CN1285138C - 固体氧化物燃料电池用复合氧化物及其制造方法 - Google Patents

固体氧化物燃料电池用复合氧化物及其制造方法 Download PDF

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CN1285138C
CN1285138C CNB028225422A CN02822542A CN1285138C CN 1285138 C CN1285138 C CN 1285138C CN B028225422 A CNB028225422 A CN B028225422A CN 02822542 A CN02822542 A CN 02822542A CN 1285138 C CN1285138 C CN 1285138C
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composite oxides
fuel cell
phase
solid oxide
oxide fuel
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CN1586020A (zh
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宗像文男
古谷健司
秦野正治
藤江良纪
数原学
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KIYOMI CHEMICAL CO Ltd
Seimi Chemical Co Ltd
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Abstract

本发明提供一种燃料电池用固体氧化物，它是可在低温下进行焙烧，目标组成以外的杂质异相少的高性能低温工作型的固体氧化物，它是具有含稀土元素的钙钛矿型晶体结构的、构成元素均质分散而成的复合氧化物，通过使用金属的碳酸盐、氧化物或氢氧化物，在水系中和柠檬酸进行反应形成异相的存在以平均面积比率表示，在0.3%以下，熔点在1470℃以上的均质的复合氧化物。

Description

固体氧化物燃料电池用复合氧化物及其制造方法
                        技术领域
本发明涉及用作采用固体电解质的燃料电池的电解质或空气极的复合氧化物及其制造方法，更加详细地涉及具有钙钛矿结构的氧离子导电性的固体氧化物燃料电池用复合氧化物及其适用于工业化的制造方法。
                        背景技术
现在，固体氧化物燃料电池(SOFC)的开发日新月异。作为该燃料电池的电解质，通常使用稳定氧化锆。但是，稳定氧化锆的电解质在低温下离子导电性低，所以要在1000℃以上的高温下使用。为此，不能使用金属来作为燃料电池的部件，而必须使用高价的陶瓷。
为了解决该问题，最近开发出LaGaO3的钙钛矿型的电解质，与稳定氧化锆相比，它可在低温下使用。其中有报告称LaSrGaMgO3显示出良好的性能(参考KHuang，R.S.Tichy，and J.B.Goodenough，J.Am.Ceram.Soc.，81，2565(1998)，美国专利6004688号，日本特许公开公报平11-335164号，日本特许公开公报平11-665165号)。
但该LaGaO3类化合物在合成时，存在典型元素Ga很难组成钙钛矿结构，必须在高温下烧成，容易残留目标组成以外的杂质异相的问题。作为该杂质异相，以熔点较钙钛矿低，大约为1400℃，氧离子导电性也低的LaSrGaO4，和熔点在1600℃以上且氧离子导电性低的LaSrGa3O7为代表。在固相合成法中，直接将作为原料的金属的氧化物、碳化物或氢氧化物粉碎混合，并进行焙烧，为此，容易产生微细混合状态的不均匀，所以容易残留杂质异相。若要合成杂质异相少的钙钛矿就必须在1500℃以上的高温下进行烧成。
另一方面，在将合成后的固体复合氧化物粉末成形为燃料电池用电解质或电极时，通常通过将固体复合氧化物粉末压制成形，加热到1300-1600℃使其烧结，制得烧结体构造物。
为此，在将固相合成法所合成的氧化物粉末压制成形，进行烧结时，该氧化物粉末所含的杂质异相熔解，烧结体的空隙被氧离子导电性低的杂质异相覆盖，很难形成均质的电极体。
如上所述，若采用以往所用的一般的合成法，即固相合成法的话，焙烧中，以目标组成物和中间体或合成原料混杂在的状态达到高温，所以其中的一部分熔融，作为杂质异相残留在最终的制品中。
作为更低温度下构成组合的一般的制造方法，采用硝酸盐和乙酸盐的方法为人所公知。但是，采用该方法，在焙烧时大量产生二氧化氮、氮氧化物、乙酸等有害气体，不适合工业制造。另外，使用乙二醇等有机溶剂来作为溶剂的溶胶-凝胶法也是较常用的方法，但因凝胶状物质粘附在容器壁上，会剧烈燃烧，所以也不适合于工业制造。
作为其它的金属复合氧化物的合成法，本发明者所提出的日本特许公开公报平7-96443号、日本特许第3081212号、日本特许公开公报平9-086928号、日本特许公开公报平08-130018号等中公开了钇-碱土金属-过渡金属复合氧化物、铋-碱土金属-过渡金属复合氧化物、镧-锶-钴复合氧化物或镧-钴-铁复合氧化物的柠檬酸合成法。但所得的氧化物的电导率在600-800℃的低温区域内都低，所以不适合作为低温工作型固体电解质电池用材料。
对于燃料电池用固体氧化物要求其为杂质异相特别少的低温工作型固体氧化物。因此，本发明的课题是提供一种低温工作型的固体氧化物燃料电池用复合氧化物及有利于其工业制造的方法。该复合氧化物可在较低温度下烧成，目标组成以外的杂质异相少并具有高性能。
                        发明内容
本发明者发现：通过采用柠檬酸合成法，在特定条件下使特定的原料化合物反应，可在中间体和合成原料不熔融的较低温度下制成所要的钙钛矿型组成物(复合氧化物)，可以制造出最终所得的复合氧化物中不同于钙钛矿相的异相少，构成元素均质分散，几乎接近于单相的组成物。利用该复合氧化物可使低温工作型固体燃料电池电极的性能提高。
即，本发明具有如下的要点。
一种固体氧化物燃料电池用复合氧化物，它是由通式Ln1-xAxGa1-y-zByCzO3-δ(1)表示的具有钙钛矿型晶体结构的固体氧化物燃料电池用复合氧化物，其特征在于，和具有钙钛矿结构的相不同的异相的存在比率按平均面积比率计，在0.3％以下，式(1)中，Ln为选自镧、铈、镨、钕、钐、钆、镝中的至少一种的元素；A为选自锶、钙及钡中至少一种的元素；B为选自镁、铝以及铟中至少一种的元素；C为选自铁、钴、镍及锰中至少一种的元素，0.05≤x≤0.4、0.02≤y≤0.4、0.1≤y+z≤0.45、0≤δ≤1。
另外，本发明还是固体氧化物燃料电池用复合氧化物的制造方法，它是由上述(1)表示的具有钙钛矿型晶体结构的固体氧化物燃料电池用复合氧化物的制造方法，其特征在于，构成复合氧化物的金属元素的原料为选自氢氧化物、氧化物或碳酸盐中的任意一种的金属化合物，对该金属化合物和柠檬酸反应所生成的反应生成物，即复合柠檬酸盐进行热分解。
                        附图说明
图1(a)是本发明的实施例1的复合氧化物的X射线解析图。
图1(b)是实施例1的烧结体的扫描型电子显微镜图像(倍率为2000倍)。
图1(c)是将图1(b)中无空隙部分切下大约8.8平方微米放大后，经图像处理而得的二值化的图像。
图2是本发明的实施例2的复合氧化物的X射线解析图。
图3是本发明的实施例3的复合氧化物的X射线解析图。
图4是本发明的实施例4的复合氧化物的X射线解析图。
图5(a)是采用以往的方法的比较例1的复合氧化物的X射线解析图。
图5(b)是比较例1的烧结体的扫描型电子显微镜图像(倍率为2000倍)。
图5(c)是将图5(b)中无空隙部分切下大约22平方微米放大后，经图像处理而得的二值化的图像。
图6是采用以往的方法的比较例2的复合氧化物的X射线解析图。
                        具体实施方式
表示上述本发明的复合氧化物的通式(1)中，0.05≤x≤0.40、0.02≤y≤0.40、0.10≤y+z≤0.45的条件是获得钙钛矿结构所必须的。δ要满足0≤δ≤1。δ在该范围外，钙钛矿结构不稳定，因此不理想。尤其是若要更容易形成钙钛矿结构，同时能够提高氧离子导电性，特好是0.10≤x≤0.25、0.05≤y≤0.25、0.15≤y+z≤0.40。
在通式(1)中，特别是Ln(镧类稀土金属)为La、A(碱土金属)为Sr、B(非过渡金属)为镁对能够提高低温时的电导率是较为理想的。另外，C(过渡金属)为Co时，对能够提高低温时的电导率是更理想的。
在制造本发明的复合氧化物时，在水中混合复合氧化物所含的金属元素的碳酸盐、氧化物或氢氧化物而成的原料浆液中，添加将全部的金属离子变为柠檬酸盐所需的化学当量的柠檬酸的25-100％，较好为60-100％的柠檬酸，较好在25-100℃，特好在50-70℃下进行反应。若将上述金属元素以硝酸盐、氯化物、硫酸盐等形态使用的话，复合柠檬酸盐合成时或热分解时会产生有害的副产气体，或热分解很难进行，因此不理想。
在本发明中，为了得到构成元素均质分散的均匀的复合柠檬酸盐，特好用氢氧化物作为Ln的镧类稀土元素原料。为使异相减少，镓特好使用氢氧化镓。对于构成成分A的碱土类金属，为减少异相，较好用碳酸盐。通过这些特定化合物的组合，可合成相当均匀的复合柠檬酸盐，其结果可使焙烧后的钙钛矿的均质性提高。
和上述柠檬酸反应后，进行干燥和脱水，热分解并进行煅烧(calcination)。此时，也可采用一段焙烧的方法进行热分解和煅烧。但若将热分解和煅烧同时进行的话，很难取得反应系统的均热，所以较好将热分解和煅烧分成2段进行。
将所生成的复合柠檬酸盐在较好的350-500℃下进行热分解后，在较好的900-1470℃进行煅烧。该发明点也是本发明的特征之一。煅烧可以直接以粉体进行，也可以利用压制等进行成形后，进行焙烧。煅烧温度若未满900℃时，烧结不充分，不能得到致密的粉体，不理想。另一方面，若煅烧温度超过1470℃的话，炉体材料容易劣化，而且，耗热量增加，不理想。
煅烧温度更好在1200-1450℃，特好在1300-1420℃。热分解及煅烧气氛无论是空气等氧化性气氛或惰性气氛都可以。可以在热分解后进行粉碎。另外，煅烧后，可以利用喷射磨、球磨机等进行粉碎。对粉碎方法无特别限制。
通过本发明，可制得烧结体组织中的和钙钛矿结构的相不同的异相的存在比率以面积比率表示，在0.3％以下的复合氧化物。若异相的存在比率超过平均面积比率0.3％时，熔点降低，烧结体的韧性减弱，并且电导率下降，不理想。异相的存在比率特好在平均面积比率0.15％以下，更好在0.1％以下。
钙钛矿复合氧化物中的异相结构在异相比率高时，可通过X射线衍射光谱检出，在异相的比率低时，可采用扫描型电子显微镜，通过反射电子像进行定量。在本发明中，钙钛矿复合氧化物中的异相的定量是通过对反射电子像进行图像解析来进行的。
本发明所制得的复合氧化物因LaSrGaO4等的杂质异相少，组合成单一的晶体结构，所以具有熔点较好在1470℃以上，特好在1500℃以上的特征。若熔点未满1470℃的话，成形时容易熔融，不理想。
利用本发明所得的复合氧化物，和以往的通过固相法所制得的复合氧化物相比，具有容易制得有韧性的成形体的优点。另外，和以往的利用固相法制得的复合氧化物相比，还具有在煅烧粉的粉碎时，很难产生微粉的特征。由此，可将粉碎后的粉体的振实密度提高，所以具有容易制得致密的成形体的优点。由此，本发明的复合氧化物的振实密度较好在1.0g/cm3以上，若振实密度未满1.0g/cm3的话，很难制得致密且高强度的成形体，不理想。特别是利用本发明，可制得振实密度在1.2g/cm3以上的复合氧化物。
本发明的复合氧化物的重量平均粒径较好有0.4-2μm。若重量平均粒径未满0.4μm的话，很难制得致密的电极成形体，不理想。另一方面，重量平均粒径超过2.0μm时，成形体的强度降低，不理想。重量平均粒径特好的范围为0.8-1.3μm。
以下，就本发明的具体的实施例1-4及比较例1，2进行说明。
在各例中，晶体结构的识别是通过X射线衍射(リガク公司制造的Cu-Kα射线)进行。熔点利用TG-DTA分析(精工公司制造)以10℃/分钟进行升温来求出。粒径分布利用激光衍射式分析(マイクロトラツク公司制造)进行测定，求出重量平均粒径。振实密度是根据JIS R9301-2-3法，利用粉体检验器(ホソカワミクロン公司制造)来求出。
在各例中，对于在烧结体组织中和具有钙钛矿结构的相不同的异相的存在比率，利用金属模型，通过流体静压对复合氧化物粉末施加2吨/cm2的压力进行成型，于1450℃进行6小时的焙烧，制得固体电解质烧结体后，得到同一烧结体的扫描型电子显微镜观察时的2000倍的图像，利用高速图像处理装置(カルツアイス公司制造VIDAS Plus)，采用高速图像处理软件(カルツアイス公司制造KS400)对1试样从5个视角(广度为2902μm2)进行取样，算出平均值，作为异相的平均面积分率求出。
(实施例1)
分别将氢氧化镧、碳酸锶、氢氧化镓、碳酸镁作为原料粉，配合成La0.87Sr0.13Ga0.8Mg0.2O3-δ，分散在水中。将温度控制在70℃，添加将全部的金属离子变为柠檬酸盐所需的柠檬酸，使其进行反应。
反应后，在120℃进行干燥，粉碎后，于400℃进行6小时的预焙烧，进行热分解。此后，再进行粉碎混合，于1450℃进行12小时的焙烧。焙烧后的形状为白色粉末。焙烧后，利用球磨机进行6小时的粉碎。制得的复合氧化物粉末的重量平均粒径为0.56μm，振实密度为1.27g/cm3，晶体结构解析结果如图1(a)所示，焙烧后的状态、熔点及X射线衍射识别结果如表1所示。
从该粉末制得烧结体，利用2000倍的扫描型电子显微镜进行观察的图像如图1(b)所示。将该图1(b)图像中无空隙(黑色的孔)的部分切下大约8.8平方微米放大后进行图像处理后的二值化的图像如图1(c)所示。以该图1(c)为基准，仅对白色部分进行计测。
通过该图像解析，对由钙钛矿构成的连续相中所存在的微粒所构成的异相，由每单位面积的粒子数和平均粒径从5个视角来求出异相的面积比率后发现，异相的面积比率分别为0.292％、0.172％、0.141％、0.0065％、0.082％，异相的平均面积比率为0.150％。
(实施例2)
分别将氢氧化镧、碳酸锶、氢氧化镓、碳酸镁作为原料粉，配合成La0.87Sr0.13Ga0.8Mg0.2O3-δ，分散在水中。将温度控制在70℃，添加将全部的金属离子变为柠檬酸盐所需的柠檬酸，使其进行反应。
反应后，在120℃进行干燥，粉碎后，于400℃进行6小时的预焙烧，进行热分解。此后，再进行粉碎混合，于1350℃进行12小时的焙烧。
焙烧后的形状为白色粉末。焙烧后，利用球磨机进行6小时的粉碎。制得的复合氧化物粉末的重量平均粒径为0.49μm，振实密度为1.21g/cm3，晶体结构解析结果如图2所示，焙烧后的状态、熔点及X射线衍射识别结果如表1所示。和实施例1一样求出的烧结体的异相的平均面积比率为0.159％。
(实施例3)
分别将氢氧化镧、碳酸锶、氢氧化镓、碳酸镁、碳酸钴作为原料粉，以配合成La0.8Sr0.2Ga0.6Mg0.2Co0.2O3-δ，分散在水中。将温度变为70℃，添加将全部的金属离子变为柠檬酸盐所需的柠檬酸，使其进行反应。
反应后，在120℃进行干燥，粉碎后，于400℃进行6小时的预焙烧，进行热分解。此后，再进行粉碎混合，于1450℃进行12小时的焙烧。
焙烧后的形状为黑色粉末。焙烧后，利用球磨机进行6小时的粉碎。制得的复合氧化物粉末的重量平均粒径为0.86μm，振实密度为1.34g/cm3，晶体结构解析结果如图3所示，焙烧后的状态、熔点及X射线衍射识别结果如表1所示。和实施例1一样求出的烧结体的异相的平均面积比率为0.107％。
(实施例4)
分别将氢氧化镧、碳酸锶、氢氧化镓、碳酸镁作为原料粉，以配合成La0.87Sr0.13Ga0.8Mg0.2O3-δ，分散在水中。将温度控制在70℃，添加将全部的金属离子变为柠檬酸盐所需的柠檬酸量的70％，使其进行反应。
反应后，在120℃进行干燥，粉碎后，于400℃进行6小时的预焙烧，进行热分解。此后，再进行粉碎混合，于1350℃进行12小时的焙烧。
焙烧后的形状为白色粉末。焙烧后，利用球磨机进行6小时的粉碎。制得的复合氧化物粉末的重量平均粒径为0.66μm，振实密度为1.22g/cm3，晶体结构解析结果如图4所示，焙烧后的状态、熔点及X射线衍射识别结果如表1所示。和实施例1一样求出的烧结体的异相的平均面积比率为0.168％。
(比较例1)
分别将氧化镧、碳酸锶、氧化镓、碳酸镁作为原料粉，配合成La0.87Sr0.13Ga0.8Mg0.2O3-δ，利用球磨机粉碎混合。将混合物于400℃下进行6小时的预焙烧，进行热分解。此后，再进行粉碎、混合，于1450℃进行12小时的焙烧。
焙烧后的形状为褐色块状。焙烧后，利用球磨机进行6小时的粉碎。制得的复合氧化物粉末的重量平均粒径为2.21μm，振实密度为0.98g/cm3，晶体结构解析结果如图5(a)所示，焙烧后的状态、熔点及X射线衍射识别结果如表1所示。
和实施例1一样观察后的2000倍的扫描型电子显微镜的图像如图5(b)所示。将该图5(b)图像中无空隙(黑色的孔)的部分切下大约22平方微米放大后进行图像处理后的二值化的图像如图5(c)所示。以该图5(c)为基准，仅对白色部分进行计测。
通过该图像解析，和实施例1一样从5个视角来求出异相的面积比率后发现，异相的面积比率分别为0.770％、0.406％、0.547％、1.234％、0.596％，异相的平均面积比率为0.711％。
(比较例2)
分别将氧化镧、碳酸锶、氧化镓、碳酸镁、氧化钴作为原料粉，配合成La0.8Sr0.2Ga0.6Mg0.2Co0.2O3-δ，利用球磨机粉碎混合。将混合物于400℃下进行6小时的预焙烧，进行热分解。此后，再进行粉碎混合，于1450℃进行12小时的焙烧。
焙烧后的形状为黑色块状。焙烧后，利用球磨机进行6小时的粉碎。制得的复合氧化物粉末的重量平均粒径为2.11μm，振实密度为0.92g/cm3，晶体结构解析结果如图6所示，焙烧后的状态、熔点及X射线衍射识别结果如表1所示。
对钙钛矿相不进行识别。
                        表1
  焙烧后的状态   熔点(℃)   X射线衍射识别结果
  实施例1   白色粉体   1500℃以上   钙钛矿结构单相
  实施例2   白色粉体   1500℃以上   钙钛矿结构单相
  实施例3   黑色粉体   1500℃以上   钙钛矿结构单相
  实施例4   白色粉体   1500℃以上   钙钛矿结构单相
  比较例1   褐色块状   1375℃   钙钛矿结构含有杂质
  比较例2   黑色块状   1420℃   未知结构
产业上利用的可能性
通过本发明，提供一种可在较低温度下焙烧、目标组成以外的杂质异相少、极其均匀的高性能低温工作型的固体氧化物燃料电池用复合氧化物。另外，和以往的制造方法比较，提供一种焙烧时不产生有害气体、有利于工业化制造，可批量生产复合氧化物的制造方法。

Claims (4)

1.一种固体氧化物燃料电池用复合氧化物，它是由通式Ln1-xAxGa1-y-zByCzO3-δ(1)表示的具有钙钛矿型晶体结构的固体氧化物燃料电池用复合氧化物，其特征在于，和具有钙钛矿结构的相不同的异相的存在比率以平均面积比率表示，在0.3％以下，复合氧化物的重量平均粒径为0.4-2μm且振实密度在1.0g/cm3以上，式(1)中，Ln为选自镧、铈、镨、钕、钐、钆、镝中的至少一种元素；A为选自锶、钙及钡中的至少一种元素；B为选自镁、铝以及铟中的至少一种元素；C为选自铁、钴、镍及锰中的至少一种的元素，0.05≤x≤0.4，0.02≤y≤0.4，0.1≤y+z≤0.45，0≤δ≤1。
2.根据权利要求1所述的复合氧化物，其特征在于，复合氧化物的熔点在1470℃以上。
3.根据权利要求1所述的复合氧化物，其特征在于，上述通(1)式中，Ln原料为La，A原料为Sr、B原料为Mg。
4.固体氧化物燃料电池用复合氧化物的制造方法，其特征在于，它是由通式Ln1-xAxGa1-y-zByCzO3-δ(1)表示的具有钙钛矿型晶体结构的固体氧化物燃料电池用复合氧化物的制造方法，其特征在于，构成复合氧化物的含Ln的金属化合物及含镓的金属化合物都为氢氧化物，而含A的金属化合物为碳酸盐，对该金属化合物以水为溶剂制成浆液，使该浆液和柠檬酸反应，将反应生成的复合柠檬酸盐在350-500℃进行热分解后，于900-1470℃进行焙烧，式(1)中，Ln为选自镧、铈、镨、钕、钐、钆、镝中的至少一种的元素；A为选自锶、钙及钡中的至少一种的元素；B为选自镁、铝以及铟中的至少一种的元素；C为选自铁、钴、镍及锰中的至少一种的元素，0.05≤x≤0.4，0.02≤y≤0.4，0.1≤y+z≤0.45，0≤δ≤1。
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