CN109053186B - 一种定磷探头用掺镧固体电解质及其制备方法 - Google Patents

一种定磷探头用掺镧固体电解质及其制备方法 Download PDF

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CN109053186B
CN109053186B CN201811249927.3A CN201811249927A CN109053186B CN 109053186 B CN109053186 B CN 109053186B CN 201811249927 A CN201811249927 A CN 201811249927A CN 109053186 B CN109053186 B CN 109053186B
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康雪
温斌
王彪
侯剑峰
王常珍
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Northeastern University Qinhuangdao Branch
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Abstract

本发明公开了一种定磷探头用掺镧固体电解质，属于固体电解质电化学传感器技术领域。本发明的掺镧固体电解质的通式为4Ca1‑ xLaxO1‑a•P2O5，其中，0＜x≤0.2，该掺镧固体电解质具有较好的稳定性、抗热震性能、电导率高、化学稳定性好，利用其制备的固体电解质管具有优良的力学性能；同时本发明的制备方法，步骤简单、易操作实现、反应条件易控制，从而保障了固体电解质的性能稳定。本发明可应用于各类金属熔体特别是铜及铁金属熔体中磷的检测。

Description

一种定磷探头用掺镧固体电解质及其制备方法
技术领域
本发明涉及固体电解质电化学传感器技术领域，尤其是涉及一种定磷探头用掺镧固体电解质。
背景技术
磷在金属冶炼中是脱除元素之一，容易产生偏析，产生冷脆而影响金属的质量。在冶炼后期，还会产生回磷，对金属冶炼过程的终点控制影响极大，快速测试磷含量是冶炼重点控制的基础，也尤为重要。而当前冶炼过程中的检测方法分为化学法和光谱法，其中化学法需要取样、称量、溶解、滴定，费时较长，制约了现场指导生产；而光谱法的应用相对节约了时间，可以在几分钟内完成，但是精确度还有待提高。
因此，金属冶炼中磷含量的在线检测成为了检测趋势。目前金属熔体中定磷探头化学传感器研究中，使用氧化镁稳定氧化锆材料作为固体电解质，用外涂辅助电极材料实现。而实际使用过程中，由于辅助电极材料容易脱落，影响测成率，现场应用受到限制。因此，发明一种化学稳定性好的适用于定磷探头的固体电解质，显得尤为必要。
发明内容
为解决现有技术的不足，本发明提供一种定磷探头用掺镧固体电解质及制备方法，所得定磷探头用固体电解质具有较好的稳定性，其制备方法步骤简单易操作。
为了实现上述目标，本发明采用如下的技术方案：一种定磷探头用掺镧固体电解质，是将干燥的CaCO3或CaO、CaHPO4∙2H2O和La2O3粉体按比例混合，烧结后得到。
一种定磷探头用掺镧固体电解质，所述电解质的通式为4Ca1-xLaxO1+a∙P2O5，其中，0＜x≤0.2。
优选的，一种定磷探头用掺镧固体电解质，所述电解质为4Ca0.9La0.1O1+a∙P2O5。
一种定磷探头用掺镧固体电解质的制备方法，制备步骤如下。
（1）将CaCO3或CaO、CaHPO4∙2H2O和La2O3粉体，脱水干燥后备用。
（2）按0.8-0.85：1：0.05摩尔比称取备用的CaCO3（CaO）、CaHPO4∙2H2O和La2O3粉体，机械混合均匀，所得混合粉体的颗粒中径粒度为10～50微米。
（3）将步骤（2）混合均匀的粉体以3℃～10℃/min的升温速率加热至1450～1580℃下进行烧结，烧结2h～5h，然后冷却至室温即得一种定磷探头用掺镧固体电解质。
本发明的有益效果。
（1）本发明的定磷探头用掺镧固体电解质，电导率高，化学稳定性和抗热震性能好，利用本发明固体电解质制备的固体电解质管具有优良的抗腐蚀性能。该电解质材料克服了由于电解质中氧化钙吸水而导致电解质潮解的问题，增加了固体电解质材料的化学稳定性及抗热震性能；通过添加La提高电导性能，与纯4CaO∙P2O5固体电解质相比，本发明的电解质电导率提升5%～10%。
（2）本发明的定磷探头用掺镧固体电解质的制备方法，其中混合采用机械混合，所得混合粉体的颗粒中径粒度10～50微米，该粒度尺寸适中，既保障了成分均匀，易于充分反应，同时粒度易控制，不会造成操作成本的增加；在烧结过程中，以3℃～8℃/min的升温速率加热至1450～1580℃下进行烧结2h～5h，不但减少了烧结能耗，同时可以得到纯的单斜晶系的结构，保障所得固体电解质符合定磷探头使用要求。本发明的制备方法，步骤简单，易操作实现，反应条件易控制，减少了烧结能耗，保障了固体电解质的性能稳定。
具体实施方式
以下结合具体实施例对本发明作进一步说明。
实施例1。
一种定磷探头用掺镧固体电解质，所述电解质的通式为4Ca1-xLaxO1+a∙P2O5，x=0.1。
一种定磷探头用掺镧固体电解质的制备方法，包括以下步骤。
（1）将CaCO3、CaHPO4∙2H2O和La2O3粉体，脱水干燥后备用。
（2）按摩尔比CaCO3：CaHPO4∙2H2O：La2O3=0.8：1：0.05取三种备用粉体，机械混合均匀，所得混合粉体的颗粒中径粒度为10～50微米。
（3）将步骤（2）混合均匀的粉体以3℃/min的升温速率加热至1450℃下进行烧结，烧结5h， 干燥气氛下冷却至室温即得一种定磷探头用掺镧固体电解质。
实施例2。
一种定磷探头用掺镧固体电解质，所述电解质的通式为4Ca1-xLaxO1+a∙P2O5，x=0.05。
一种定磷探头用掺镧固体电解质的制备方法，包括以下步骤。
（1）将CaCO3、CaHPO4∙2H2O和La2O3粉体，脱水干燥后备用。
（2）按摩尔比CaCO3：CaHPO4∙2H2O：La2O3=0.8：1：0.025取三种备用粉体，机械混合均匀，所得混合粉体的颗粒中径粒度为20微米。
（3）将步骤（2）混合均匀的粉体以8℃/min的升温速率加热至1550℃下进行烧结，烧结5h， 干燥气氛下冷却至室温即得一种定磷探头用掺镧固体电解质。
对比例1。
一种定磷探头用固体电解质，化学成分组成为65%CaO + 35% 4CaO∙P2O5。
（1）将CaO、CaHPO4∙2H2O粉体，脱水干燥后备用。
（2）按摩尔比CaO：CaHPO4∙2H2O =7:1取两种备用粉体，机械混合均匀。
（3）将步骤（2）混合均匀的粉体以3℃/min的升温速率加热至1450℃下进行烧结，烧结5h， 干燥气氛下冷却至室温一种定磷探头用固体电解质。
将实施例1与对比例1中制得的两种材料进行性能检测，1000℃下检测结果见下表。
Figure DEST_PATH_IMAGE001

Claims (2)

1.一种定磷探头用掺镧固体电解质，其特征在于，所述固体电解质由干燥的CaCO3或CaO、CaHPO4∙2H2O和La2O3粉体按比例混合，烧结后得到；所述固体电解质的通式为4Ca1- xLaxO1+a∙P2O5，其中，0＜x≤0.2。
2.一种定磷探头用掺镧固体电解质，其制备步骤如下：
（1）将CaCO3或CaO、CaHPO4∙2H2O和La2O3粉体，脱水干燥后备用；
（2）按0.8-0.85：1：0.05摩尔比称取备用的CaCO3或CaO、CaHPO4∙2H2O和La2O3粉体，机械混合均匀，所得混合粉体的颗粒中径粒度为10～50微米；
（3）将步骤（2）混合均匀的粉体以3℃～10℃/min的升温速率加热至1450～1580℃下进行烧结，烧结2h～5h，然后冷却至室温即得一种定磷探头用掺镧固体电解质。
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