CN106927823A - 一种铌酸盐快离子导体及其制备方法 - Google Patents

一种铌酸盐快离子导体及其制备方法 Download PDF

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CN106927823A
CN106927823A CN201710222865.6A CN201710222865A CN106927823A CN 106927823 A CN106927823 A CN 106927823A CN 201710222865 A CN201710222865 A CN 201710222865A CN 106927823 A CN106927823 A CN 106927823A
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苏聪学
覃杏柳
梁文丽
方亮
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Abstract

本发明公开了一种用于快离子导体的铌酸盐Sr3Li6Nb2O11及其制备方法。所述制备方法为按Sr3Li6Nb2O11的化学计量比称取相应的原料，然后通过球磨，高温预烧并快速取出冷却，再球磨，最后冷等静压后烧结得到Sr3Li6Nb2O11。制备方法简单，适合大规模生产。该方法合成的Sr3Li6Nb2O11高温度下具有较高的离子导电性、具有较高的热稳定性及化学稳定性，是一种优良的快离子导体材料。

Description

一种铌酸盐快离子导体及其制备方法
技术领域
本发明属于无机材料技术领域，具体涉及一种铌酸盐快离子导体及其制备方法。
背景技术
随着人类社会的发展以及工业化程度的进一步提高，开发高效、清洁、安全及经济的新型绿色能源成为了未来能源发展的必然趋势。由于离子导体具有重要的理论和实际应用价值，已在很多应用领域发展成为很有价值的材料或器件。作为离子导体中的一种材料，快离子导体材料，也称固体电解质，在高性能储能装置、燃料电池新能源材料、钠硫电池及氧分析器等领域的应用备受关注。比如氧离子导体和氢离子导体都可用作燃料电池的电解质隔膜，从而使可燃气体与氧气经电化学方法发生反应转变为电能。用氧化锆和其它快离子导体制成的气体探测器，不仅可以控制汽车发动机和锅炉燃烧室的燃烧过程以节约燃料和减少污染，而且还可以监测一些有害气体从而对环境保护作出贡献。用Na-β-Al2O3作电解质的钠-硫电池具有比铅酸电池高4～5倍的能量密度，它既可用作车辆的动力源，也可作为贮能电池使用。用快离子导体制作的固体电池具有自放电小、贮存寿命长和抗振动等优点，已在心脏起搏器电子手表、计算器和一些军用设备上获得应用。
高温燃料电池作为快离子导体(固体电解质)中的一种应用，近年来备受关注。高温燃料电池也称固体氧化物燃料电池，它们大多为基于氧空位机理的高对称的八面体和立方结构，如萤石基、钙钛矿基、Bi2O3基等固体电解质材料，但近年来，人们在低对称结构体系(如四面体、立方体、单斜等)中也寻找到高电导率的电解质材料，如黄长石结构体系，磷灰石结构体系，白钨矿结构等体系材料，而且导电机理不局限于氧空位。另外，在已报道的固体电解质材料来看，普遍存在实用性能差的缺点，主要体现在：一、工作温度过高，启动时间长，器件各组分间化学和力学兼容性差；二、导电率低；只能在800-1000℃高温下使用；三、还原气氛下某些元素如Ce部分还原成Ce3+，致使产生电子导电，甚至某些固体电解质材料在还原气氛下易分解；四、某些元素如Ga的挥发，而且工艺复杂，组件间化学兼容性差。由此可见，在理论上，人们难以通过结构来判断化合物是否具备作为快离子导体的应用；在实际应用上，人们难以找到具有实用的快离子导体材料，即具备较高的离子导电性、较低的工作温度(500℃左右)、使用温度下较高的热稳定性及化学稳定性、大规模生产的可操作性等特点。目前铌氧八面体构成的铌酸盐作为快离子导体鲜有报道，如能在铌酸盐体系中开发出新型快离子导体将是重要发现。
发明内容
本发明的目的是提供一种用于快离子导体的铌酸盐Sr3Li6Nb2O11及其制备方法。
本发明涉及的用于快离子导体的铌酸盐的化学表示式为:Sr3Li6Nb2O11。
所述铌酸盐的制备方法具体步骤为：
(1)将Li2CO3、SrCO3和Nb2O5的原始粉末按Sr3Li6Nb2O11的组成称量配料并放入球磨罐中，加入直径为7mm的氧化锆球和去离子水，球磨2小时，混合均匀磨细，取出烘干得到粉末原料；
(2)将步骤(1)烘干后的粉末原料压成柱状样品，置于陶瓷承烧板上，用坩埚罩住样品，然后置于管式炉中，600℃煅烧，保温2小时，然后从600℃的管式炉中用钳子夹住承烧板并快速取出，使陶瓷承烧板上，坩埚内的样品快速冷却，冷却至室温后捣碎研磨成粉末；
(3)将步骤(2)研磨所得的粉末放入球磨罐中，加入直径分别为2mm和7mm的氧化锆球，粉末和氧化锆球在球磨罐里球磨15个小时，混合均匀磨细，得到粉末原料；
(4)将步骤(3)球磨后的粉末原料冷等静压20MPa成型为直径1.3cm，厚度0.3cm的圆片，然后在马弗炉中650-700℃烧结，保温6小时后，自然冷却至室温，得到铌酸盐Sr3Li6Nb2O11。
本发明的优点：通过本制备方法得到的铌酸盐Sr3Li6Nb2O11具有较高的离子导电性、使用温度下具有较高的热稳定性及化学稳定性；在烧结温度下结构保持不变，在300-500℃时电导率为10-3～10-2S/cm，是一种优良的快离子导体材料。另外制备方法简单、合成温度低，绿色环保成本低，相对于其他固体电解质材料的湿化学法制备工艺，本方法更适合工业生产与应用。
附图说明
图1为Sr3Li6Nb2O11样品的晶体结构图。
具体实施方式
下面结合实施例对本发明作进一步的说明，但本领域的技术人员了解，下述实施例不是对发明保护范围的限制，任何在本发明基础上的改进和变化都在本发明的保护范围之内。
实施例1：
(1)将Li2CO3、SrCO3和Nb2O5的原始粉末按Sr3Li6Nb2O11的组成称量配料并放入球磨罐中，加入直径为7mm的氧化锆球和去离子水，球磨2小时，混合均匀磨细，取出烘干得到粉末原料；
(2)将步骤(1)烘干后的粉末原料压成柱状样品，置于陶瓷承烧板上，用坩埚罩住样品，然后置于管式炉中，600℃煅烧，保温2小时，然后从600℃的管式炉中用钳子夹住承烧板并快速取出，使陶瓷承烧板上，坩埚内的样品快速冷却，冷却至室温后捣碎研磨成粉末；
(3)将步骤(2)研磨所得的粉末放入球磨罐中，加入直径分别为2mm和7mm的氧化锆球，粉末和氧化锆球在球磨罐里球磨15个小时，混合均匀磨细，得到粉末原料；
(4)将步骤(3)球磨后的粉末原料冷等静压20MPa成型为直径1.3cm，厚度0.3cm的圆片，然后在马弗炉中650℃烧结，保温6小时后，自然冷却至室温，得到铌酸盐Sr3Li6Nb2O11。
本实施例所得到的铌酸盐Sr3Li6Nb2O11，在两底面涂上金胶，在550℃下烧结1小时。使用Solartron1260(英国Solartron公司)阻抗分析仪在不同温度下测定其交流阻抗。测定结果为300℃时电导率达到7.66×10-3S/cm，在500℃时电导率快速升到5.24×10-2S/cm。
实施例2：
(1)将Li2CO3、SrCO3和Nb2O5的原始粉末按Sr3Li6Nb2O11的组成称量配料并放入球磨罐中，加入直径为7mm的氧化锆球和去离子水，球磨2小时，混合均匀磨细，取出烘干得到粉末原料；
(2)将步骤(1)烘干后的粉末原料压成柱状样品，置于陶瓷承烧板上，用坩埚罩住样品，然后置于管式炉中，600℃煅烧，保温2小时，然后从600℃的管式炉中用钳子夹住承烧板并快速取出，使陶瓷承烧板上，坩埚内的样品快速冷却，冷却至室温后捣碎研磨成粉末；
(3)将步骤(2)研磨所得的粉末放入球磨罐中，加入直径分别为2mm和7mm的氧化锆球，粉末和氧化锆球在球磨罐里球磨15个小时，混合均匀磨细，得到粉末原料；
(4)将步骤(3)球磨后的粉末原料冷等静压20MPa成型为直径1.3cm，厚度0.3cm的圆片，然后在马弗炉中680℃烧结，保温6小时后，自然冷却至室温，得到铌酸盐Sr3Li6Nb2O11。
本实施例所得到的铌酸盐Sr3Li6Nb2O11，在两底面涂上金胶，在550℃下烧结1小时。使用Solartron1260(英国Solartron公司)阻抗分析仪在不同温度下测定其交流阻抗。测定结果为300℃时电导率达到8.56×10-3S/cm，在500℃时电导率快速升到5.74×10-2S/cm。
实施例3：
(1)将Li2CO3、SrCO3和Nb2O5的原始粉末按Sr3Li6Nb2O11的组成称量配料并放入球磨罐中，加入直径为7mm的氧化锆球和去离子水，球磨2小时，混合均匀磨细，取出烘干得到粉末原料；
(2)将步骤(1)烘干后的粉末原料压成柱状样品，置于陶瓷承烧板上，用坩埚罩住样品，然后置于管式炉中，600℃煅烧，保温2小时，然后从600℃的管式炉中用钳子夹住承烧板并快速取出，使陶瓷承烧板上，坩埚内的样品快速冷却，冷却至室温后捣碎研磨成粉末；
(3)将步骤(2)研磨所得的粉末放入球磨罐中，加入直径分别为2mm和7mm的氧化锆球，粉末和氧化锆球在球磨罐里球磨15个小时，混合均匀磨细，得到粉末原料；
(4)将步骤(3)球磨后的粉末原料冷等静压20MPa成型为直径1.3cm，厚度0.3cm的圆片，然后在马弗炉中700℃烧结，保温6小时后，自然冷却至室温，得到铌酸盐Sr3Li6Nb2O11。
本实施例所得到的铌酸盐Sr3Li6Nb2O11，在两底面涂上金胶，在550℃下烧结1小时。使用Solartron1260(英国Solartron公司)阻抗分析仪在不同温度下测定其交流阻抗。测定结果为300℃时电导率达到8.41×10-3S/cm，在500℃时电导率快速升到5.21×10-2S/cm。
由于钠离子和锂离子在快离子导体中经常作为迁移离子，又考虑到Sr和Ba，Nb和Ta具有类似的化学性质，因此在本申请的实验条件下，制备Sr3Na6Nb2O11、Ba3Li6Nb2O11以及Sr3Li6Ta2O11陶瓷片，并在相同条件下测试其电导率，结果发现只有Sr3Li6Ta2O11具有最高的电导率3.16×10-5S/cm，而Ba3Li6Nb2O11和Sr3Na6Nb2O11因热稳定性差而产生电子电导，无法作为快离子导体。

Claims (1)

1.一种铌酸盐作为快离子导体的应用，其特征在于所述铌酸盐具有如下化学表示式：Sr3Li6Nb2O11；
所述铌酸盐在300-500℃时电导率为10-3～10-2S/cm；
所述铌酸盐的制备方法具体步骤为：
(1)将Li2CO3、SrCO3和Nb2O5的原始粉末按Sr3Li6Nb2O11的组成称量配料并放入球磨罐中，加入直径为7mm的氧化锆球和去离子水，球磨2小时，混合均匀磨细，取出烘干得到粉末原料；
(2)将步骤(1)烘干后的粉末原料压成柱状样品，置于陶瓷承烧板上，用坩埚罩住样品，然后置于管式炉中，600℃煅烧，保温2小时，然后从600℃的管式炉中用钳子夹住承烧板并快速取出，使陶瓷承烧板上，坩埚内的样品快速冷却，冷却至室温后捣碎研磨成粉末；
(3)将步骤(2)研磨所得的粉末放入球磨罐中，加入直径分别为2mm和7mm的氧化锆球，粉末和氧化锆球在球磨罐里球磨15个小时，混合均匀磨细，得到粉末原料；
(4)将步骤(3)球磨后的粉末原料冷等静压20MPa成型为直径1.3cm，厚度0.3cm的圆片，然后在马弗炉中650-700℃烧结，保温6小时后，自然冷却至室温，得到铌酸盐Sr3Li6Nb2O11。
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