CN110892537A - 镁系热电转换材料、镁系热电转换元件及镁系热电转换材料的制造方法 - Google Patents
镁系热电转换材料、镁系热电转换元件及镁系热电转换材料的制造方法 Download PDFInfo
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- CN110892537A CN110892537A CN201880047442.8A CN201880047442A CN110892537A CN 110892537 A CN110892537 A CN 110892537A CN 201880047442 A CN201880047442 A CN 201880047442A CN 110892537 A CN110892537 A CN 110892537A
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- magnesium
- thermoelectric conversion
- conversion material
- based thermoelectric
- sintering
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- 239000011777 magnesium Substances 0.000 title claims abstract description 144
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 139
- 239000000463 material Substances 0.000 title claims abstract description 128
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 122
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- 239000002245 particle Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 238000005245 sintering Methods 0.000 claims description 95
- 239000000843 powder Substances 0.000 claims description 59
- 239000002994 raw material Substances 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052787 antimony Inorganic materials 0.000 claims description 12
- 239000002019 doping agent Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 230000002093 peripheral effect Effects 0.000 claims description 9
- 150000002681 magnesium compounds Chemical class 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910019739 Mg2Si1-xSnx Inorganic materials 0.000 claims description 4
- 229910006990 Si1-xGex Inorganic materials 0.000 claims description 4
- 229910007020 Si1−xGex Inorganic materials 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- YTHCQFKNFVSQBC-UHFFFAOYSA-N magnesium silicide Chemical compound [Mg]=[Si]=[Mg] YTHCQFKNFVSQBC-UHFFFAOYSA-N 0.000 description 34
- 229910021338 magnesium silicide Inorganic materials 0.000 description 34
- 238000010248 power generation Methods 0.000 description 16
- 238000004453 electron probe microanalysis Methods 0.000 description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 230000005678 Seebeck effect Effects 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000005679 Peltier effect Effects 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910000953 kanthal Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 2
- 239000011863 silicon-based powder Substances 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910019752 Mg2Si Inorganic materials 0.000 description 1
- 229910017625 MgSiO Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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Abstract
一种镁系热电转换材料(11),其由镁系化合物的烧结体形成,该镁系热电转换材料(11)的特征在于,在所述烧结体的截面中,在镁系化合物粒子的晶界局部存在Si浓度高于所述镁系化合物粒子的内部的富含Si金属相(15),富含Si金属相(15)所占的面积率在2.5%以上且10%以下的范围内,面积为1μm2以上的富含Si金属相(15)的数密度在1800个/mm2以上且14000个/mm2以下的范围内。
Description
技术领域
本发明涉及一种热电转换效率优异的镁系热电转换材料、使用了该镁系热电转换材料的镁系热电转换元件及镁系热电转换材料的制造方法。
本申请主张基于2017年8月15日于日本申请的专利申请2017-156729号的优先权,并将其内容援用于此。
背景技术
热电转换元件为塞贝克效应、珀尔帖效应之类的、能够将热和电相互转换的电子元件。塞贝克效应为将热能转换为电能的效果,并且为若在热电转换材料的两端产生温差则产生电动势的现象。这种电动势根据热电转换材料的特性来确定。近年来,正积极开发利用了该效果的热电发电。
另一方面,珀尔帖效应为将电能转换为热能的效果,并且为若在热电转换材料的两端形成电极等而在电极之间产生电位差,则在热电转换材料的两端产生温差的现象。尤其,将具有这种效果的元件称为珀尔帖元件,并且用于精密设备、小型冰箱等的冷却、温度控制(例如,参考专利文献1)。
近年来,使用利用了塞贝克效应的热电发电装置来有效利用废热的技术备受瞩目。例如,提出了如下内容:在汽车发动机废气的排放管、工厂、成套设备等中的供高温流体流动的管道的壁面安装使用了这种塞贝克元件的热电发电装置,并且在热电发电装置的另一个表面安装散热器等热交换部件而进行散热,由此将这些管道的热转换为电力而利用。
作为这种热电发电装置,例如,已知有一种如下热电发电装置,即,将内置有进行了模块化的多个热电转换元件的筒状热电发电装置以垂直的方式配置于供废气及冷却水通过的一个通道中,在各热电发电装置的内部形成供冷却水或废气通过的另一个通道,并利用并列的多个筒状热电发电单元的内部与外部的温差来进行热电发电(例如,参考专利文献2)。
并且,还已知有一种热电发电系统,其中,在内置分别进行了模块化的多个热电转换元件的筒状热电发电装置上安装鳍片而进行盒式化,并且并列配置多个经盒式化的热电发电装置(例如,参考专利文献3)。
专利文献1:日本特开2011-249742号公报(A)
专利文献2:日本特表2012-533972号公报(A)
专利文献3:美国专利申请公开第2013/0186448号(A)说明书
然而,如上述的专利文献1~3中所记载那样的、用于热电发电元件的现有的热电转换材料具有如下问题:热电转换效率低,且为了产生必要的电力而需要大面积的热电发电元件。
发明内容
该发明是鉴于前述的情况而完成的,目的在于提供一种高热电转换效率的镁系热电转换材料、使用了该镁系热电转换材料的镁系热电转换元件及镁系热电转换材料的制造方法。
为了解决上述课题,本发明采取以下方案。
本发明的一方案的镁系热电转换材料(以下,称为“本发明的镁系热电转换材料”)由镁系化合物的烧结体形成,该镁系热电转换材料的特征在于,在所述烧结体的截面中,在镁系化合物粒子的晶界局部存在Si浓度高于所述镁系化合物粒子的内部的富含Si金属相,所述富含Si金属相所占的面积率在2.5%以上且10%以下的范围内,面积为1μm2以上的所述富含Si金属相的数密度在1800个/mm2以上且14000个/mm2以下的范围内。
由镁系化合物的烧结体形成的镁系热电转换材料中,在镁系化合物的晶界形成并存在MgO。该MgO的导电率低。因此,有可能在通常的镁系热电转换材料中,晶界处的电阻增加,镁系热电转换材料的热电转换效率下降。
本发明的镁系热电转换材料中,在镁系化合物的晶界局部存在Si浓度高于所述镁系化合物粒子的内部的富含Si金属相。由于该富含Si金属相的导电率高于MgO,因此在本发明的镁系热电转换材料中,晶界处的电阻比通常低。由此,能够提高镁系热电转换材料的热电转换效率。
并且,本发明的镁系热电转换材料中,所述富含Si金属相所占的面积率在2.5%以上且10%以下的范围内,面积为1μm2以上的所述富含Si金属相的数密度在1800个/mm2以上且14000个/mm2以下的范围内。因此,导电率比较高的富含Si金属相被均匀且充分地分散于整个镁系化合物的烧结体中,能够提高镁系热电转换材料的热电转换效率。
在此,本发明的镁系热电转换材料中,所述镁系化合物优选为MgxSiy、Mg2Si1-xGex、Mg2Si1-xSnx中的任意一种。
在该情况下,在包含MgxSiy、Mg2Si1-xGex、Mg2Si1-xSnx的烧结体的晶界局部存在Si浓度高于所述镁系化合物粒子的内部的富含Si金属相,由此能够获得热电转换效率优异的镁系热电转换材料。
并且,本发明的镁系热电转换材料可以包含Li、Na、K、B、Al、Ga、In、N、P、As、Sb、Bi、Ag、Cu、Y中的至少一种以上作为掺杂剂。
在该情况下,能够设为特定的半导体型(即,n型或p型)的热电转换材料。
本发明的镁系热电转换元件的特征在于,具备上述镁系热电转换材料及电极,所述电极分别与所述镁系热电转换材料的一个表面及与其对向的另一个表面接合。
根据本发明的镁系热电转换元件,由于包含上述的镁系热电转换材料,因此能够获得晶界处的电阻低且热电转换效率优异的镁系热电转换元件。
作为本发明的另一方案的镁系热电转换材料的制造方法(以下,称为“本发明的镁系热电转换材料的制造方法”)中,该镁系热电转换材料由镁系化合物的烧结体形成,该镁系热电转换材料的制造方法的特征在于,具备:烧结原料粉末形成工序,在镁系化合物的原料粉末中混合硅氧化物而获得烧结原料粉末;及烧结工序,一边对所述烧结原料粉末进行加压一边进行加热而形成烧结体,在所述烧结工序中,使用通电加热法,在烧结时以规定的时间间隔变更一对电极部的极性,所述通电加热法中,一边用一对电极部对所述烧结原料粉末进行加压一边进行通电。
根据该结构的镁系热电转换材料的制造方法,设为如下结构:在所述烧结工序中,使用一边用一对电极对所述烧结原料粉末进行加压一边进行通电的通电加热法,在烧结时以规定的时间间隔变更一对电极部的极性。因此,在一个电极部的附近和另一个电极部的附近的自身发热状态中不容易产生差异,烧结体被均匀地烧结。其结果,能够使Si浓度高于镁系化合物粒子的内部的富含Si金属相相对均匀地分散于整个烧结体中,从而能够获得热电转换效率优异的镁系热电转换材料。
在此,本发明的镁系热电转换材料的制造方法中,优选设为如下结构,在所述烧结工序中,通过配置于所述烧结原料粉末的外周侧的加热器,进一步对所述烧结原料粉末进行加热。
在该情况下,与通电加热一起通过配置于所述烧结原料粉末的外周侧的加热器进行加热,因此能够减小烧结原料的内周侧与外周侧的温差,能够对烧结原料进一步均匀地进行加热。
根据本发明,能够提供一种高热电转换效率的镁系热电转换材料、使用了该镁系热电转换材料的镁系热电转换元件及镁系热电转换材料的制造方法。
附图说明
图1是表示作为本发明的一实施方式的热电转换材料及使用了该热电转换材料的热电转换元件的剖视图。
图2是表示作为本发明的一实施方式的热电转换材料的截面观察结果的图。
图3是表示作为本发明的一实施方式的热电转换材料的制造方法的流程图。
图4是表示作为本发明的一实施方式的热电转换材料的制造方法中所使用的烧结装置的一例的剖视图。
图5A是在实施例中例示通过EPMA观察镁系热电转换材料的截面而得的结果的照片。
图5B是在实施例中例示通过EPMA观察镁系热电转换材料的截面而得的结果的照片。
图6是表示在实施例中对富含Si金属相进行俄歇电子能谱分析而得的结果的图。
具体实施方式
以下,参考附图对作为本发明的一实施方式的镁系热电转换材料、镁系热电转换元件及镁系热电转换材料的制造方法进行说明。另外,关于以下所示的各实施方式,为了更好地理解发明的宗旨而具体地进行说明,只要无特别说明,则并不限定本发明。并且,以下说明中所使用的附图中,为了易于理解本发明的特征,为了方便起见,有时放大示出成为主要部分的部分,各构成要件的尺寸比率等不一定与实际相同。
在图1中示出作为本发明的实施方式的镁系热电转换材料11及使用了该镁系热电转换材料11的镁系热电转换元件10。
该镁系热电转换元件10具备作为本实施方式的镁系热电转换材料11、形成于该镁系热电转换材料11的一个表面11a及与其对向的另一个表面11b的金属化层18a、18b以及层叠于该金属化层18a、18b的电极19a、19b。
金属化层18a、18b中使用镍、银、钴、钨、钼等。该金属化层18a、18b能够通过通电烧结、电镀、电沉积等来形成。
电极19a、19b由导电性优异的金属材料、例如铜、铝等的板材形成。本实施方式中,使用铝的轧制板。并且,热电转换材料11(金属化层18a、18b)和电极19a、19b能够通过Ag钎焊、镀Ag等而接合。
并且,镁系热电转换材料11被设为镁系化合物的烧结体,在本实施方式中,被设为在硅化镁(Mg2Si)中添加了锑(Sb)作为掺杂剂的材料。例如,本实施方式的镁系热电转换材料11被设为在Mg2Si中包含0.1原子%以上且2.0原子%以下的范围内的锑的组成。另外,本实施方式的镁系热电转换材料11中,通过添加作为5价供体的锑而设为高载流子密度的n型热电转换材料。
另外,作为构成热电转换材料11的材料,还能够同样地使用Mg2SiXGe1-X、Mg2SiXSn1-x等在硅化镁中添加其他元素而得的化合物。
并且,作为用于将镁系热电转换材料11设为n型热电转换元件的供体,除了锑(Sb)以外,还能够使用铋(Bi)、铝(Al)、磷(P)、砷(As)等。
并且,也可以将镁系热电转换材料11设为p型热电转换元件,在该情况下,能够通过添加锂(Li)、银(Ag)等掺杂剂作为受体而获得。
并且,作为本实施方式的镁系热电转换材料11中,如图2所示,在烧结体的截面中,在镁系化合物(硅化镁)的晶界主要局部存在Si浓度高于镁系化合物粒子的内部的富含Si金属相15。
在此,在烧结体的截面中,上述富含Si金属相15所占的面积率在2.5%以上且10%以下的范围内。
而且,面积为1μm2以上的富含Si金属相15的数密度在1800个/mm2以上且14000个/mm2以下的范围内。
另外,包含镁系化合物(硅化镁)的烧结体的镁系热电转换材料11中,在镁系化合物(硅化镁)的晶界存在MgO。由于该MgO的导电率低,因此晶界的电阻增加。
本实施方式的镁系热电转换材料11中,如上所述,在镁系化合物(硅化镁)的晶界局部存在富含Si金属相15,由此能够降低晶界的电阻。
另一方面,Si的导热系数在室温下为168W/(m·K),硅化镁(Mg2Si)的导热系数在室温下为9W/(m·K)。因此,若Si的含量增加,则有可能镁系热电转换材料11的导热系数提高,镁系热电转换材料11的一端侧与另一端侧之间的温差减小,热电转换效率下降。
在此,在富含Si金属相15的面积率小于2.5%的条件下,有可能无法充分地降低晶界的电阻。
另一方面,若富含Si金属相15的面积率超过10%,则有可能Si的含量增加,镁系热电转换材料11的导热系数提高。
根据以上内容,在本实施方式中,将富含Si金属相15所占的面积率限定在2.5%以上且10%以下的范围内。
另外,富含Si金属相15的面积率的下限优选设为3.5%以上,进一步优选设为4.5%以上。并且,富含Si金属相15的面积率的上限优选设为9%以下,进一步优选设为8%以下。
并且,在面积为1μm2以上的富含Si金属相15的数密度小于1800个/mm2的条件下,有可能无法充分地降低晶界的电阻。
另一方面,若面积为1μm2以上的富含Si金属相15的数密度超过14000个/mm2,则有可能Si的含量增加,镁系热电转换材料11的导热系数提高。
根据以上内容,在本实施方式中,将面积为1μm2以上的富含Si金属相15的数密度限定在1800个/mm2以上且14000个/mm2以下的范围内。
另外,面积为1μm2以上的富含Si金属相15的数密度的下限优选设为2500个/mm2以上,进一步优选设为5000个/mm2以上。并且,面积为1μm2以上的富含Si金属相15的数密度的上限优选设为12500个/mm2以下,进一步优选设为10000个/mm2以下。
并且,优选在该富含Si金属相15中含有极少量的Sb及Al等。若在局部存在于镁系化合物(硅化镁)的晶界处的富含Si金属相15中含有极少量的Sb及Al等,则通过这些元素的掺杂效应,晶界的电阻进一步下降。另外,本实施方式中,镁系化合物(硅化镁)中所包含的Sb以极少量包含于富含Si金属相15中。
在此提及的极少量是指0.005原子%~0.1原子%。
以下,参考图3及图4,对作为本实施方式的镁系热电转换材料11的制造方法进行说明。
(硅化镁粉末准备工序S01)
首先,制造成为作为镁系热电转换材料11的烧结体的母相的硅化镁(Mg2Si)的粉末。
本实施方式中,硅化镁粉末准备工序S01具备:块状硅化镁形成工序S11,获得块状硅化镁;及粉碎工序S12,粉碎该块状硅化镁(Mg2Si)而制成粉末。
块状硅化镁形成工序S11中,分别计量硅粉末、镁粉末及掺杂剂并进行混合。例如,在形成n型热电转换材料的情况下,混合锑、铋等5价的材料、铝作为掺杂剂,并且在形成p型热电转换材料的情况下,混合锂、银等材料作为掺杂剂。本实施方式中,为了获得n型热电转换材料而使用锑作为掺杂剂,其添加量在0.1原子%以上且2.0原子%以下的范围内。
并且,将该混合粉末例如导入到氧化铝坩埚中,加热至800℃以上且1150℃以下的范围内,并进行冷却而使其固化。由此,例如获得块状硅化镁。
另外,在加热时少量的镁升华,由此优选在计量原料时相对于Mg:Si=2:1的化学计量组成例如增加5原子%左右的镁。
粉碎工序S12中,利用粉碎机来粉碎所获得的块状硅化镁,从而形成硅化镁粉末。关于粉碎,优选在非活性气体、例如Ar中进行。
在此,优选硅化镁粉末的平均粒径在0.5μm以上且100μm以下的范围内。
另外,在使用市售的硅化镁粉末、已添加掺杂剂的硅化镁粉末的情况下,还能够省略块状硅化镁形成工序S11及粉碎工序S12。
(烧结原料粉末形成工序S02)
接着,在所获得的硅化镁粉末中混合硅氧化物而获得烧结原料粉末。
关于硅氧化物,能够使用非晶SiO2、方石英、石英、鳞石英、柯石英(coesite)、斯石英(stishovite)、塞石英(seifertite)、冲击石英等SiOx(x=1~2)。
硅氧化物的混合量在0.5mol%以上且13.0mol%以下的范围内。可更优选设为0.7mol%以上且7.0mol%以下。可以将硅氧化物设为粒径为0.5μm以上且100μm以下的粉末状。本实施方式中,使用中心粒径为20μm的SiO2粉末作为硅氧化物。
(烧结工序S03)
接着,一边对以上述方式获得的烧结原料粉末进行加压一边进行加热而获得烧结体。
本实施方式中,在烧结工序S03中,使用图4所示的烧结装置(通电烧结装置100)。
图4所示的烧结装置(通电烧结装置100)例如具备:耐压壳体101;真空泵102,对该耐压壳体101的内部进行减压;中空圆柱形的碳质模型103,配置于耐压壳体101内;一对电极部105a、105b,对填充到碳质模型103内的烧结原料粉末Q进行加压并且施加电流;及电源装置106,对该一对电极部105a、105b之间施加电压。并且,在电极部105a、105b与烧结原料粉末Q之间分别配置碳板107、碳片108。除此以外,还具有未图示的温度计、位移计等。
并且,本实施方式中,在碳质模型103的外周侧配设有加热器109。加热器109以覆盖碳质模型103的外周侧的整个表面的方式配置于四个侧表面。作为加热器109,能够利用碳加热器、镍铬合金丝加热器、钼加热器、康泰尔(Kanthal)丝加热器、高频加热器等。
烧结工序S03中,首先,将烧结原料粉末Q填充到图4所示的通电烧结装置100的碳质模型103内。碳质模型103中,例如,内部被石墨片、碳片覆盖。并且,使用电源装置106,使直流电流在一对电极部105a、105b之间流动,并使电流在烧结原料粉末Q中流动,由此通过自身发热而升温(通电加热)。并且,使一对电极部105a、105b中的可动侧的电极部105a向烧结原料粉末Q移动,并在该可动侧的电极部105a与固定侧的电极部105b之间以规定的压力对烧结原料粉末Q进行加压。并且,使加热器109进行加热。
由此,通过来自烧结原料粉末Q的自身发热及加热器109的热和加压,使烧结原料粉末Q烧结。
本实施方式中,烧结工序S03中的烧结条件被设为烧结原料粉末Q的烧结温度在800℃以上且1020℃以下的范围内、且该烧结温度下的保持时间在0.15分钟以上且5分钟以下的范围内。并且,加压负荷在20MPa以上且50MPa以下的范围内。
并且,可以将耐压壳体101内的气氛设为氩气氛等非活性气氛、真空气氛。在设为真空气氛的情况下,可以将压力设为5Pa以下。
在此,在烧结原料粉末Q的烧结温度小于800℃的情况下,无法充分地去除在烧结原料粉末Q的各粉末的表面所形成的氧化膜,导致氧化膜残留于晶界,并且烧结体的密度下降。因此,有可能导致所获得的热电转换材料的电阻增加。
另一方面,在烧结原料粉末Q的烧结温度超过1020℃的情况下,有可能导致在短时间内进行硅化镁的分解,导致产生组成偏差,而电阻上升并且塞贝克系数下降。
因此,本实施方式中,将烧结工序S03中的烧结温度设定在800℃以上且1020℃以下的范围内。
另外,烧结工序S03中的烧结温度的下限优选设为850℃以上,进一步优选设为900℃以上。另一方面,烧结工序S03中的烧结温度的上限优选设为1000℃以下,进一步优选设为980℃以下。
并且,在烧结温度下的保持时间小于0.15分钟的情况下,有可能烧结不充分而导致所获得的热电转换材料的电阻增加。
另一方面,在烧结温度下的保持时间超过5分钟的情况下,有可能导致进行硅化镁的分解,导致产生组成偏差,而电阻上升并且塞贝克系数下降。
因此,本实施方式中,将烧结工序S03中的烧结温度下的保持时间设定在0.15分钟以上且5分钟以下的范围内。
另外,烧结工序S03中的烧结温度下的保持时间的下限优选设为0.15分钟以上,进一步优选设为0.5分钟以上。另一方面,烧结工序S03中的烧结温度下的保持时间的上限优选设为5分钟以下,进一步优选设为3分钟以下。
而且,在烧结工序S03中的加压负荷小于20MPa的情况下,有可能密度不会增加,而导致热电转换材料的电阻增加。
另一方面,在烧结工序S03中的加压负荷超过50MPa的情况下,有可能导致用于制作烧结体的碳质模型的寿命缩短、或者根据情况而破损。
因此,本实施方式中,将烧结工序S03中的加压负荷设定在20MPa以上且50MPa以下的范围内。
另外,烧结工序S03中的加压负荷的下限优选设为20MPa以上,进一步优选设为25MPa以上。另一方面,烧结工序S03中的加压负荷的上限优选设为50MPa以下,进一步优选设为40MPa以下。
并且,该烧结工序S03中,在使直流电流在烧结原料粉末Q中流动时,以规定的时间间隔变更一个电极部105a和另一个电极部105b的极性。即,交替地实施将一个电极部105a设为阳极且将另一个电极部105b设为阴极而进行通电的状态、及将一个电极部105a设为阴极且将另一个电极部105b设为阳极而进行通电的状态。本实施方式中,将规定的时间间隔设定在10秒以上且300秒以下的范围内。在规定的时间间隔小于10秒的条件下,规定的时间内的烧结原料粉末Q的温度上升幅度小且改变极性的效果小。另一方面,是因为:在规定的时间间隔长于300秒的情况下,有可能规定的时间内的烧结原料粉末Q的温度上升幅度大,一个极性的效果变大,无法充分地获得均匀性。
通过以上工序,可制造作为本实施方式的镁系热电转换材料11。
根据设为如上述的结构的本实施方式的镁系热电转换材料11,在镁系化合物的晶界局部存在Si浓度高于所述镁系化合物粒子的内部的富含Si金属相15,因此晶界处的电阻下降。由此,能够提高镁系热电转换材料11的热电转换效率。
并且,富含Si金属相15所占的面积率在2.5%以上且10%以下的范围内,且面积为1μm2以上的富含Si金属相15的数密度在1800个/mm2以上且14000个/mm2以下的范围内,因此导电率比较高的富含Si金属相15被均匀且充分地分散,能够提高镁系热电转换材料11的热电转换效率。
根据作为本实施方式的镁系热电转换材料11的制造方法,设为如下结构:在烧结工序S03中,使用一边用一对电极部105a、105b对烧结原料粉末Q进行加压一边进行通电的通电加热法,在烧结时以规定的时间间隔变更一对电极部105a、105b的极性,因此烧结体被均匀地烧结。
并且,本实施方式中,通过配置于烧结原料粉末Q的外周侧的加热器109还从外周侧对烧结原料粉末Q进行加热,因此能够对烧结原料进一步均匀地进行加热。
由此,能够使Si浓度高于镁系化合物粒子的内部的富含Si金属相15分散于整个烧结体中,从而能够获得热电转换效率优异的镁系热电转换材料11。
以上,对本发明的实施方式进行了说明,但本发明并不限定于此,可以在不脱离该发明的技术思想的范围内进行适当变更。
例如,本实施方式中,作为构成如图1所示的结构的镁系热电转换元件的镁系热电转换材料而进行了说明,但是并不限定于此,若使用本发明的镁系热电转换材料,则对金属化层、电极的结构及配置等并无特别限制。
而且,本实施方式中,作为将作为掺杂剂而添加了锑(Sb)的硅化镁的粉末用作烧结原料的镁系热电转换材料而进行了说明,但是并不限定于此,例如可以是包含选自Li、Na、K、B、Al、Ga、In、N、P、As、Bi、Ag、Cu、Y中的一种或两种以上作为掺杂剂的镁系热电转换材料,也可以除了Sb以外还包含这些元素。
并且,本实施方式中,列举硅化镁(Mg2Si)作为镁系化合物而进行了说明,但是并不限定于此,可以是Mg2Si1-xGex、Mg2Si1-xSnx中的任意一种。
实施例
以下,对为了确认本发明的效果而实施的实验结果进行说明。
分别计量了纯度为99.9质量%的Mg(Kojundo Chemical Lab.Co.,Ltd.制造,平均粒径为180μm)、纯度为99.99质量%的Si(Kojundo Chemical Lab.Co.,Ltd.制造,平均粒径为300μm)、纯度为99.9质量%的Sb(Kojundo Chemical Lab.Co.,Ltd.制造,平均粒径为300μm)。将这些粉末在研钵中充分地混合,放入到氧化铝坩埚中,并在Ar-5体积%H2中以850℃加热了2小时。考虑由Mg的升华引起的与Mg:Si=2:1的化学计量组成的偏差,多混合了5原子%的Mg。由此,获得了含有作为掺杂剂的1原子%的Sb的块状硅化镁(Mg2Si)。
接着,在研钵中细粉碎该块状硅化镁(Mg2Si),并对其进行分级而获得了平均粒径为30μm的硅化镁粉末(Mg2Si粉末)。
并且,混合硅化镁粉末和硅氧化物粉(TATSUMORI LTD.制造的SiO2粉末,平均粒径为20μm)而获得了烧结原料粉末。
将所获得的烧结原料粉末填充到由碳片覆盖了内侧的碳质模型。并且,通过图4所示的烧结装置(通电烧结装置100),在表1所示的条件下进行了通电烧结。
关于所获得的热电转换材料,对于富含Si金属相的面积率、面积为1μm2以上的富含Si金属相的数密度、热电特性,以如下步骤进行了评价。
(富含Si金属相的面积率及数密度)
提取测定试样并对切割面进行抛光,使用EPMA装置(JEOL Ltd.制造的JXA-8800RL),在加速电压为15kV、射束电流为50nA、光束直径为1μm、映射测定点数为200×200pixel(像素)的条件下,进行了EPMA观察。
在EPMA分析中,通过电子束在测定试样内的扩散,检测比初级光束直径宽的区域的元素信息(元素浓度)。在如Si的轻元素的情况下,检测来自光束直径的3倍的的元素信息(元素浓度)。因此,在进行映射时,若检测物的尺寸小,则除了检测物以外,还一并检测检测物周边元素的浓度信息,并将其平均值设为浓度。因此,在本发明中,富含Si金属相被设为Si浓度比硅化镁粒子的内部的平均Si浓度高2wt%以上的区域。
在图5A及图5B中示出EPMA观察结果的一例。图5A及图5B中,由白色表示比硅化镁粒子的内部的平均Si浓度高2wt%以上的高硅浓度的相,并测定了富含Si金属相所占的面积率。在此,设为富含Si金属相所占的面积率(%)=(富含Si金属相的面积)/(EPMA映射的一个视场的面积)。
并且,基于如图5A及图5B所示的映射图,测定了面积为1μm2以上的富含Si金属相的数密度。在个数测定中不考虑尺寸,而对于连续存在的金属相将其作为一个富含Si金属相而进行了测量。
并且,通过EPMA观察来进行观察的试样中,对包含Si浓度高的区域的部位进行俄歇电子能谱分析,并确认到Si浓度高的区域为Si金属相。使用俄歇分析装置(ULVAC-PHI,Inc.制造的PHI700Xi),将观察条件设为加速电压为10kV、射束电流为15nA、光束直径为15nm,并将蚀刻条件设为离子种类为Ar+、加速电压为500V、射束电流为2.7nA、蚀刻时间为10分钟、离子枪附近的真空度为10mPa、分析室内压力为10-9Torr。
其结果,如图6所示,在表示Si金属相的1620eV处观察到峰,由此确认到通过EPMA观察来观察到的Si浓度高的区域为Si金属相。
(热电特性)
关于热电特性,从所烧结的热电转换材料切出4mm×4mm×15mm的长方体,并使用热电特性评价装置(ADVANCE RIKO,Inc.制造的ZEM-3),求出了各试样在550℃下的功率因数(PF)。
[表1]
将富含Si金属相的面积率设为小于2.5%,且将面积为1μm2以上的富含Si金属相的数密度设为小于1800个/mm2的比较例1、比较例2中,550℃下的功率因数下降。推测是因为晶界处的电阻的下降未充分地发挥作用。
富含Si金属相的面积率超过10%,且面积为1μm2以上的富含Si金属相的数密度超过14000个/mm2的比较例3中,550℃下的功率因数下降。推测这是因为:SiO2改性而得的MgSiO及Si的含量增加,导热系数提高,并且塞贝克系数减小。
相对于此,富含Si金属相所占的面积率在2.5%以上且10%以下的范围内,且面积为1μm2以上的所述富含Si金属相的数密度在1800个/mm2以上且14000个/mm2以下的范围内的本发明例1-6中,550℃下的功率因数提高。
由以上内容确认到:根据本发明例,能够提供一种热电特性优异的热电转换材料。
产业上的可利用性
根据本发明,能够提供一种热电转换效率更高的热电转换元件,由此能够更有效地利用废热。
符号说明
10-镁系热电转换元件,11-镁系热电转换材料,15-富含Si金属相,19a、19b-电极。
Claims (6)
1.一种镁系热电转换材料,其由镁系化合物的烧结体形成,该镁系热电转换材料的特征在于,
在所述烧结体的截面中,在镁系化合物粒子的晶界局部存在Si浓度高于所述镁系化合物粒子的内部的富含Si金属相,
所述富含Si金属相所占的面积率在2.5%以上且10%以下的范围内,
面积为1μm2以上的所述富含Si金属相的数密度在1800个/mm2以上且14000个/mm2以下的范围内。
2.根据权利要求1所述的镁系热电转换材料,其特征在于,
所述镁系化合物为MgxSiy、Mg2Si1-xGex、Mg2Si1-xSnx中的任意一种。
3.根据权利要求1或2所述的镁系热电转换材料,其特征在于,
所述镁系热电转换材料包含Li、Na、K、B、Al、Ga、In、N、P、As、Sb、Bi、Ag、Cu、Y中的至少一种以上作为掺杂剂。
4.一种镁系热电转换元件,其特征在于,
所述镁系热电转换元件具备权利要求1至3中任一项所述的镁系热电转换材料及电极,所述电极分别与所述镁系热电转换材料的一个表面及与其对向的另一个表面接合。
5.一种镁系热电转换材料的制造方法,该镁系热电转换材料由镁系化合物的烧结体形成,该镁系热电转换材料的制造方法的特征在于,具备:
烧结原料粉末形成工序,在镁系化合物的原料粉末中混合硅氧化物而获得烧结原料粉末;及烧结工序,一边对所述烧结原料粉末进行加压一边进行加热而形成烧结体,
在所述烧结工序中,使用通电加热法,在烧结时以规定的时间间隔变更一对电极部的极性,所述通电加热法中,一边用一对电极部对所述烧结原料粉末进行加压一边进行通电。
6.根据权利要求5所述的镁系热电转换材料的制造方法,其特征在于,
在所述烧结工序中,通过配置于所述烧结原料粉末的外周侧的加热器,进一步对所述烧结原料粉末进行加热。
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Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000261046A (ja) * | 1999-03-10 | 2000-09-22 | Sumitomo Special Metals Co Ltd | 熱電変換材料とその製造方法 |
US20020088485A1 (en) * | 2000-08-18 | 2002-07-11 | Osamu Yamashita | Thermoelectric conversion material, and method for manufacturing same |
US7002071B1 (en) * | 1999-03-10 | 2006-02-21 | Sumitomo Special Metals Co. Ltd. | Thermoelectric conversion material and method of producing the same |
US20060057015A1 (en) * | 2003-01-08 | 2006-03-16 | Katsuyoshi Kondoh | Magnesium composite powder, method for producing same, magnesium base composite material and method for producing same |
JP2010010009A (ja) * | 2008-06-30 | 2010-01-14 | Kurosaki Harima Corp | 溶造Si電熱合金の抵抗温度曲線を平坦化する方法 |
US20120097205A1 (en) * | 2009-06-30 | 2012-04-26 | Tokyo University Of Science Educational Foundation Administrative Organization | Magnesium-silicon composite material and process for producing same, and thermoelectric conversion material, thermoelectric conversion element, and thermoelectric conversion module each comprising or including the composite material |
JP2012104596A (ja) * | 2010-11-09 | 2012-05-31 | Kobe Univ | Mgドープp型Siの作製方法および熱電変換材料 |
JP2012533972A (ja) * | 2009-07-17 | 2012-12-27 | エミテック ゲゼルシヤフト フユア エミツシオンス テクノロギー ミツト ベシユレンクテル ハフツング | 管束を備える熱電デバイス |
US20130153811A1 (en) * | 2011-12-20 | 2013-06-20 | Teruyuki Ikeda | Method of manufacturing thermoelectric material, thermoelectric material, and thermoelectric conversion element |
CN103172346A (zh) * | 2013-03-29 | 2013-06-26 | 太原理工大学 | 电场反应热压法制备多孔纳米镁硅基块体热电材料的方法 |
JP2015168603A (ja) * | 2014-03-07 | 2015-09-28 | 宮川化成工業株式会社 | 熱電対用導電性セラミックスおよび熱電対 |
WO2016056278A1 (ja) * | 2014-10-07 | 2016-04-14 | 日立化成株式会社 | 熱電変換素子、その製造方法および熱電変換モジュール |
JP2016219666A (ja) * | 2015-05-22 | 2016-12-22 | トヨタ自動車株式会社 | 熱電材料及びその製造方法 |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003089804A (ja) * | 2001-09-18 | 2003-03-28 | Mitsubishi Heavy Ind Ltd | BiTe系熱電材料の製造方法 |
CN100567529C (zh) * | 2001-09-25 | 2009-12-09 | 株式会社东京大学Tlo | 镁复合材料 |
WO2003027341A1 (fr) * | 2001-09-25 | 2003-04-03 | Center For Advanced Science And Technology Incubation, Ltd. | Materiau composite a base de magnesium |
US7052526B2 (en) * | 2002-02-15 | 2006-05-30 | Toudai Tlo, Ltd. | Magnesium base composite material and its manufacturing method |
CN101589480B (zh) * | 2006-12-20 | 2011-08-24 | 昭和Kde株式会社 | 热电转换材料、其制造方法及热电转换元件 |
US8813522B2 (en) * | 2008-10-14 | 2014-08-26 | University Of Central Florida Research Foundation, Inc. | Silicon photonic fiber and method of manufacture |
JP5598792B2 (ja) * | 2010-05-28 | 2014-10-01 | 株式会社三徳 | マグネシウム−シリコン系熱電変換材料およびその製造方法 |
US8518288B2 (en) * | 2010-07-27 | 2013-08-27 | Toyota Motor Engineering & Manufacturing North America, Inc. | Synthesis of nanocomposite thermoelectric material |
US8535554B2 (en) * | 2010-07-27 | 2013-09-17 | Toyota Motor Engineering & Manufacturing North America, Inc. | High-Ph synthesis of nanocomposite thermoelectric material |
US8568607B2 (en) * | 2011-02-08 | 2013-10-29 | Toyota Motor Engineering & Manufacturing North America, Inc. | High-pH synthesis of nanocomposite thermoelectric material |
JP2012244001A (ja) * | 2011-05-20 | 2012-12-10 | Toyota Motor Corp | ナノコンポジット熱電材料およびその製造方法 |
WO2013047474A1 (ja) | 2011-09-26 | 2013-04-04 | 学校法人東京理科大学 | 焼結体、熱電変換素子用焼結体、熱電変換素子及び熱電変換モジュール |
JP5760917B2 (ja) * | 2011-09-30 | 2015-08-12 | 日立化成株式会社 | 熱電変換素子の製造方法 |
US20130186448A1 (en) | 2012-01-20 | 2013-07-25 | Gentherm, Inc. | Catalyst-thermoelectric generator integration |
JP6603518B2 (ja) | 2015-09-04 | 2019-11-06 | 株式会社日立製作所 | 熱電変換材料および熱電変換モジュール |
ES2704132T3 (es) * | 2016-01-21 | 2019-03-14 | Evonik Degussa Gmbh | Procedimiento racional para la producción pulvimetalúrgica de componentes termoeléctricos |
JP6798339B2 (ja) * | 2016-02-24 | 2020-12-09 | 三菱マテリアル株式会社 | マグネシウム系熱電変換材料の製造方法、マグネシウム系熱電変換素子の製造方法、マグネシウム系熱電変換材料、マグネシウム系熱電変換素子、熱電変換装置 |
JP2017156729A (ja) | 2016-03-04 | 2017-09-07 | 株式会社コシダカホールディングス | なりきりcv専用機 |
US11306002B2 (en) * | 2017-03-07 | 2022-04-19 | Toyota Motor Europe | Process for synthesis of MG2SI/MGO nanocomposites |
-
2017
- 2017-08-15 JP JP2017156729A patent/JP6981094B2/ja active Active
-
2018
- 2018-05-11 EP EP18846157.8A patent/EP3671870B1/en active Active
- 2018-05-11 KR KR1020207002996A patent/KR102409289B1/ko active IP Right Grant
- 2018-05-11 WO PCT/JP2018/018373 patent/WO2019035253A1/ja unknown
- 2018-05-11 US US16/632,686 patent/US11462671B2/en active Active
- 2018-05-11 CN CN201880047442.8A patent/CN110892537B/zh active Active
- 2018-05-17 TW TW107116729A patent/TWI768045B/zh active
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7002071B1 (en) * | 1999-03-10 | 2006-02-21 | Sumitomo Special Metals Co. Ltd. | Thermoelectric conversion material and method of producing the same |
JP2000261046A (ja) * | 1999-03-10 | 2000-09-22 | Sumitomo Special Metals Co Ltd | 熱電変換材料とその製造方法 |
US20020088485A1 (en) * | 2000-08-18 | 2002-07-11 | Osamu Yamashita | Thermoelectric conversion material, and method for manufacturing same |
US20060057015A1 (en) * | 2003-01-08 | 2006-03-16 | Katsuyoshi Kondoh | Magnesium composite powder, method for producing same, magnesium base composite material and method for producing same |
JP2010010009A (ja) * | 2008-06-30 | 2010-01-14 | Kurosaki Harima Corp | 溶造Si電熱合金の抵抗温度曲線を平坦化する方法 |
US20120097205A1 (en) * | 2009-06-30 | 2012-04-26 | Tokyo University Of Science Educational Foundation Administrative Organization | Magnesium-silicon composite material and process for producing same, and thermoelectric conversion material, thermoelectric conversion element, and thermoelectric conversion module each comprising or including the composite material |
CN102804433A (zh) * | 2009-06-30 | 2012-11-28 | 学校法人东京理科大学 | 镁-硅复合材料及其制造方法、以及采用该复合材料的热电转换材料、热电转换元件及热电转换模块 |
JP2012533972A (ja) * | 2009-07-17 | 2012-12-27 | エミテック ゲゼルシヤフト フユア エミツシオンス テクノロギー ミツト ベシユレンクテル ハフツング | 管束を備える熱電デバイス |
JP2012104596A (ja) * | 2010-11-09 | 2012-05-31 | Kobe Univ | Mgドープp型Siの作製方法および熱電変換材料 |
US20130153811A1 (en) * | 2011-12-20 | 2013-06-20 | Teruyuki Ikeda | Method of manufacturing thermoelectric material, thermoelectric material, and thermoelectric conversion element |
CN103172346A (zh) * | 2013-03-29 | 2013-06-26 | 太原理工大学 | 电场反应热压法制备多孔纳米镁硅基块体热电材料的方法 |
JP2015168603A (ja) * | 2014-03-07 | 2015-09-28 | 宮川化成工業株式会社 | 熱電対用導電性セラミックスおよび熱電対 |
WO2016056278A1 (ja) * | 2014-10-07 | 2016-04-14 | 日立化成株式会社 | 熱電変換素子、その製造方法および熱電変換モジュール |
JP2016219666A (ja) * | 2015-05-22 | 2016-12-22 | トヨタ自動車株式会社 | 熱電材料及びその製造方法 |
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