thermoelectric conversion material represented by the chemical formula Mg 3.07 Sb 1.47 Bi 0.53 was obtained.
- the starting Mg: Sb: Bi: Se molar ratio was 0.096: 0.045: 0.015: 0, ie 3.2: 1.5: 0.5: 0. there were.
- Table 2 below shows the Seebeck coefficient S and the thermoelectric conversion performance index ZT of the thermoelectric conversion material according to Comparative Example 1.
- thermoelectric conversion material formed from the MgD alloy not containing Se is p-type. Addition of Se to the MgD alloy dramatically improves the thermoelectric conversion performance index ZT. Moreover, the addition of Se to the MgD alloy causes the value of the Seebeck coefficient S to be negative. This means that the addition of Se to the MgD alloy makes the thermoelectric conversion material n-type.
- Example 2 to 4 and Comparative Example 2 In Examples 2 to 4 and Comparative Example 2, the same experiment as in Example 1 except that the molar ratio of the starting material Mg: Sb: Bi: Se was the molar ratio shown in Table 3. Was done.
- thermoelectric conversion material that is, the molar ratio of Se contained in the thermoelectric conversion material
- e that is, the molar ratio of Se contained in the thermoelectric conversion material
- Comparative Example 1 when the value of e is equal to 0, the thermoelectric conversion material is p-type.
- Comparative Example 2 when the value of e is equal to 0.08, the values of ZT max , ZT 330K , and S 330K are all low. This means that the thermoelectric conversion material according to Comparative Example 2 has low performance.
- Example 5 to 8 and Comparative Example 3 In Examples 5 to 8 and Comparative Example 3, Te was used instead of Se.
- the same experiment as in Example 1 was performed except that the molar ratio of the starting material Mg: Sb: Bi: Te was the molar ratio shown in Table 4.
- the thermoelectric conversion material according to Example 6 was subjected to X-ray diffraction analysis.
- FIG. 2C shows the result.
- FIG. 2B that is, Example 1
- FIG. 2C revealed that the thermoelectric conversion material according to Example 6 also has a La 2 O 3 type crystal structure.
- FIG. 2C revealed that the thermoelectric conversion material containing Te instead of Se also has a La 2 O 3 type crystal structure.
- the value of e (that is, the molar ratio of Te contained in the thermoelectric conversion material) is preferably 0.001 or more and 0.04 or less. Considering Table 3, even when Te is used instead of Se, if the value of e is 0.06 or less, the thermoelectric conversion material will have high performance. As is clear from Comparative Example 3, when the value of e is equal to 0.09, the values of ZT max , ZT 330K , and S 330K are all low. This means that the thermoelectric conversion material according to Comparative Example 3 has low performance.
- Example 9 to 12 In Examples 9 to 12, the same experiment as in Example 1 was performed, except that the molar ratio of the starting material Mg: Sb: Bi: Se was the molar ratio shown in Table 5.
- thermoelectric conversion material according to the present invention has high performance even when either one of Sb and Bi is not contained.
- thermoelectric conversion materials according to Examples 13 to 20 and Comparative Example 4 further contained at least one selected from the group consisting of Ca, Sr, Ba, and Yb.
- the starting Mg: A: Sb: Bi: Se molar ratio A is selected from the group consisting of Ca, Sr, Ba, and Yb.
- the same experiment as in Example 1 was conducted except that the molar ratio shown in Table 6 was at least one.
- Ca powder, Sr powder, Ba powder, and Yb powder were dissolved together with granular Bi and granular Sb by an arc melting method.
- thermoelectric conversion material according to the present invention may further contain at least one selected from the group consisting of Ca, Sr, Ba, and Yb.
- thermoelectric conversion materials according to Examples 21 to 26 and Comparative Examples 5 to 6 further contained at least one selected from the group consisting of Mn and Zn.
- the molar ratio of the starting material Mg: B: Sb: Bi: Se B is selected from the group consisting of Mn and Zn.
- the experiment similar to Example 1 was conducted except that the molar ratio shown in Table 7 was at least one).
- the Mn powder was dissolved by the arc melting method together with the granular Bi and the granular Sb. Zn powder was introduced into the carbon crucible with the tablet.
- thermoelectric conversion material according to the present invention can further contain at least one selected from the group consisting of Mn and Zn.
- Example 27 to 29 In Examples 27 to 29, an experiment similar to Example 1 was performed, except that the molar ratio of the starting material Mg: Sb: Bi: Se was the molar ratio shown in Table 8.
- thermoelectric conversion materials according to Examples 27 to 29 also have a high thermoelectric conversion performance index ZT.
- FIG. 3 is a graph showing the relationship between the temperature and the thermoelectric conversion performance index ZT of the thermoelectric conversion materials according to Example 1, Example 6, and Comparative Example 1.
- FIG. 4 is a graph showing the relationship between the temperature and the Seebeck coefficient S of the thermoelectric conversion materials according to Example 1, Example 6, and Comparative Example 1.
- the addition of Se to the MgD alloy dramatically improves the thermoelectric conversion performance index ZT. Moreover, the addition of Se to the MgD alloy causes the value of the Seebeck coefficient S to be negative. This means that the addition of Se to the MgD alloy makes the thermoelectric conversion material n-type.
- thermoelectric conversion material by this invention can be used for the thermoelectric conversion apparatus which converts a thermal energy into an electrical energy.
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Abstract
Description
非特許文献2は、化学式Mg3Sb2-xBix(0≦x≦0.4)により表される熱電変換材料を開示している。
非特許文献3は、化学式Mg3-xMnxSb2(0≦x≦0.4)により表される熱電変換材料を開示している。
Mg3+mAaBbD2-eEe (I)
ここで、
元素Aは、Ca、Sr、Ba、およびYbからなる群から選択される少なくとも1種を表し、
元素Bは、MnおよびZnからなる群から選択される少なくとも1種を表し、
mの値は-0.39以上0.42以下であり、
aの値は0以上0.12以下であり、
bの値は0以上0.48以下であり、
元素Dは、SbおよびBiからなる群から選択される少なくとも1種を表し、
元素Eは、SeおよびTeからなる群から選択される少なくとも1種を表し、
eの値は、0.001以上0.06以下であり、
前記熱電変換材料は、La2O3型の結晶構造を有し、かつ
前記熱電変換材料は、n型である。
本発明による熱電変換材料は、以下の化学式(I)により表される。
Mg3+mAaBbD2-eEe (I)
元素Aは、Ca、Sr、Ba、およびYbからなる群から選択される少なくとも1種を表し、
元素Bは、MnおよびZnからなる群から選択される少なくとも1種を表し、
mの値は-0.39以上0.21以下であり、
aの値は0以上0.12以下であり、
bの値は0以上0.48以下であり、
元素Dは、SbおよびBiからなる群から選択される少なくとも1種を表し、
元素Eは、SeおよびTeからなる群から選択される少なくとも1種を表し、かつ
eの値は、0.001以上0.06以下である。
本発明による熱電変換材料は、La2O3型の結晶構造を有し、かつn型である。
a=b=0 (III)
m=m’-a-b (II)
ここで、
m’は、0以上0.42以下である。
m’の値が0に等しい場合については、実施例26を参照せよ。m’ の値が0.42に等しい場合は、実施例29を参照せよ。
本発明による熱電変換材料の製造方法の一例が、以下、説明される。まず、アンチモン-ビスマス合金が、摂氏1000度~摂氏1500度の温度でアンチモンおよびビスマスをアーク溶解法に溶解させることにより得られる。次に、アンチモン-ビスマス合金、マグネシウム粉末、およびセレン粉末がるつぼに投入される。るつぼが摂氏800度~摂氏1500度の温度に加熱され、MgSbBiSe合金が得られる。
(実施例1)
(製造方法)
実施例1では、化学式Mg3.08Sb1.49Bi0.49Se0.02により表され、かつLa2O3結晶構造を有する熱電変換材料が以下のように製造された。
実施例1による熱電変換材料の化学組成が、エネルギー分散型X線分光法(以下、「EDX」という)により分析された。具体的には、実施例1による熱電変換材料は、X線分光器(Bruker社製、商品名:XFlash6|10)に供された。図5は、実施例1におけるEDXの結果を示すグラフである。図5より、実施例1による熱電変換材料は、Mg3.08Sb1.49Bi0.49Se0.02の組成を有していることが明らかとなった。
実施例1による熱電変換材料は、X線回折分析に供された。図2Bは、その結果を示す。図2Aは、0.460ナノメートルのa軸方向格子定数、0.460ナノメートルのb軸方向格子定数、および0.729ナノメートルのc軸方向格子定数を有するLa2O3型結晶構造(またはCaAl2Si2型構造)のX線回折スペクトルを示すグラフである。実施例1における回折スペクトルに含まれるピークは、図2Aにおける回折ピークと一致する。従って、図2Bより、実施例1による熱電変換材料は、La2O3型結晶構造を有していることが明らかとなった。
実施例1による熱電変換材料は、331Kの温度下でも、0.58という高い熱電変換性能指数ZTを有する。同様に、実施例1による熱電変換材料は、713Kの温度下で1.49という高い熱電変換性能指数ZTを有する。
粒状アンチモン、粒状ビスマス、マグネシウム粉末、およびセレン粉末の重さがそれぞれ5.48グラム(すなわち、0.045モル)、3.13グラム(すなわち、0.015モル)、2.33グラム(すなわち、0.096モル)、および0グラム(すなわち、0モル)であったこと以外は、実施例1と同様の実験が行われた。比較例1ではセレンが用いられなかったことに留意せよ。比較例1では、化学式Mg3.07Sb1.47Bi0.53により表される熱電変換材料が得られた。比較例1において、出発物質のMg:Sb:Bi:Seのモル比は、0.096:0.045:0.015:0、すなわち、3.2:1.5:0.5:0であった。
実施例2~実施例4および比較例2においては、出発物質のMg:Sb:Bi:Seのモル比が、表3に示されるモル比であったこと以外は、実施例1と同様の実験が行われた。
実施例5~実施例8および比較例3においては、Seに代えて、Teが用いられた。出発物質のMg:Sb:Bi:Teのモル比が、表4に示されるモル比であったこと以外は、実施例1と同様の実験が行われた。実施例6による熱電変換材料は、X線回折分析に供された。図2Cは、その結果を示す。図2B(すなわち、実施例1)の場合と同様、図2Cより、実施例6による熱電変換材料もまた、La2O3型結晶構造を有していることが明らかとなった。言い換えれば、図2Cにより、Seに代えてTeを含有する熱電変換材料もまた、La2O3型結晶構造を有していることが明らかとなった。
実施例9~実施例12では、出発物質のMg:Sb:Bi:Seのモル比が、表5に示されるモル比であったこと以外は、実施例1と同様の実験が行われた。
実施例13~実施例20および比較例4による熱電変換材料は、Ca、Sr、Ba、およびYbからなる群から選択される少なくとも1種をさらに含有していた。言い換えれば、実施例13~実施例20および比較例4においては、出発物質のMg:A:Sb:Bi:Seのモル比(Aは、Ca、Sr、Ba、およびYbからなる群から選択される少なくとも1種を表す)が、表6に示されるモル比であったこと以外は、実施例1と同様の実験が行われた。Ca粉末、Sr粉末、Ba粉末、およびYb粉末は、粒状Biおよび粒状Sbと共にアーク溶解法により溶解された。
実施例21~実施例26および比較例5~比較例6による熱電変換材料は、MnおよびZnからなる群から選択される少なくとも1種をさらに含有していた。言い換えれば、実施例21~実施例26および比較例5~比較例6においては、出発物質のMg:B:Sb:Bi:Seのモル比(Bは、MnおよびZnからなる群から選択される少なくとも1種を表す)が、表7に示されるモル比であったこと以外は、実施例1と同様の実験が行われた。Mn粉末は、粒状Biおよび粒状Sbと共にアーク熔解法により溶解された。Zn粉末は、タブレットと共にカーボンるつぼに導入された。
実施例27~実施例29では、出発物質のMg:Sb:Bi:Seのモル比が、表8に示されるモル比であったこと以外は、実施例1と同様の実験が行われた。
Claims (5)
- 以下の化学式(I)により表される熱電変換材料。
Mg3+mAaBbD2-eEe (I)
ここで、
元素Aは、Ca、Sr、Ba、およびYbからなる群から選択される少なくとも1種を表し、
元素Bは、MnおよびZnからなる群から選択される少なくとも1種を表し、
mの値は-0.39以上0.42以下であり、
aの値は0以上0.12以下であり、
bの値は0以上0.48以下であり、
元素Dは、SbおよびBiからなる群から選択される少なくとも1種を表し、
元素Eは、SeおよびTeからなる群から選択される少なくとも1種を表し、
eの値は、0.001以上0.06以下であり、
前記熱電変換材料は、La2O3型の結晶構造を有し、かつ
前記熱電変換材料は、n型である。 - 請求項1に記載の熱電変換材料であって、
以下の数式(II)が充足される
m=m’-a-b (II)
ここで、
aおよびbの値の少なくとも一方が0よりも大きく、かつ
m’の値は、0以上0.21以下である。 - 請求項1に記載の熱電変換材料であって、
eの値が、0.004以上0.020以下である。 - 請求項2に記載の熱電変換材料であって、
eの値が、0.004以上0.020以下である。 - 請求項1に記載の熱電変換材料であって、
以下の数式(III)が充足される。
a=b=0 (III)
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