CN100413807C - 生产钙钛矿型复合氧化物的方法 - Google Patents

生产钙钛矿型复合氧化物的方法 Download PDF

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CN100413807C
CN100413807C CNB2005800201442A CN200580020144A CN100413807C CN 100413807 C CN100413807 C CN 100413807C CN B2005800201442 A CNB2005800201442 A CN B2005800201442A CN 200580020144 A CN200580020144 A CN 200580020144A CN 100413807 C CN100413807 C CN 100413807C
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高桥恒
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Abstract

本发明提供一种生产高度结晶的钙钛矿型复合化合物的方法，该化合物即使在较高温度下也稳定地显示高塞贝克系数和低电阻率。本发明也提供一种生产具有较小环境负载的复合钙钛矿型化合物的方法。该方法包括将含有稀土元素的硝酸盐、含有碱土金属元素的硝酸盐、含有锰的硝酸盐和有机聚合物溶解在溶剂中以形成溶液的步骤，混合和搅拌溶液的步骤，通过加热和干燥从溶液制备前体粉末的步骤，和将前体粉末在大气中煅烧的步骤。

Description

生产钙钛矿型复合氧化物的方法
技术领域
本发明涉及生产用作热电变换材料的钙钛矿型复合氧化物的方法，尤其是生产含有稀土元素、碱土金属元素和锰的钙钛矿型复合氧化物的方法。
背景技术
复合钙钛矿化合物具有介电性能和/或压电性能，因此被广泛用作介电材料、压电材料等，并且也已经被用作热电变换元件装置的材料(此后称为“热电变换材料”)。热电变换是指通过塞贝克效应或珀耳帖效应，热能与电能之间的变换。通过使用热电变换，有可能使用塞贝克效应从热流产生电能，或使用珀耳帖效应通过使电流流动而引起吸热冷却现象。由金属或半导体形成的单元件装置一般用作热电变换元件装置，其性能指标取决于更高次结构，如结晶度。因此，对于热电变换材料，需要具有较少结构缺陷的化合物，以提供具有更高性能指标的单元件装置。
这些热电变换材料的优选化合物的实例是Bi-Te、Pb-Te和Si-Ge化合物等。在这些化合物中，Bi-Te和Pb-Te化合物在室温左右和300至500℃的中等温度下可显示优异的热电性能。然而，这些化合物在更高温度下的热阻很差，因此很难在更高温度下使用。而且，存在的问题是这些化合物含有昂贵的稀有金属，如Te、Sb和Se，因此其生产成本可能较高，而且也含有环境负载元素，如剧毒的Te、Sb、Se和Pb。
与此相反，氧化物陶瓷类的热电变换材料不含有稀有元素或环境负载元素，其具有以下特征：由于结构缺陷较少，热阻较高，且在长期使用的条件下，在较高温度下热电性能的下降较少；因此，作为化合物半导体的替代材料，它们引起了人们的注意。CaMnO3的钙钛矿型化合物，例如，被建议其中10％的Ca位点被Bi、La和Ce之类的金属元素替换(见非专利文件1)。另外，价格便宜的、热稳定的、和环境负载较小的含钴氧化物也引起人们的注意。
非专利文件1：Michitaka Ohtaki等人，Journal of Solid StateChemistry 120，105-111(1995)
发明内容
本发明要解决的问题
非专利文件1公开了作为高电阻n-型半导体之一的CaMnO3中，Ca位点部分替换为具有较高原子价的元素，这样可使电导率显著增加，替换的元素Bi可导致最高的功率因数。然而，由于塞贝克系数与载体浓度之间负相关，因此载体浓度的增加非常不利地降低了塞贝克系数，限制了可获得的性能指标。而且，由于其主要成分Co很昂贵，就热电变换模块的大型化和推广而言，含钴氧化物是不实用的。
本发明就是要解决上述的这些问题；本发明的一个目的是提供一种生产高度结晶化的钙钛矿型复合化合物的方法，所述化合物即使在较高温度下也可稳定地显示高塞贝克系数和低电阻率。本发明的另一个目的是提供一种生产具有较少环境负载的复合钙钛矿型化合物的方法。
解决问题的方式
具体来说，本发明提供了下面的项目。
根据制造钙钛矿型复合氧化物的方法的第一个方面，其包括将含有稀土元素的硝酸盐、含有碱土金属元素的硝酸盐、含有锰的硝酸盐和有机聚合物溶解在溶剂中形成溶液的步骤，混合和搅拌该溶液的步骤，通过加热和干燥从溶液制备前体粉末的步骤，和在大气中煅烧该前体粉末的步骤。
根据本发明的第一个方面，其包括将含有稀土元素的硝酸盐、含有碱土金属元素的硝酸盐、和含有锰的硝酸盐溶解在溶剂中的步骤，这有可能将这些溶质均匀地分散在溶剂中，因此引起均匀反应。因此，可生产较现有技术中的氧化物具有更高结晶度的氧化物，现有技术的氧化物是通过将粉末混合，然后再使其反应而产生的。另外，反应温度可以低于传统的方法。
根据生产如本发明第一个方面中所述的钙钛矿型复合氧化物的方法的第二个方面，进一步包括使前体粉末成型的步骤。
根据本发明的第二个方面，其包括使煅烧的粉末成型的步骤，这有可能用作热电变换材料。
根据生产如本发明第一个和第二个方面所述的钙钛矿型复合氧化物的方法的第三个方面，其中钙钛矿型复合氧化物表示为通式Ca(1-x)MxMn03(M是钇或镧系元素，0.001≤x≤0.05)。
根据本发明的第三个方面，具有通式Ca(1-x)MxMnO3(M是钇或镧系元素，0.001≤x≤0.05)的钙钛矿型复合氧化物有可能在较高的温度下仍然可以提高热阻。
根据生产根据本发明的钙钛矿型复合氧化物的方法，使用稀土元素作为替代元素Mx，且使用在较高温度下具有较高稳定性的Ca和Mn，有可能达到较高的塞贝克系数以及较低的电阻率。另外，能够生产如下钙钛矿型复合氧化物——在较高温度下显示优异的化学稳定性，且在较高的温度下在大气中稳定显示较高的热电性能。
附图说明
图1是显示实施例1和对比例中样品的X射线衍射谱的视图。
具体实施方式
本发明的制造钙钛矿型复合氧化物的方法在下面进行详细地解释。
本发明的生产钙钛矿型复合氧化物的方法包括将含有稀土元素的硝酸盐、含有碱土金属元素的硝酸盐、含有锰的硝酸盐、和有机聚合物溶解在溶剂中的步骤。含有稀土元素的硝酸盐的实例包括硝酸钇四水合物、硝酸钇六水合物、硝酸钆、硝酸钆六水合物、硝酸铈、硝酸铈铵、硝酸镧(lantern)等；优选硝酸钇四水合物和硝酸钇六水合物。
含有碱土金属元素的硝酸盐的实例包括硝酸铍、硝酸镁、硝酸镁六水合物、硝酸钙、硝酸钙四水合物等；优选硝酸钙和硝酸钙四水合物。
含有锰的硝酸盐是指硝酸锰六水合物。有机聚合物是指水溶性聚合物；其具体实例包括天然淀粉、明胶；纤维素衍生物，如半合成的羧甲基纤维素(CMC)和甲基纤维素(MC)；粘稠的或可凝结的水溶性聚合物，如聚乙烯醇(PVA)、聚丙烯酸聚合物和聚丙烯酰胺(PAM)和聚氧化乙烯(PEO)。优选使用聚乙烯醇。溶剂是指水、醇等。
本发明的生产钙钛矿型复合氧化物的方法包括通过加热和干燥制备前体粉末的步骤。前体粉末是指钙钛矿型复合氧化物的前体。加热和干燥优选在150至200℃，更优选在175至185℃进行。本发明也包括将前体粉末在大气中煅烧的步骤。钙钛矿型复合氧化物通过此步骤产生。煅烧温度优选800至1300℃，更优选1000至1200℃。本发明可进一步包括使前体粉末成型的步骤。可通过如冲压成型、挤出成型、粉浆浇铸和刮墨刀片法的方法进行成型，优选冲压成型。冲压成型时的压力优选0.5至2t/cm2，更优选0.8至1.2t/cm2(1kgf/cm2＝9.80665×104(Pa))。
根据本发明获得的钙钛矿型复合氧化物是由Ca(1-x)MxMnO3表示的氧化锰组合物。微量的元素Mx(替换元素)是将载体导入进氧化锰中的元素。优选Mx是三价或更高价的元素，更优选稀土元素。“x”的值优选不超过0.5，因为在“x”大于0.5时，塞贝克系数显著降低。
钙钛矿型化合物由通式ABO3表示。氧过量或氧缺乏的发生可取决于其生产条件，在本发明中氧过量或氧缺乏都是允许的。钙钛矿型化合物可有多种晶体结构，如立方、四方和斜方体系；在本发明中任何晶系都是允许的，没有限制。在此，需要立方、四方或斜方体系，因为晶体结构的结晶度越高，载体移动性越高。
通过本发明的生产钙钛矿型复合氧化物的方法获得的复合氧化物，除了用作热电变换材料以外，也可用作热电材料或压电材料。
实施例
实施例1
将总共0.0975mol硝酸钙、0.1mol硝酸锰和0.0025mol硝酸钇溶解于100ml纯水中，向其中加入20g 20质量％的聚乙烯醇(PVA)水溶液，并搅拌混合。使用干燥机在180℃将得到的水溶液加热并干燥，从而制备黑褐色的前体粉末。此后，将粉末粉碎，然后通过单轴压制在1t/cm2的压力下成型。成型体在大气中于1100℃下煅烧5小时，获得杆状单元的烧结体。烧结密度为3.11g/cm3，为理论密度的68％。
实施例2
将总共0.099mol硝酸钙、0.1mol硝酸锰和0.001mol硝酸钇溶解于100ml纯水中，向其中加入20g 20质量％的PVA水溶液，并搅拌混合。使用干燥机在180℃将得到的水溶液加热并干燥，从而制备黑褐色的前体粉末。此后，将粉末粉碎，然后通过单轴压制在1t/cm2的压力下成型。成型体在大气中于1100℃下煅烧5小时，获得杆状烧结体。烧结密度为3.20g/cm3，大约为理论密度的70％。
实施例3
将总共0.095mol硝酸钙、0.1mol硝酸锰和0.005mol硝酸钇溶解于100ml纯水中，向其中加入20g 20质量％的PVA水溶液，并搅拌混合。使用干燥机在180℃将得到的水溶液加热并干燥，从而制备黑褐色的前体粉末。此后，将粉末粉碎，然后通过单轴压制在1t/cm2的压力下成型。成型体在大气中于1100℃下煅烧5小时，获得杆状烧结体。烧结密度为3.05g/cm3，大约为理论密度的66％。
实施例4
将总共0.0975mol硝酸钙、0.1mol硝酸锰和0.0025mol硝酸镧溶解于100ml纯水中，向其中加入20g 20质量％的PVA水溶液，并搅拌混合。使用干燥机在180℃将得到的水溶液加热并干燥，制备黑褐色的前体粉末。此后，将粉末粉碎，然后通过单轴压制在1t/cm2的压力下成型。成型体在大气中于1100℃下煅烧5小时，获得杆状烧结体。烧结密度为3.16g/cm3，大约为理论密度的69％。
对比例
称量0.0975mol碳酸钙、0.1mol碳酸锰和0.00125mol氧化钇，使用自动研钵将它们混合搅拌1小时，然后在大气中于1000℃预热10小时。将得到的预热粉末粉碎，然后通过单轴压制在1t/cm2的压力下成型，其在大气中于1100℃下煅烧5小时获得杆状烧结体。烧结密度为3.84g/cm3，大约为理论密度的84％。
根据实施例1和对比例中获得的烧结粉末样品，显示X-射线衍射谱。使用X-射线衍射装置进行测量(CuKα射线：λ＝1.54nm，电流：40mA，电压：40kV)。图1显示了所获得的峰，证明对应于实施例1样品的(121)(002)面和(202)(040)面的峰强度高于对比例，而且从实施例1的峰形均更为尖锐这一事实可以看出，实施例1样品的晶体结构比对比例的更均一。
从实施例1至4和对比例的样品制备烧结体，并通过包被和烘烤Ag糊，在得到的烧结体的两端形成电极，然后测量塞贝克系数和电阻率。在热电变换元件装置的上面和下面之间施加温度差，以此方式得到塞贝克系数，且得到的电压差使用S＝dV/dT(S：塞贝克系数，dV：两点之间的电压差，dT：两点之间的温度差)进行推算。通过双端法测定电阻率。双端法是指两个电极端与样品的两个末端连接在一起，测量流过相同电极的电流和在此时产生的电压差。结果显示在表1中。从实施例1的样品显示最高的热电变换效率这一事实可以证明，根据本发明的生产方法可提供具有较高热电性能的钙钛矿型复合氧化物。
表1
  塞贝克系数(μV/K) 电阻率(Ω·cm)   功率因数(x 10-4W)
  实施例1   -347   0.07   1.72
  实施例2   -430   0.15   1.23
  实施例3   -212   0.04   1.12
  实施例4   -342   0.08   1.46
  对比例   -182   0.28   1.18
功率因子(x 10-4W/(m·K2))＝(塞贝克系数)2/电阻率

Claims (2)

1. 一种生产钙钛矿型复合氧化物的方法，所述钙钛矿型复合氧化物表示为通式Ca(1-x)MxMnO3，其中M是钇或镧系元素，且0.001≤x≤0.05，所述方法包括：
将含有钇或镧系元素的硝酸盐、含有钙的硝酸盐、含有锰的硝酸盐和有机聚合物溶解在溶剂中以形成溶液的步骤，
混合和搅拌所述溶液的步骤，
通过加热和干燥从所述溶液制备前体粉末的步骤，和
在大气中煅烧所述前体粉末的步骤。
2. 根据权利要求1所述的生产钙钛矿型复合氧化物的方法，其特征在于进一步包括使所述前体粉末成型的步骤。
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