CN112299835A - 一种a位部分掺杂碱金属离子钙钛矿透氧膜材料的制备方法 - Google Patents
一种a位部分掺杂碱金属离子钙钛矿透氧膜材料的制备方法 Download PDFInfo
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Abstract
本发明属合成高性能陶瓷透氧膜研发领域，特别涉及一种在钙钛矿A位部分掺杂碱金属离子的陶瓷透氧膜制备方法，其具体步骤如下：（1）以锶离子盐、钴离子盐、铁离子盐和碱金属离子盐为原料，形成均匀混合水溶液A；（2）向混合溶液A中加入络合剂、分散剂和弱碱，磁力搅拌数小时至所有物质完全溶解，形成溶胶B；（3）对溶胶B进行加热逐步蒸发其水分获得凝胶C；（4）将凝胶C进行高温焙烧处理获得钙钛矿粉体E；（5）将E进行压片、焙烧、打磨即可以即得A位部分掺杂碱金属离子的钙钛矿陶瓷透氧膜目标产物。本发明设备简单，流程简化，投资成本低廉，目标产物为稳定性与透氧量兼具的一类钙钛矿透氧膜新材料。
Description
技术领域
本发明属合成高性能陶瓷透氧膜材料领域，特别涉及一种钙钛矿A位部分掺杂碱金属离子的陶瓷透氧膜制备方法。
背景技术
混合导体陶瓷透氧膜材料以其优异的透氧性能在纯氧分离、甲烷部分氧化、富氧燃烧以及固体氧化物燃料电池领域展现出良好的应用前景。制约混合导体透氧膜材料发展有3个关键因素，一是透氧膜材料的透氧量，二是透氧膜在应用气氛中的稳定性，尤其是在还原气氛或者低氧分压状态下的结构稳定性和化学稳定性。三是透氧膜材料组件也应该具备较高的机械强度，因为透氧膜组件通常会在较大的压力差环境中使用。研究表明当前发展的诸多钙钛矿材料透氧量较高，但稳定性不足，因此发展高稳定性钙钛矿透氧膜材料成为透氧膜领域发展的关键。钙钛矿材料的离子掺杂可变性较大，元素周期表中大多数金属离子都可以掺杂到钙钛矿结构，但是氧离子传导能力与晶相结构、A-O和B-O键能等诸多因素有关，因此不同离子及同种离子不同掺杂量都会对材料透氧性能有极大影响，例如，SrCo0.8Fe0.2O3-δ具有较高的透氧量，但SCF的结构稳定性较差，尤其是在低氧分压下膜片容易粉化解体，从而限制了它的实际应用。
为了优化钙钛矿透氧膜材料的稳定性和透氧量，本发明首次将优选碱金属离子部分掺杂到钙钛矿材料A位晶格中制备了A位部分掺杂碱金属的纯相钙钛矿材料，该材料实现了钙钛矿透氧膜材料稳定性和透氧量的有效结合，具有较好的工业应用前景。
发明内容
本发明的目的在于克服现有钙钛矿透氧膜材料稳定性的不足之处，提供一种设备简单，流程简化，投资成本低廉，目标产物稳定性高，透氧量较大，能够有效平衡稳定性与透氧量的钙钛矿A位部分掺杂碱金属离子的陶瓷透氧膜制备方法。
为解决上述技术问题，本发明是这样实现的：
一种钙钛矿A位部分掺杂碱金属离子的陶瓷透氧膜制备方法,按如下步骤依次实施：
(1)以锶离子源、钴离子源、铁离子源和碱金属离子源为原料，形成均匀混合溶液A；
(2)向步骤(1)所得混合溶液A中加入络合剂、分散剂和碱溶液，磁力搅拌数小时至所有物质完全溶解，形成溶液B；
(3)将步骤(2)所得溶液B进行加热获得胶体溶液C；
(4)将步骤(3)所得胶体溶液C加热形成混合氧化物粉体D；
(5)将步骤(4)所得混合氧化物粉体D进行高温焙烧获得钙钛矿透氧膜材料E；
(6)将步骤(5)所得钙钛矿透氧膜材料E进行压片、焙烧、打磨，即得目的产物钙钛矿A位部分掺杂碱金属离子的钙钛矿陶瓷透氧膜。
作为一种优选方案，本发明所述钙钛矿A位部分掺杂碱金属离子为ABO3型钙钛矿材料的A位部分掺杂碱金属离子。
进一步地，本发明所述步骤(1)中，碱金属离子源中碱金属离子在ABO3型钙钛矿材料的A位掺杂比例为5～30％。
进一步地，本发明所述步骤(1)中，锶离子源中锶离子含量高于碱金属离子源中碱金属离子含量。
进一步地，本发明所述的碱金属离子源为碱金属的硝酸盐或碳酸盐。
进一步地，本发明所述步骤(1)中，所述锶离子源中钴离子与铁离子源中铁离子的摩尔比为1:1。
进一步地，本发明所述步骤(2)中，分散剂为PVP、EDTA酸与柠檬酸的混合物；所述碱溶液为KOH或氨水。
进一步地，本发明所述步骤(4)中，高温焙烧温度为800～1000℃。
进一步地，本发明所述步骤(5)中的焙烧温度为1000～1250℃。
本发明能够很好的应用于纯氧分离、水分解催化剂和低碳烃氧化等领域，使钙钛矿材料制备流程简化、设备减少，从而降低投资等问题。本发明基于碱金属离子具有更低的价态和稳定性，通过在钙钛矿A位的部分掺杂，可以在钙钛矿晶格中创造更多氧空位，并通过碱金属离子与晶格中氧离子较高的键能赋予钙钛矿材料更高的稳定性。所制备的A位部分掺杂的钙钛矿材料具有纳米粒子尺寸，并且高度分散，相对传统A位没有掺杂碱金属离子的钙钛矿透氧膜氧化物具有更高的稳定性。
附图说明
下面结合附图和具体实施方式对本发明作进一步说明。本发明的保护范围不仅局限于下列内容的表述。
图1：Li0.1Sr0.9Co0.5Fe0.5O3-δ的钙钛矿材料的XRD分析；
图2：Cs0.1Sr0.9Co0.5Fe0.5O3-δ的钙钛矿材料的XRD分析
图3：Cs0.1Sr0.9Co0.5Fe0.5O3-δ的钙钛矿材料透氧稳定性测试。
具体实施方式
下面结合实施例对本发明作进一步描述。本发明所涉及的材料包含并不局限于以下实施例中的表述。
本发明一种A位部分掺杂碱金属离子钙钛矿透氧膜材料的制备方法，下述的实例中所用的水均为去离子水；所用试剂除特别说明的外，均采用分析纯试剂；实施例中，采用SU8010扫描电镜对不同条件下制得的钙钛矿透氧膜材料的微观形貌进行了表征。XRD表征采用日本理学公司D8 AdvanceX射线衍射仪，其实验条件为：Cu Kα辐射(λ＝0.15418nm)，管压：40Kv，管流：30mA，使用连续扫描方式，步长0.02°，扫描速率6°(2θ)/min。
实施例1
称取0.2g Li2CO3粉体用稀硝酸溶解、称取Sr(NO3)27.0906g、Fe(NO3)2.9H2O5.468g、Co(NO3)2.6H2O 3.9392g溶于上述溶液，形成混合溶液A；称取15.8224g EDTA酸溶于上述混合溶液A，磁力搅拌1h，接着加入柠檬酸15.6034g，搅拌1h 后，缓慢加入氨水调节溶液pH值接近于中性，最后加入分散剂PVP(聚乙烯吡咯烷酮)6.42g，继续搅拌直到形成透明溶液B；将上述溶液B放到磁力搅拌器上加热搅拌，逐渐蒸发溶液中的水分，直至形成一个棕红色粘性胶体溶液C；将胶体溶液C转移到坩埚中用电加热炉加热到150℃逐渐形成凝胶，继续加热凝胶逐步燃烧，形成混合氧化物粉体D；然后将混合氧化物粉体D转移到马弗炉中900℃焙烧6h获得Li0.1Sr0.9Co0.5Fe0.5O3-δ钙钛矿透氧膜材料E，将钙钛矿透氧膜材料E用 40MPa压力压制成膜片，然后1150℃焙烧5h就可以得到所需透氧膜片材料，该材料在透氧过程中展现较高的稳定性与透氧量。
实施例2
称取0.23g NaNO3粉体用稀硝酸溶解、称取Sr(NO3)27.0906g、Fe(NO3)2.9H2O5.468g、Co(NO3)2.6H2O 3.9392g溶于上述溶液，形成混合溶液A；称取15.8224g EDTA酸溶于上述混合溶液A，磁力搅拌1h，接着加入柠檬酸15.6034g，搅拌1h 后，缓慢加入氨水调节溶液PH值接近于中性，最后加入分散剂PVP(聚乙烯吡咯烷酮)6.42g，继续搅拌直到形成透明溶液B；将上述溶液B放到磁力搅拌器上加热搅拌，逐渐蒸发溶液中的水分，直至形成一个棕红色粘性胶体溶液C；将胶体溶液C转移到坩埚中用电加热炉150℃加热逐渐形成凝胶，继续加热凝胶逐步燃烧，形成混合氧化物粉体D；然后将混合氧化物粉体D转移到马弗炉中850℃加热焙烧6h获得Na0.1Sr0.9Co0.5Fe0.5O3-δ钙钛矿透氧膜材料E，将钙钛矿透氧膜材料E用40MPa压力压制成膜片，然后1200℃焙烧5h就可以得到所需透氧膜片材料，该材料在透氧过程中展现较高的稳定性与透氧量。
实施例3
称取0.748g K2CO3粉体用稀硝酸溶解、称取Sr(NO3)27.0906g、Fe(NO3)2.9H2O5.468g、Co(NO3)2.6H2O 3.9392g溶于上述溶液，形成混合溶液A；称取15.8224g EDTA酸溶于上述混合溶液A，磁力搅拌1h，接着加入柠檬酸15.6034g，搅拌1h 后，缓慢加入氨水和KOH调节溶液pH值接近于中性，最后加入分散剂PVP(聚乙烯吡咯烷酮)6.42g，继续搅拌直到形成透明溶液B；将上述溶液B放到磁力搅拌器上加热搅拌，逐渐蒸发溶液中的水分，直至形成一个棕红色粘性胶体溶液C；将胶体溶液C转移到坩埚中用电加热炉150℃加热逐渐形成凝胶，继续加热凝胶逐步燃烧，形成混合氧化物粉体D；然后将混合氧化物粉体D转移到马弗炉中950℃焙烧5h获得K0.1Sr0.9Co0.5Fe0.5O3-δ钙钛矿透氧膜材料E,将该材料用 40MPa压力压制成膜片，然后1200℃被烧5h就可以得到所需透氧膜片材料，该材料在透氧过程中展现较高的稳定性与透氧量。
实施例4
称取0.882g Cs2CO3粉体用稀硝酸溶解、称取Sr(NO3)27.0906g、Fe(NO3)2.9H2O5.468g、Co(NO3)2.6H2O 3.9392g溶于上述溶液，形成混合溶液A；称取15.8224g EDTA酸溶于上述混合溶液A，磁力搅拌1h，接着加入柠檬酸15.6034g，搅拌1h 后，缓慢加入氨水调节溶液PH值接近于中性，最后加入分散剂PVP(聚乙烯吡咯烷酮)6.42g，继续搅拌直到形成透明溶液B；将上述溶液B放到磁力搅拌器上加热搅拌，逐渐蒸发溶液中的水分，直至形成一个棕红色粘性胶体溶液C；将胶体溶液C转移到坩埚中用电加热炉150℃加热逐渐形成凝胶，继续加热凝胶逐步燃烧，形成混合氧化物粉体D；然后将混合氧化物粉体D转移到马弗炉中900℃加热焙烧5h可以获得CS0.1Sr0.9Co0.5Fe0.5O3-δ钙钛矿透氧膜材料E，将钙钛矿透氧膜材料E用40MPa压力压制成膜片，然后1180℃焙烧5h就可以得到所需透氧膜片材料，该材料在透氧过程中展现较高的稳定性与透氧量。
可以理解的是，对于本领域的普通技术人员来说，可以根据本发明的技术构思做出其它各种相应的改变与变形，而所有这些改变与变形都应属于本发明权利要求的保护范围。
Claims (9)
1.一种钙钛矿A位部分掺杂碱金属离子的陶瓷透氧膜制备方法, 其特征在于，按如下步骤依次实施：
（1）以锶离子源、钴离子源、铁离子源和碱金属离子源为原料，形成均匀混合溶液A；
（2）向步骤（1）所得混合溶液A中加入络合剂、分散剂和碱，磁力搅拌数小时至所有物质完全溶解，形成溶液B；
（3）将步骤（2）所得溶液B进行加热获得胶体溶液C；
（4）将步骤（3）所得胶体溶液C加热形成混合氧化物粉体D；
（5）将步骤（4）所得混合氧化物粉体D进行高温焙烧获得钙钛矿透氧膜材料E；
（6）将步骤（5）所得钙钛矿透氧膜材料E进行压片、焙烧、打磨，即得目的产物钙钛矿A位部分掺杂碱金属离子的钙钛矿陶瓷透氧膜。
2.根据权利要求1所述的一种钙钛矿A位部分掺杂碱金属离子的陶瓷透氧膜制备方法,其特征在于：所述钙钛矿A位部分掺杂碱金属离子为ABO3型钙钛矿材料的A位部分掺杂碱金属离子。
3.根据权利要求2所述的一种钙钛矿A位部分掺杂碱金属的陶瓷透氧膜制备方法, 其特征在于：所述步骤（1）中，碱金属离子源中碱金属离子在ABO3型钙钛矿材料的A位掺杂比例为5～30%。
4.根据权利要求3所述的一种钙钛矿A位部分掺杂碱金属离子的陶瓷透氧膜制备方法,其特征在于：所述步骤（1）中，锶离子源中锶离子含量高于碱金属离子源中碱金属离子含量。
5.根据权利要求4所述的一种钙钛矿A位部分掺杂碱金属离子的陶瓷透氧膜制备方法,其特征在于：所述的碱金属离子源为碱金属的硝酸盐或碳酸盐。
6.根据权利要求5所述的一种钙钛矿A位部分掺杂碱金属离子的陶瓷透氧膜制备方法,其特征在于：所述步骤（1）中，所述锶离子源中钴离子与铁离子源中铁离子的摩尔比为1:1。
7.根据权利要求6所述的一种钙钛矿A位部分掺杂碱金属离子的陶瓷透氧膜制备方法,其特征在于：所述步骤（2）中，分散剂为PVP, 络合剂为EDTA酸与柠檬酸的混合物, 所述碱溶液为KOH或氨水。
8.根据权利要求7所述的一种钙钛矿A位部分掺杂碱金属离子的陶瓷透氧膜制备方法,其特征在于：所述步骤（4）中，高温焙烧温度为800～1000oC。
9.根据权利要求8所述的一种钙钛矿A位部分掺杂碱金属离子的陶瓷透氧膜制备方法,其特征在于：所述步骤（5）中的焙烧温度为1000～1250oC。
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