CN101542762B - 热电转换材料和热电转换元件 - Google Patents

热电转换材料和热电转换元件 Download PDF

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CN101542762B
CN101542762B CN200780043906XA CN200780043906A CN101542762B CN 101542762 B CN101542762 B CN 101542762B CN 200780043906X A CN200780043906X A CN 200780043906XA CN 200780043906 A CN200780043906 A CN 200780043906A CN 101542762 B CN101542762 B CN 101542762B
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thermo
thermoelectric conversion
electric converting
converting material
sintered body
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CN101542762A (zh
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内田义男
当间哲朗
贞冈和男
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Sumitomo Chemical Co Ltd
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Abstract

本发明提供在高温空气中的实用环境下，稳定地显示输出因子等热电转换特性的热电转换材料。所述热电转换材料含有复合金属氧化物，该复合金属氧化物作为金属元素，含有M1、M2A和M2B，M1∶M2A∶M2B的摩尔比为2∶1∶1，且结晶构造是钙钛矿型，其中，M1是选自La、Y和镧系元素中的至少一种M1A，或者是M1A与选自碱土类金属元素中的至少一种M1B的组合；M2A是选自原子价能够成为二价的金属元素的至少一种；M2B是选自原子价能够成为四价的金属元素的至少一种；M1、M2A和M2B不相同，并且M2A和M2B可以含有掺杂元素。

Description

热电转换材料和热电转换元件
技术领域
本发明涉及热电转换材料和热电转换元件。 
背景技术
所谓热电转换发电，是指利用通过对热电转换材料赋予温度差而产生热电动势的塞贝克效应，将热能转换成电能的发电。热电转换发电由于可以将地热、焚烧炉的热等排热作为热能利用，因此被期待作为环保型的发电。 
热电转换材料的将热能转换成电能的效率(以下称为“能量转换效率”)依赖于热电转换材料的性能指数(Z)。性能指数(Z)是用热电转换材料的塞贝克系数(α)、电导率(σ)和热导率(κ)，通过式(1)求出的。 
                Z＝α2×σ/κ    (1) 
如果使用性能指数(Z)大的热电转换材料，则可以得到能量转换效率良好的热电转换元件。式(1)中的α2×σ被称为输出因子(PF)，其值越大的热电转换材料，热电转换元件的每单位温度的输出越大。 
热电转换材料有塞贝克系数为正的p型热电转换材料、以及塞贝克系数为负的n型热电转换材料。通常，热电转换发电中使用将p型热电转换材料和n型热电转换材料电串联连接而成的热电转换元件。热电转换元件的能量转换效率依赖于p型热电转换材料和n型热电转换材料的性能指数(Z)。为了得到能量转换效率良好的热电转换元件，要求性能指数(Z)大的p型热电转换材料和n型热电转换材料。 
例如，在特表2001-512910号公报(第2-8页)中，公开了以RBa2Cu3O7-δ表示的热电转换材料。 
然而，公报记载的热电转换材料在高温(约600℃)空气中的实用环境下热电转换特性(例如输出因子)不稳定、且不好。 
发明内容
本发明的目的在于提供一种在实用环境下具有稳定且良好的热电转换特性的材料。 
本发明人等进行了各种研究，结果完成了本发明。 
即，本发明提供一种热电转换材料，其特征在于，含有复合金属氧化物，该复合金属氧化物含有M1、M2A和M2B作为金属元素，M1∶M2A∶M2B的摩尔比为2∶1∶1，且结晶构造是钙钛矿型，其中， 
M1是选自La、Y和镧系元素中的至少一种M1A，或者是M1A与选自碱土类金属元素中的至少一种M1B的组合； 
M2A是选自原子价能够成为二价的金属元素中的至少一种； 
M2B是选自原子价能够成为四价的金属元素中的至少一种； 
M1、M2A和M2B不相同，并且M2A和M2B可以含有掺杂元素。 
此外，本发明还提供含有上述热电转换材料的热电转换元件。 
附图说明
图1表示实施例1的烧结体1的X射线衍射图形。 
具体实施方式
热电转换材料 
本发明的热电转换材料含有复合金属氧化物。复合金属氧化物含有M1、M2A和M2B作为金属元素。 
M1是M1A、或者是M1A与M1B的组合。M1A可以是La、Y、镧系元素，优选是其中原子价能够成为三价的金属元素。M1A通常是La、Y、Ce、Pr、Nd、Pm、Sm、Eu和Gd，优选是La。它们可以是单独一种，也可以是组合。M1B是碱土类金属元素，优选是Ca、Sr、Ba。它们可以是单独一种，也可以是组合。M1是M1A与M1B的组合时，M1B的量通常以M1A∶M1B的摩尔比计为1∶0.01～1∶1。 
M2A是原子价能够成为二价的金属元素，优选为Cu、Ni、Zn、Ag，更优选为Cu。它们可以是单独一种，也可以是组合。 
此外，M2A可以是原子价能够成为二价的金属元素与二价以外的金属元素(掺杂元素I，例如Li、Na、Al、Ga、In、Bi、Sb)的组合，还可以是前者的一部分被后者置换而成的物质。含有这样的掺杂元素I的热电转换材料有时显示高的热电转换特性。 
M2B是原子价能够成为四价的金属元素，优选是Ti、V、Cr、Mn、Fe、Co、Zr、Nb、Mo、Tc、Ru、Os、Ir、Pt、Au、Sn，更优选是Sn、Ti、Mn。它们可以是单独一种，也可以是组合。此外，M2B可以是原子价能够成为四价的金属元素与四价以外的金属元素(掺杂元素II，例如Mg、Ca、Cu、Ni、Zn、Ag、Sc、Al、Ga、In、Bi、Sb)的组合，还可以是前者的一部分被后者置换而成的物质。含有这样的掺杂元素II的热电转换材料有时也同样地显示高的热电转换特性。 
M1、M2A和M2B不相同。例如，M1是M1A与M1B的组合时，M2A不含M1B的金属元素。例如，M2A为二价的Sn时，M2B不含四价的Sn。 
M1∶M2A∶M2B的摩尔比为2∶1∶1。 
复合金属氧化物的结晶构造是钙钛矿型。 
以下，给出复合金属氧化物的具体例。M1A是La的复合金属氧化物，例如： 
La2CuSnO6(M2A是Cu、M2B是Sn)、 
La2CuTiO6(M2A是Cu、M2B是Ti)、 
La2NiSnO6(M2A是Ni、M2B是Sn)、 
La2ZnSnO6(M2A是Zn、M2B是Sn)、 
La2ZnTiO6(M2A是Zn、M2B是Ti)、 
La2ZnZrO6(M2A是Zn、M2B是Zr)、 
La2-xCaxCu2Sn2O11(M1B是Ca、M2A是Cu、M2B是Sn、0.01≤x/(2-x)≤1)、 
La2-xCaxCu2Ti2O11(M1B是Ca、M2A是Cu、M2B是Ti、0.01≤x/(2-x)≤1)、 
La2-xCaxZn2Sn2O11(M1B是Ca、M2A是Zn、M2B是Sn、0.01≤x/(2-x)≤1)、 
La2-xCaxZn2Ti2O11(M1B是Ca、M2A是Zn、M2B是Ti、0.01≤x/(2-x)≤1)、 
La2-xCaxNi2Sn2O11(M1B是Ca、M2A是Ni、M2B是Sn、0.01≤x/(2-x)≤1)、 
La2-xBaxCu2Sn2O11(M1B是Ba、M2A是Cu、M2B是Sn、0.01≤x/(2-x)≤1)、 
La2-xBaxCu2Ti2O11(M1B是Ba、M2A是Cu、M2B是Ti、0.01≤x/(2-x)≤1)、 
La2-xBaxZn2Sn2O11(M1B是Ba、M2A是Zn、M2B是Sn、0.01≤x/(2-x)≤1)、 
La2-xBaxZn2Ti2O11(M1B是Ba、M2A是Zn、M2B是Ti、0.01≤x/(2-x)≤1)、 
La2-xBaxNi2Sn2O11(M1B是Ba、M2A是Ni、M2B是Sn、0.01≤x/(2-x)≤1)、 
La2-xSrxCu2Sn2O11(M1B是Sr、M2A是Cu、M2B是Sn、0.01≤x/(2-x)≤1)、 
La2-xSrxCu2Ti2O11(M1B是Sr、M2A是Cu、M2B是Ti、0.01≤x/(2-x)≤1)、 
La2-xSrxZn2Sn2O11(M1B是Sr、M2A是Zn、M2B是Sn、0.01≤x/(2-x)≤1)、 
La2-xSrxZn2Ti2O11(M1B是Sr、M2A是Zn、M2B是Ti、0.01≤x/(2-x)≤1)、 
La2-xSrxNi2Sn2O11(M1B是Sr、M2A是Ni、M2B是Sn、0.01≤x/(2-x)≤1)。 
M1A是La以外的原子价能够成为三价的金属元素(Y、Ce、Pr、Nd、Pm、Sm、Eu、Gd)的复合金属氧化物，是用这些金属元素置换La的物质，M1A是Eu的复合金属氧化物，例如有： 
Eu2CuSnO6(M2A是Cu、M2B是Sn)、 
Eu2CuTiO6(M2A是Cu、M2B是Ti)、 
Eu2NiSnO6(M2A是Ni、M2B是Sn)、 
Eu2ZnSnO6(M2A是Zn、M2B是Sn)、 
Eu2ZnTiO6(M2A是Zn、M2B是Ti)、 
Eu2ZnZrO6(M2A是Zn、M2B是Zr)、 
Eu2Ba2Cu2Sn2O11(M1B是Ba、M2A是Cu、M2B是Sn)、 
Eu2Ba2Cu2Ti2O11(M1B是Ba、M2A是Cu、M2B是Ti)、 
Eu2Ba2Zn2Sn2O11(M1B是Ba、M2A是Zn、M2B是Sn)、 
Eu2Ba2Zn2Ti2O11(M1B是Ba、M2A是Zn、M2B是Ti)、 
Eu2Ba2Ni2Sn2O11(M1B是Ba、M2A是Ni、M2B是Sn)。 
由于Y、Ce、Pr、Nd、Pm、Sm、Eu、Gd的原子价能够成为三价，且离子半径也与La为同等程度，因此可以进行上述那样的置换，所得热电转换材料也发挥同样的效果。 
此外，La的40％被Eu置换而成的复合金属氧化物，例如有：(La0.6Eu0.4)2CuSnO6、(La0.6Eu0.4)2CuTiO6、(La0.6Eu0.4)2NiSnO6、(La0.6Eu0.4)2ZnSnO6、(La0.6Eu0.4)2ZnTiO6、(La0.6Eu0.4)2ZnZrO6、(La0.6Eu0.4)2Ba2Cu2Sn2O11、(La0.6Eu0.4)2Ba2Cu2Ti2O11、(La0.6Eu0.4)2Ba2Zn2Sn2O11、(La0.6Eu0.4)2Ba2Zn2Ti2O11、(La0.6Eu0.4)2Ba2Ni2Sn2O11。 
热电转换材料的形态例如为粉体、烧结体、薄膜，优选为烧结体。热电转换材料的形态为烧结体时，形状和尺寸可以适合作为热电转换元件，形状例如为板、圆柱、棱柱。 
从电导率(σ)和机械强度的观点出发，热电转换材料优选为致密，其相对密度优选为60％以上，更优选为80％以上，进一步优选为90％以上。此外，这样的热电转换材料典型的形态是取向烧结体、单晶。 
热电转换材料在使用环境条件下有时被氧化或还原而性能降低，在这种情况下，可以用不透气膜被覆其表面。不透气膜例如由氧化铝、氧化钛、氧化锆、碳化硅等形成。在无损热电转换材料的功能的范围内，不透气膜可以将表面或其一部分覆盖。 
本发明的热电转换材料可以采用烧结法制造，例如，可以采用将金属或金属化合物的混合物烧结的方法来制造。混合物可以通过以金属或金属化合物成为规定组成的方式进行称量、混合的方法来制备。 
热电转换材料可以如下制造，具体地说，通过将含有M1的化合物、含有M2A的化合物、含有M2B的金属化合物称量、混合，制备M1∶M2A∶M2B的摩尔比满足2∶1∶1的混合物，并将该混合物烧结的方法来制造；通过Y2CuSnO6所表示的复合金属氧化物使用氧化钇(Y2O3)、氧化铜(CuO)、氧化锡(SnO2)作为金属化合物，将它们以Y∶Cu∶Sn的摩尔比满足2∶1∶1的方式称量、混合而得到混合物，并将该混合物烧结的方法来制造。 
金属化合物是含有M1、M2A或M2B的金属元素的化合物，例如在高温下分解和/或氧化而形成氧化物的氢氧化物、碳酸盐、硝酸盐、卤化物、硫酸盐、有机酸盐，或者是氧化物。 
此外，热电转换材料可以通过例如将含有M1的化合物、含有M2A的化合物、含有M2B的金属化合物称量、混合，制备M1∶M2A∶M2B的摩尔比满足2∶1∶1的混合物，并将该混合物烧结的方法来制造；此时，M1A是La，M2A是Cu，M2B是Sn。含有La的化合物例如是氧化镧、氢氧化镧、硝酸镧，优选是氧化镧。含有Cu的化合物，例如是氧化亚铜、氧化铜、硝酸铜，优选为氧化铜。含有Sn的化合物，例如是氧化锡、硝酸锡、氯化锡，优选为氧化锡。 
混合可以采用例如球磨机、V型混合机、振动式磨机、立式球磨机、珠磨机(Dyno-mill)、动态磨机来进行。此外，混合可以采用湿式、干式的任一种来进行。从得到良好的热电转换材料的观点出发，混合优选采用得到金属化合物的均匀混合物的方法来进行。 
混合物可以含有粘合剂、分散剂、脱模剂之类的添加剂。添加剂可以在混合化合物时添加，此外，还可以添加到混合物、后述的烧成品或粉碎品中。混合物根据需要可以进行烧成。混合物含有在高温下分解和/或氧化而形成氧化物的氢氧化物、碳酸盐、硝酸盐、卤化物、有机酸盐等时，通过烧成，将它们变成氧化物，可以从它们中除去二氧化碳、结晶水，或者提高烧结体组成的均一性、烧结体结构的均一性，或者抑制烧结体的变形。烧成可以根据混合物的组成设定适宜条件来进行，例如，混合物含有碳酸盐时，烧成可以在温度：600℃～1200℃、环境气氛：空气、保持时间：5～24小时的条件下进行。混合物可以进行粉碎。粉碎可以采用例如球磨机、振动式磨机、立式球磨机、珠磨机、动态磨机来进行。此外，混合物可以进行成型。成型可以在板、棱柱、圆柱等作为热电转换元件为适当形状的条件下进行。成型可以使用例如单螺杆冲压、冷等静压(CIP)、机械冲压、热压、热等静压(HIP)来进行。 
热电转换材料优选通过将混合物、烧成品或粉碎品进行成型，并将成型体烧结的方法来制造；进一步优选通过将混合物烧成、粉碎，接着进行成型，将所得到的成型体烧结的方法来制造。 
烧结可以在温度：700℃～1700℃、优选900℃～1500℃、进一步优选1000℃～1400℃、保持时间：0.5～48小时、环境气氛：空气、氧、真空或惰性气体(氮、稀有气体)的条件下进行。烧结温度小于700℃时，难以烧结，根据复合金属氧化物的组成，有时热电转换材料的电导率(σ)降低。另一方面，烧结温度超过1500℃时，根据复合金属氧化 物的组成，有时产生异常颗粒生长、熔融，热电转换材料的性能指数(Z)降低。 
烧结体可以根据需要进行粉碎，并将其烧结。烧结可以在与上述相同的条件下进行。 
热电转换材料可以通过将混合物烧成、粉碎，并将所得粉碎品采用HIP等进行成型和同时进行烧结的方法来制造。 
热电转换材料的制造中，可以通过改变混合物、烧成品、粉碎品的粒子尺寸或者成型压力、烧结温度、烧结时间等来控制烧结体的相对密度。 
热电转换材料在使用环境条件下有时被氧化或还原而性能降低，在这种情况下，可以用不易透过气体的不透气膜被覆其表面。不透气膜例如由氧化铝、氧化钛、氧化锆、碳化硅等形成。被覆可以采用例如气溶胶淀积、喷涂、CVD(化学气相淀积)来进行。 
热电转换材料也可以通过其他方法制造。作为其他方法，可以列举例如含有共沉淀工序、水热工序、干燥(dry up)工序、溅射工序、采用CVD的工序、气溶胶凝胶工序、FZ(浮游带区域熔融法)工序、或者采用TSCG(模板型单晶生长法)的工序的方法等。 
热电转换元件 
热电转换元件含有上述的热电转换材料。 
上述的热电转换材料通常是p型，因此热电转换元件含有上述的p型热电转换材料和n型热电转换材料。作为n型热电转换材料，可以使用例如Zn0.98Al0.02O、SrTiO3(参照特开平8-186293号公报、特开平8-231223号公报)。热电转换元件例如可以以形成特开平5-315657号公报公开的结构的方式来制作。 
实施例
通过实施例更加详细地说明本发明，但本发明并不限于这些实施例。热电转换材料的诸特性用以下的方法进行测定。 
结晶构造 
使用X射线衍射测定装置(RINT2500TTR型、株式会社理学制)，采用粉末X射线衍射法，在线源：CuKα的条件下测定试样(烧成品、烧结体)的结晶构造。 
塞贝克系数(α、μV/K) 
将试样(烧结体)加工成棱柱状，得到试验片。用银浆在试验片的两端安装R热电偶和铂线，在空气中，在室温～1073K的条件下，测定试验片的温度和热电动势。此外，使流入空气的玻璃管与试验片的单面接触，并将试验片冷却，从而形成低温部。用R热电偶测定此时的试验片两端，同时测定在试验片两端面之间产生的热电动势(ΔV)。试验片两端的温度差(ΔT)通过控制空气流量而控制在1～10℃的范围。由ΔT与ΔV的斜率算出塞贝克系数(α)。 
电导率(σ、S/m) 
在与塞贝克系数(α)测定同样地，在得到的试验片上，用银浆安装铂线，通过直流四端子法，在空气中，在室温～1073K的条件下进行测定。 
热导率(κ、W/mK) 
使用热导率测定装置(TC-7000型、真空理工株式会社制)，采用激光闪光法，在测定温度为室温的条件下测定试样(烧结体)的电导率。 
相对密度(％) 
采用阿基米德法算出试样(烧结体)的相对密度。 
实施例1 
作为原料，称取CuO(株式会社高纯度化学研究所制)3.074g、SnO2(株式会社高纯度化学研究所制)5.825g、La2O3(株式会社高纯度化学研究所制)12.593g，使用湿式球磨机(介质：氧化锆制球)混合20小时。将混合物在空气下、在1100℃烧成24小时，使用湿式球磨机(介质：氧化锆制球)粉碎20小时，得到粉末。采用单螺杆冲压(成型压力：1000kg/cm2)将粉末成型，得到圆盘状成型体。将成型体在100％氧气氛围下、在1100℃烧结24小时，得到烧结体1。将烧结体1的诸物性示于表1中。将烧结体1的X射线衍射图形示于图1中。此外，烧结体1的相对密度为95％，在室温(约25℃)的热导率为5.61W/mK。 
实施例2 
作为原料，使用CuO(株式会社高纯度化学研究所制)1.537g、SnO2(株式会社高纯度化学研究所制)2.912g、La2O3(株式会社高纯度化学研究所制)6.139g、CaCO3(商品名：CS3N-A、宇部Material株式会社制)0.097g，除此之外，进行与实施例1同样的操作，得到烧结体2。 将烧结体2的诸物性示于表1中。烧结体2在室温(约25℃)的热导率为3.63W/mK。 
实施例3 
作为原料，使用CuO(株式会社高纯度化学研究所制)1.537g、SnO2(株式会社高纯度化学研究所制)2.912g、La2O3(株式会社高纯度化学研究所制)6.139g、BaCO3(商品名：LC-1、日本化学工业株式会社制)0.191g，除此之外，进行与实施例1同样的操作，得到烧结体3。将烧结体3的诸物性示于表1中。此外，烧结体3在室温(约25℃)的热导率为3.30W/mK。 
实施例4 
作为原料，使用CuO(株式会社高纯度化学研究所制)1.537g、SnO2(株式会社高纯度化学研究所制)2.912g、La2O3(株式会社高纯度化学研究所制)6.139g、SrCO3(商品名：SW-K、界化学株式会社制)0.143g，除此之外，进行与实施例1同样的操作，得到烧结体4。将烧结体4的诸物性示于表1中。 
实施例5 
作为原料，使用CuO(株式会社高纯度化学研究所制)1.537g、SnO2(株式会社高纯度化学研究所制)2.767g、La2O3(株式会社高纯度化学研究所制)6.297g、MgO(和光纯药株式会社制)0.039g，除此之外，进行与实施例1同样的操作，得到烧结体5。将烧结体5的诸物性示于表1中。 
表1  烧结体的诸物性 
      金属元素比   结晶构造
 实施例1   烧结体1   La∶Cu∶Sn为2∶1∶1   钙钛矿
 实施例2   烧结体2   La∶Ca∶Cu∶Sn＝1.95∶0.05∶1∶1   钙钛矿
 实施例3   烧结体3   La∶Ba∶Cu∶Sn＝1.95∶0.05∶1∶1   钙钛矿
 实施例4   烧结体4   La∶Sr∶Cu∶Sn＝1.95∶0.05∶1∶1   钙钛矿
 实施例5   烧结体5   La∶Cu∶Sn∶Mg＝2∶1∶0.95∶0.05   钙钛矿
表1 烧结体的诸物性(续) 
Figure GA20191857200780043906X01D00101
产业实用性 
根据本发明，提供在高温空气中的环境下，稳定地显示输出因子等热电转换特性的热电转换材料。热电转换材料在被期待作环保性发电的热电转换发电中有用。 

Claims (10)

1.一种热电转换材料，其特征在于，含有复合金属氧化物，该复合金属氧化物含有M1、M2A和M2B作为金属元素，M1∶M2A∶M2B的摩尔比为2∶1∶1，且结晶构造是钙钛矿型，其中，
M1是选自La、Y和镧系元素中的至少一种M1A，或者是M1A与选自碱土类金属元素中的至少一种M1B的组合；
M2A是选自原子价能够成为二价的金属元素中的至少一种；
M2B是选自原子价能够成为四价的金属元素中的至少一种；
M1、M2A和M2B不相同，并且M2A和M2B可以含有掺杂元素。
2.如权利要求1所述的材料，其特征在于，M1A是选自La、Y、Ce、Pr、Nd、Pm、Sm、Eu和Gd中的至少一种。
3.如权利要求2所述的材料，其特征在于，M1A是La。
4.如权利要求1所述的材料，其特征在于，M2A是选自Cu、Ni、Zn和Ag中的至少一种。
5.如权利要求4所述的材料，其特征在于，M2A是Cu。
6.如权利要求1所述的材料，其特征在于，M2B是选自Ti、V、Cr、Mn、Fe、Co、Zr、Nb、Mo、Tc、Ru、Os、Ir、Pt、Au和Sn中的至少一种。
7.如权利要求6所述的材料，其特征在于，M2B是选自Sn、Ti和Mn中的至少一种。
8.如权利要求1所述的材料，其特征在于，形状为烧结体，相对密度为60％以上。
9.如权利要求8所述的材料，其特征在于，表面被不透气膜被覆。
10.一种热电转换元件，其特征在于，含有权利要求1～9中任一项所述的材料。
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