CN114349508A - 一种具有氧化物薄层的多层陶瓷膜制备方法和应用 - Google Patents
一种具有氧化物薄层的多层陶瓷膜制备方法和应用 Download PDFInfo
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- CN114349508A CN114349508A CN202210044306.1A CN202210044306A CN114349508A CN 114349508 A CN114349508 A CN 114349508A CN 202210044306 A CN202210044306 A CN 202210044306A CN 114349508 A CN114349508 A CN 114349508A
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Abstract
本发明涉及一种具有氧化物薄层的多层陶瓷膜制备方法和应用，将由萤石型氧化物和钙钛矿型或尖晶石型氧化物构成的复合材料预成型，然后在与Al2O3接触条件下高温热处理，即得到具有萤石型氧化物薄层的多层陶瓷膜。其中萤石型氧化物薄层的致密度可调，厚度可控且最薄可达约1微米，多层陶瓷各层之间兼容良好，无剥离或分层现象。另外，本发明提供的多层陶瓷制备工艺简易，重复性好，易于规模化放大。这种多层陶瓷作为混合导体膜时，在含H2、CO2、CH4、H2S气氛下连续稳定工作超过1000个小时，作为透氧膜稳定高效地进行工业副产氢驱动水分解制氢。另外，本发明提供的多层陶瓷制备技术有望被用于固体氧化物燃料电池、高温电解电池、气体传感器等领域。
Description
技术领域
本发明涉及一种具有氧化物薄层的多层陶瓷膜制备方法和应用，所制备的多层陶瓷膜可作为混合导体透氧膜兼具稳定性和透氧性能，被用于提纯工业副产氢获取氢气，此外本发明涉及的多层陶瓷简易制备技术有望被用于固体氧化物燃料电池、高温电解池、气体传感器等领域。
背景技术
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。
多层陶瓷是许多能量转换和电子器件的基本结构。例如，固体氧化物燃料电池(SOFC)和电解电池(SOEC)主要由电解质层、负极(阴极)层和正极(阳极)层构成；陶瓷电容器主要包括三层：陶瓷介质、内电极和外电极；氧气传感器由固态电解质和两侧扩散电极层构成；陶瓷催化膜反应器主要包括多孔支撑层、致密分离层和多孔催化层构成。因此，多层陶瓷的可控制备是上述能量转换和电子器件广泛应用的关键技术，尤其是具有致密薄层、层与层之间兼容性良好、热化学稳定的多层陶瓷是高效低成本能量转换和电子器件的重点和难点。
下面以陶瓷催化膜反应器在氢气提纯领域的应用为例详细介绍多层陶瓷技术的发展现状和面临的问题。氢能产业是具有战略性和先导性的新兴产业，代表未来技术变革和能源发展的重要方向。通过提纯工业副产氢获取燃料氢气是现阶段比较现实和价廉的制氢方式，有利于降低氢燃料电池的运行成本。燃料氢气中微量CO杂质的存在能够快速毒化燃料电池催化剂，因此开发不含CO的氢气(CO≦0.2ppm)制备技术成为氢能研究的一个重要方向。
由于氧离子-电子混合导体透氧膜对氧气的传输具有100％的选择性，将高温水分解反应和工业副产氢燃烧反应耦合在混合导体透氧膜的两侧，低纯氢气的燃烧可以促进陶瓷膜另一侧水分解所生成氧气的原位移除，从而可以高效地促进水分解，直接获得不含CO的氢气。但是传统钴基、铁基透氧膜难以兼具稳定性和透氧性能。尤其在富含H2、CH4、CO等还原性气体或CO2和H2S酸性气氛下，膜材料中的Co或Fe离子易于被深度还原或者膜表面形成碳酸盐或硫酸盐，致使膜结构降解，透氧性能和机械强度降低。为此，有学者设计开发出不含Co或Fe的掺杂CeO2(Ce0.9Gd0.1O2-δ、PrxCe0.9-xGd0.1O1.95-δ)，它们在低氧分压气氛下表现出氧离子-电子混合导电性，而且在含H2、CO2、CO、H2S等苛刻气氛中具有优异的稳定性，有望作为透氧膜耦合水分解和工业副产氢氧化制取不含CO的氢气。
为了提高氢气的产率，要求尽可能减小掺杂CeO2致密层的厚度，因此将CeO2薄层担载在支撑层上形成多层非对称结构透氧膜是关键核心技术。目前常见制备多层陶瓷的工艺包括流延-层压-烧结、干压-涂敷-烧结、磁控溅射、喷雾热解等。这些方法通常需要经历多步热处理、特殊的设备，工艺繁琐、耗时、操作不便。另外，由于不同层之间的热化学膨胀系数不同，高温热处理时层与层之间易分层剥离，制约透氧膜在副产氢提纯领域的广泛应用。
发明内容
本发明针对常见混合导体膜在氢气提纯条件下不能兼具稳定性和氧渗透性能的难题，提出采用界面反应诱导策略构筑具有掺杂氧化铈薄层的多层陶瓷膜，同时该策略同样适用于制备掺杂氧化锆基多层结构，用于固体氧化物燃料电池、电解电池和气体传感器。
为实现上述技术目的，本发明采用如下技术方案：
本发明的第一个方面，提供了一种具有氧化物薄层的多层陶瓷膜制备方法，包括：
以萤石型氧化物和钙钛矿型或尖晶石型氧化物为原料制成复合材料，然后，预成型，得到坯体；
将所述坯体的表面与Al2O3接触，进行烧结，即得。
本发明制得了兼具稳定性和氧渗透性能的多层陶瓷膜，且制备方法具有简易、高效、重复性好的特点。
本发明的第二个方面，提供了上述的方法制备的具有氧化物薄层的多层陶瓷膜，所述多层陶瓷膜包括两层或三层结构；
其中，两层结构由单相萤石型CAO或BZO薄层和复合材料层构成；
三层结构包括一侧单相CAO或BZO薄层、中间复合材料致密层、另一侧复合材料多孔层；或者包括一侧单相CAO或BZO薄层、中间复合材料致密层、另一侧CAO或BZO薄层。
本发明的第三个方面，提供了上述的多层陶瓷膜在从含氧混合气中选择性分离氧以及用于烃类的催化部分氧化、分解H2O制氢或制备燃料电池中的应用。
本发明的有益效果在于：
(1)与传统的多层陶瓷制备方法不同，本发明方法利用界面诱导相分离策略，将萤石结构氧化物(掺杂氧化铈或氧化锆)和钙钛矿或尖晶石结构氧化物均匀混合得到复合粉末，经过预成型后，与氧化铝进行表面接触(以氧化铝作为界面诱导剂)，在一定温度下使原本混合均匀的双相复合材料产生界面相分离，形成双层或三层结构，即得到掺杂氧化铈或氧化锆基多层陶瓷，其中掺杂氧化铈或氧化锆层致密度可调，厚度可调节并且可达到～1微米，各层之间热兼容，没有出现鼓起或分层等现象。
(2)需要特别说明的是，与传统方法将萤石结构氧化物作为薄层原料溅射、喷涂或沉积在支撑层形成多层结构不同，本发明首次发现：可以采用氧化铝作为诱导剂与多相复合陶瓷材料接触，在一定温度下，氧化铝诱导复合陶瓷材料的界面发生相分离，直接得到由氧化物薄层(来源于本体材料)和本体复合材料支撑层构成的多层结构，其中氧化物薄层致密度和厚度易于调节，例如：两层结构由单相萤石型CAO或BZO薄层和本体复合材料层构成；或，三层结构包括一侧单相CAO或BZO薄层、中间复合材料致密层、另一侧复合材料多孔层；或者包括一侧单相CAO或BZO薄层、中间复合材料致密层、另一侧CAO或BZO薄层。
(3)本发明提供的萤石型氧化物基多层陶瓷制备方法简单，重复性好，易于规模化放大，突破传统多步法制备工艺。这种多层结构作为混合导体膜时，在含H2、CO2、CH4、H2S苛刻环境下连续稳定工作超过1000个小时，同时兼具优异的氧离子传输能力，作为新型强韧陶瓷透氧膜稳定高效地进行工业副产氢驱动的水分解制氢。
(4)由本发明提供的一种制备掺杂氧化铈或氧化锆基多层陶瓷简易制备技术有望被用于固体氧化物燃料电池、高温电解池、气体传感器等领域。
(5)本申请的操作方法简单、成本低、具有普适性，易于规模化生产。
附图说明
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。
图1为本发明实施例2制得的CGO/(CGO-GSFT)两层结构膜的X射线衍射和扫描电镜表征图。
图2为本发明实施例2提供的60CGO-40GSFT坯体在1350℃保温10个小时后，CGO/(CGO-GSFT)两层结构的扫描电镜表征图。
图3为本发明实施例2提供的CGO-GSFT坯体表面滴涂纳米Al2O3胶体溶液后，经高温烧结后的样品表面SEM-EDX图。
图4为本发明实施2提供的CSO-SSFT中空纤维膜坯体表面喷涂Al2O3胶体溶液后，经过高温烧结后样品表面SEM图。
图5为本发明实施例3制得的CGO/(CGO-GSFT)/(CGO-GSFT)三层陶瓷膜扫描电镜表征图。
图6为本发明实施例4提供的尺寸大于5cm x 5cm的CGO/(CGO-GSFT)两层陶瓷的扫描电镜表征图。
图7为本发明实施例5提供的采用界面自组装策略制备的其他多层陶瓷的X射线衍射图，包含60mol.％Ce0.9Gd0.1O2-δ-40mol.％Gd0.1Sr0.9FeO3-δ(CGO-GdSF)、60mol.％Ce0.9Gd0.1O2-δ-40mol.％SrFe0.8Co0.2O3-δ(CGO-SFCo)、60mol.％Ce0.9Gd0.1O2-δ-40mol.％SrFe0.5Ce0.5O3-δ(CGO-SFCe)、60mol.％Ce0.9Gd0.1O2-δ-40mol.％La0.2Sr0.8Fe0.8Co0.2O3-δ(CGO-LaSFCo)、60mol.％Ce0.9Pr0.1O2-δ-40mol.％Pr0.6Sr0.4FeO3-δ(CPO-PrSF)、60mol.％Ce0.9Pr0.1O2-δ-40mol.％Pr0.6Sr0.4Fe0.8Co0.2O3-δ(CPO-PrSFCo)、60mol.％Ce0.9Sm0.1O2-δ-40mol.％La0.1Sr0.9FeO3-δ(CSO-LaSF)、60mol.％Ce0.9Sm0.1O2-δ-40mol.％Sm0.1Sr0.9FeO3-δ(CSO-SmSF)。
图8为本发明实施例5提供的采用界面自组装策略一步热处理60mol.％Ce0.8Gd0.1O2-δ-40mol.％NiFe2O4(CGO-NFO)和60mol.％Ce0.9Pr0.1O2-δ-40mol.％Mn1.5Co1.5O4(CPO-MCO)复合坯体后样品的上下表面的X射线衍射图和截面扫描电镜图。
图9为本发明实施例6提供的采用界面自组装策略一步热处理Y0.08Zr0.92O2-δ-CoFe2O4(YSZ-CFO)复合坯体后样品的上下表面的X射线衍射图和截面扫描电镜图。
图10为本发明实施例2提供的CGO/(CGO-GSFT)两层陶瓷作为混合导体透氧膜进行空气分离、甲烷氧化和水分解制氢性能测试。
具体实施方式
应该指出，以下详细说明都是示例性的，旨在对本发明提供进一步的说明。除非另有指明，本发明使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。
一种具有氧化物薄层的多层陶瓷膜制备方法和应用，其特征在于，包含以下步骤：将由萤石型氧化物和钙钛矿型或尖晶石型氧化物构成的复合材料预成型，然后在与Al2O3接触条件下高温热处理，即得到萤石型氧化物薄层的多层陶瓷膜。
所述的萤石型氧化物化学组成表达式为Ce1-aAaO2-δ(CAO)或BbZr1-bO2-δ(BZO)，其中A选自La、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb中的一种或几种，0≤a≤1,δ为氧晶格缺陷数。B选自Y、Sc、Yb、Pr、Bi、Er、Ce中的一种或几种，0≤b≤1，δ为氧晶格缺陷数。
所述的钙钛矿型氧化物化学组成表达式为MmSr1-mFe1-nNnO3-δ(MSFNO)，其中M选自La、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Ba、Ca、Bi中的一种或几种；N选自Mg、Ca、Sc、Ti、V、Cr、Mn、Co、Ni、Cu、Zn、Zr、Y、Nb、Mo、Tc、Ru、Rh、Pd、Ag、Al、In、W、La、Gd、Ce中的一种或几种；0≤m≤0.5，0≤n≤0.5，δ为氧晶格缺陷数。
所述的尖晶石型氧化物化学组成表达式为X3-yYyO4(XYO)，其中X选自Mg、Fe、Co、Ni、Mn、Zn、Cd中的一种或几种，Y选自Al、Fe、Co、Cr、Ga、Mn中的一种或几种，0≤y≤3。
所述复合材料的制备方法包括但不限于球磨混合法、固相反应法、溶胶-凝胶法，只需将粉末混合均匀即可。所述预成型方法包括干压法、相转化法和挤压成型法。
所述Al2O3是Al2O3刚玉片、Al2O3粉末或纳米Al2O3胶体溶液。
所述与Al2O3的接触方式包括预成型复合体放置在Al2O3刚玉片上面，或者夹在两个Al2O3刚玉片中间，或者涂敷纳米Al2O3胶体溶液。
所述具有萤石型氧化物薄层的多层陶瓷膜包括两层或三层结构，层与层之间粘连良好。两层结构由单相萤石型CAO或BZO薄层和复合材料层构成。三层结构包括一侧单相CAO或BZO薄层、中间复合材料致密层、另一侧复合材料多孔层；或者包括一侧单相CAO或BZO薄层、中间复合材料致密层、另一侧CAO或BZO薄层。
所述具有萤石型氧化物薄层的多层陶瓷膜用于从含氧混合气中选择性分离氧以及用于烃类的催化部分氧化、分解H2O制氢或燃料电池领域。
下面结合具体的实施例，对本发明做进一步的详细说明，应该指出，所述具体实施例是对本发明的解释而不是限定。
实施例1：溶胶-凝胶法制备CGO-GSFT复合粉末
按照60mol.％Ce0.9Gd0.1O2-δ-40mol.％Gd0.1Sr0.9Fe0.9Ti0.1O3-δ化学计量比将Ce(NO3)4、Gd(NO3)3、Sr(NO3)2和Fe(NO3)3分别溶于水中，之后向混合液中加入柠檬酸和乙二胺四乙酸(EDTA)，其中柠檬酸、乙二胺四乙酸及金属离子的摩尔比为1.5：1：1，搅拌一段时间后，再加入适量氨水调节溶液pH值为9，获得澄清溶液。之后将化学计量比的钛酸四丁酯溶于等摩尔比的乳酸、乙醇和冰醋酸，形成的含Ti离子溶液与之前的澄清溶液混合，形成60CGO-40GSFT前驱体溶液。搅拌一段时间后，将前驱体溶液于120℃脱水处理获得深色溶胶，然后以5℃/min的升温速率从室温升至950℃煅烧10个小时，再以相同的速率降至室温获得混合均匀的60CGO-40GSFT粉体。
实施例2：掺杂CeO2基双层陶瓷膜的制备
称取适量60CGO-40GSFT粉体，150MPa的压力下制得坯体，将坯体放置在Al2O3基底上，从室温升至1450℃，保温10个小时后降至室温，获得(60CGO-40GSFT)/CGO双层结构膜。如图1所示，烧结后的样品上表面呈现立方萤石和立方钙钛矿双相结构，但是与Al2O3基底接触的下表面只有CGO相，扫描电镜发现下表面CGO层致密、厚度大约为5μm，说明与Al2O3基底接触的界面在高温热处理时发生相分离，界面自组装形成(60CGO-40GSFT)/CGO双层结构。
在上述基础上，降低烧结温度至1350℃，与Al2O3基底接触的下表面CGO致密层厚度降低为大约1μm，如图2所示。另外，在CGO-GSFT坯体表面滴涂纳米Al2O3胶体溶液，经过高温烧结后，表面涂敷有Al2O3胶体的一侧出现CGO富集，如图3所示。对于相转化预成型坯体，首先配置一定固含量的铸膜液，经过球磨混合和脱泡后，采用干湿相转化纺丝技术制备预成型的60mol％Ce0.8Sm0.2O2-δ–40mol％Sm0.2Sr0.8Fe0.6Ti0.4O3-δ(CSO-SSFT)中空纤维膜坯体，然后在坯体表面喷涂Al2O3胶体溶液，经高温烧结后，涂敷Al2O3胶体的表面出现CSO富集，如图4所示。以上结果表明，界面富集的萤石型氧化物薄层的厚度可以通过改变烧结条件进行调控，不同氧化铝都能够引起复合材料坯体界面富集。
实施例3：掺杂CeO2基三层陶瓷的制备
按照本发明实施例1制备CGO-GSFT粉末，然后称取适量CGO-GSFT粉末与淀粉、碳纤维球磨混合(质量比为70：24：6)，球磨转速为500转/min，球磨后干燥备用。相似地，称取适量CGO-GSFT粉末与淀粉球磨混合(质量比为90：10)，球磨转速为500转/min，球磨后干燥备用。
分别称取0.15g CGO-GSFT粉体、0.15g含淀粉的CGO-GSFT粉末、0.9g含淀粉和碳纤维的CGO-GSFT粉末(淀粉和碳纤维在高温时被气化使陶瓷形成多孔结构)，按照先后顺序铺覆在磨具中，150MPa的压力下制得坯体，将坯体放置α-Al2O3基底上，经过一次烧结后，获得(CGO-GSFT)/(CGO-GSFT)/CGO三层结构透氧膜。如图5所示，扫描电镜图表明烧结后的样品呈现三层结构，与Al2O3基底接触的表面为CGO致密层，厚度约3μm；与之相连的是致密度较高、厚度大约100μm的CGO-GSFT中间层；与中间层相连的是CGO-GSFT多孔支撑层。通过电镜发现，三层之间粘连良好，没有出现分层、脱落和鼓起现象。
实施例4：大尺寸掺杂CeO2基双层陶瓷的制备
按照本发明实施例1制备CGO-GSFT粉末，称取约20g 60CGO-40GSFT粉体，均匀放置在8cm*10cm的长方形磨具中，70MPa的压力下等待2分钟后制得坯体，将坯体裁剪为～7cm*7cm的正方形坯体，然后将其放在Al2O3粉末上面，从室温升至1450℃，保温10个小时后降至室温，获得大小约5cm*5cm的(CGO-GSFT)/CGO双层结构透氧膜。如图6所示，烧结后的片状样品平整、没有发现弯曲、分层或者裂纹，同时与Al2O3粉末接触的下表面呈现立方萤石结构，CGO层的厚度大约3-5μm。
实施例5：其他CeO2基双层陶瓷膜的制备
按照实施例1中采用溶胶-凝胶法制备CGO-GdSF、CGO-SFCo、CGO-SFCe、CGO-LaSFCo、CPO-PrSF、CPO-PrSFCo、CSO-LaSF、CSO-SmSF八种不同的粉末。分别称取适量复合粉体，150MPa的压力下制得坯体，将坯体放置α-Al2O3基底上，从室温升至1400℃，保温10个小时后降至室温，获得八种氧化铈基双层陶瓷。如图7所示八种坯体经过一步烧结后双层陶瓷的上下表面X射线衍射图，发现八种样品的下表面均只有氧化铈的衍射峰，上表面包含萤石相和钙钛矿相，说明以上八种坯体经过热处理后，与Al2O3接触的一侧均发生界面相分离，自组装形成双层结构。
另外，按照实施例2制备CGO-NFO和CPO-MCO粉末，然后分别称取适量复合粉体，150MPa的压力下制得坯体，将坯体放置Al2O3基底上，从室温升至1400℃，保温10个小时后降至室温。如图8为烧结后样品上下表面X射线衍射图和横截面扫描电镜图，发现CGO-NFO烧结后样品的下表面呈现CGO衍射峰，没有发现NFO尖晶石结构。相似地，CPO-MCO烧结后样品的下表面保存CPO衍射峰，但是MCO衍射峰消失，说明CGO-NFO和CPO-MCO坯体经过热处理后，与Al2O3接触的一侧发生界面相分离形成双层结构。
实施例6 YSZ基多层陶瓷的制备
按照实施例1采用EDTA-柠檬酸法制备Y0.08Zr0.92O2-δ-CoFe2O4(YSZ-CFO)复合粉末，经过压制成型后放置在Al2O3基底上烧结，烧结温度为1450℃，保温时间为5个小时。图9为烧结后样品上下表面X射线衍射图和横截面扫描电镜图，发现YSZ-CFO烧结后样品的下表面呈现YSZ衍射峰，没有发现CFO尖晶石结构，说明界面自组装策略也适用于YSZ-CFO体系。
对上述实施例2获得的多层陶瓷作为混合导体透氧膜进行空气分离、甲烷氧化和水分解制氢性能测试：
将实例2中所制备的(CGO-GSFT)/CGO两层透氧膜密封后放置在高温管式炉中，当温度达到925℃时，将膜两侧分别通入Air和He(F(Air)＝30cm3 min-1；F(He)＝20cm3 min-1)、Air和CO2(F(Air)＝20cm3 min-1；F(CO2)＝10cm3 min-1)、Air和CH4(F(Air)＝20cm3 min-1；F(CH4)＝6cm3 min-1)、H2O-Ar和CH4(F(H2O)＝16cm3 min-1；F(Ar)＝4cm3 min-1；F(CH4)＝6cm3 min-1)、H2O-He和CH4-H2-CO2-N2(F(H2O)＝16cm3 min-1；F(He)＝4cm3 min-1；F(CH4)＝4cm3 min-1；F(H2)＝6cm3min-1；F(CO2)＝1cm3 min-1,F(N2)＝2cm3 min-1)、H2O-He和CH4-H2-CO2-N2-H2S(F(H2O)＝16cm3min-1；F(He)＝4cm3 min-1；F(CH4)＝4cm3 min-1；F(H2)＝6cm3 min-1；F(CO2)＝1cm3 min-1,F(N2)＝2cm3 min-1；H2S＝37ppm)六种不同的工况下。采用气相色谱仪对透氧膜两侧出口气体在线检测，如图10所示，在超过1000个小时内，透氧膜在以上六种不同工况下的氧渗透通量随时间的变化。随着膜两侧氧分压梯度的增加，CGO/(CGO-GSFT)两层透氧膜的氧渗透透量逐渐增加，在Air/CH4工况下耦合氧分离和甲烷转化反应，氧渗透性能达到0.6cm3 min-1cm-2。另外，当CGO/(CGO-GSFT)透氧膜暴露在模拟焦炉煤气和水蒸汽气氛，透氧膜依然能够连续稳定运行超过700个小时，水分解制氢产率基本稳定在0.8cm3 min-1cm-2，这说明CGO/(CGO-GSFT)透氧膜不仅具有较高的氧渗透性能，同时再次证实了其在苛刻的工作环境下具有优异的稳定性。
最后应该说明的是，以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (10)
1.一种具有氧化物薄层的多层陶瓷膜制备方法，其特征在于，包括：
以萤石型氧化物和钙钛矿型或尖晶石型氧化物为原料制成复合材料，然后，预成型，得到坯体；
将所述坯体的表面与Al2O3接触，进行烧结，即得。
2.如权利要求1所述的具有氧化物薄层的多层陶瓷膜制备方法，其特征在于，所述的萤石型氧化物化学组成表达式为Ce1-aAaO2-δ或BbZr1-bO2-δ，其中A选自La、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb中的一种或几种，0≤a≤1,δ为氧晶格缺陷数；B选自Y、Sc、Yb、Pr、Bi、Er、Ce中的一种或几种，0≤b≤1，δ为氧晶格缺陷数。
3.如权利要求1所述的具有氧化物薄层的多层陶瓷膜制备方法，其特征在于，所述的钙钛矿型氧化物化学组成表达式为MmSr1-mFe1-nNnO3-δ，其中M选自La、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Ba、Ca、Bi中的一种或几种；N选自Mg、Ca、Sc、Ti、V、Cr、Mn、Co、Ni、Cu、Zn、Zr、Y、Nb、Mo、Tc、Ru、Rh、Pd、Ag、Al、In、W、La、Gd、Ce中的一种或几种；0≤m≤0.5，0≤n≤0.5，δ为氧晶格缺陷数。
4.如权利要求1所述的具有氧化物薄层的多层陶瓷膜制备方法，其特征在于，所述的尖晶石型氧化物化学组成表达式为X3-yYyO4，其中X选自Mg、Fe、Co、Ni、Mn、Zn、Cd中的一种或几种，Y选自Al、Fe、Co、Cr、Ga、Mn中的一种或几种，0≤y≤3。
5.如权利要求1所述的具有氧化物薄层的多层陶瓷膜制备方法，其特征在于，所述复合材料的制备方法包括球磨混合法、固相反应法或溶胶-凝胶法。
6.如权利要求1所述的具有氧化物薄层的多层陶瓷膜制备方法，其特征在于，所述预成型方法包括干压法、相转化法和挤压成型法。
7.如权利要求1所述的具有氧化物薄层的多层陶瓷膜制备方法，其特征在于，所述坯体的表面与Al2O3接触的具体方式为将胚体放置在Al2O3刚玉片上面，或者夹在两个Al2O3刚玉片中间，或者涂敷纳米Al2O3胶体溶液。
8.如权利要求1所述的具有氧化物薄层的多层陶瓷膜制备方法，其特征在于，所述Al2O3是Al2O3刚玉片、Al2O3粉末或纳米Al2O3胶体溶液。
9.权利要求1-8任一项所述的方法制备的具有氧化物薄层的多层陶瓷膜，其特征在于，所述多层陶瓷膜包括两层或三层结构；
优选地，两层结构由单相萤石型CAO或BZO薄层和复合材料层构成；
或，三层结构包括一侧单相CAO或BZO薄层、中间复合材料致密层、另一侧复合材料多孔层；或者包括一侧单相CAO或BZO薄层、中间复合材料致密层、另一侧CAO或BZO薄层。
10.权利要求9所述的多层陶瓷膜在从含氧混合气中选择性分离氧以及用于烃类的催化部分氧化、分解H2O制氢或制备燃料电池中的应用。
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| CN1198213A (zh) * | 1995-09-29 | 1998-11-04 | 松下电器产业株式会社 | 气体传感器及其制造工艺 |
| CN101733048A (zh) * | 2009-12-25 | 2010-06-16 | 中国科学技术大学 | 用于气相氧化反应的中空纤维膜反应器及其制备和应用 |
| CN113332863A (zh) * | 2021-07-09 | 2021-09-03 | 辽宁石油化工大学 | 一种具有高表面催化活性双相透氧膜的制备方法 |
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| WO2023134092A1 (zh) * | 2022-01-14 | 2023-07-20 | 中国科学院青岛生物能源与过程研究所 | 一种具有氧化物薄层的多层陶瓷膜制备方法和应用 |
| CN114920549A (zh) * | 2022-05-30 | 2022-08-19 | 东南大学 | 一种以前驱液为粘结剂制备氧化物陶瓷纳米纤维膜的方法 |
| CN115714194A (zh) * | 2022-12-01 | 2023-02-24 | 中国科学院青岛生物能源与过程研究所 | 一种具有电解质薄层的固体氧化物半电池及其制备方法 |
| CN116283309A (zh) * | 2022-12-07 | 2023-06-23 | 中国科学院青岛生物能源与过程研究所 | 一种具有双保护层的陶瓷透氧膜及其制备方法与应用 |
| CN116514549A (zh) * | 2023-05-05 | 2023-08-01 | 上海大学 | 一种三相混合导体透氧膜材料及其制备方法 |
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| WO2023134092A1 (zh) | 2023-07-20 |
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