CN111574244B - 一种固体氧化物电池阻隔层致密化的方法 - Google Patents

一种固体氧化物电池阻隔层致密化的方法 Download PDF

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CN111574244B
CN111574244B CN202010361004.8A CN202010361004A CN111574244B CN 111574244 B CN111574244 B CN 111574244B CN 202010361004 A CN202010361004 A CN 202010361004A CN 111574244 B CN111574244 B CN 111574244B
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朱腾龙
吕秋秋
宋佳宁
钟秦
韩敏芳
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Abstract

本发明公开了一种固体氧化物电池阻隔层致密化的方法，固体氧化物电池常用电解质材料为YSZ(8％molY2O3稳定ZrO2，化学式为：Zr0.84Y0.16O2‑x)，YSZ与很多高活性阴、阳极钙钛矿材料的化学兼容性较差，在高温制备以及长期运行过程中容易发生反应。氧化铈基电解质材料多与YSZ等电解质组成双电解质层，或作为隔离层以防止在高温制备和长期运行过程中电极材料与电解质之间发生反应。致密的GDC隔离层可以有效降低燃料电池的欧姆阻抗，提高电池的导电率和催化性能。Ge(NO3)3·6H2O与Ce(NO3)3·6H2O按0.1:0.9的摩尔比例(Ce0.9Gd0.1O2‑m)配成水热溶液，将丝印过GDC阻隔层的电池通过水热的方法，在180℃下反应24h，之后制备成完整的电池。从而得到的电池具有更高的导电性能和催化活性以及较低的欧姆阻抗。

Description

一种固体氧化物电池阻隔层致密化的方法
技术领域
本发明涉及一种固体氧化物电池阻隔层致密化的方法，用于固体氧化物燃料电池领域。
背景技术
固体氧化物燃料电池是一种全固态的能量转换装置，能将化学能直接转化为电能，具有能量转化率高、环境友好、噪音低和可靠性强等优点，而且能够直接利用现有的各种含碳燃料，被认为是目前最有应用前景的发电系统。氧化锆基陶瓷薄膜作为常用的电解质仍存在一定缺点，氧化锆基陶瓷薄膜易与钙钛矿型阴极材料反应生成绝缘相La2Zr2O7和SrZrO3，使得电池性能与稳定性降低。目前解决此问题常用的方法是在氧化锆基陶瓷材料电解质与钙钛矿阴极之间加入一层氧化铈基陶瓷薄膜作隔层来阻挡氧化锆基电解质与钙钛矿阴极的反应。
CeO2基隔离层(如GDC,Gd0.1Ce0.9O2)可以防止YSZ电解质与LSCF等阴极在高温制备和长时间运行过程中发生反应。但GDC与YSZ薄膜很难实现共烧结，而且在～1200℃以上也会发生反应。除先进镀膜工艺外，大多单电池通过丝网印刷在致密YSZ表面制备GDC，但只能获得多孔隔离层。致密的GDC隔离层可以有效降低燃料电池的欧姆阻抗，提高电池的导电率和催化性能。通过传统方法烧结的氧化钆掺杂氧化铈(GDC)在1550℃才能获得95％以上的致密度。DTU、韩国KIER等开展了GDC隔离层的致密化修饰工作，通过在多孔GDC中浸渍GDC前驱体溶液或助烧剂的盐溶液显著提高了隔离层致密度，但需要重复多次且仍需高温下烧结(1150-1275℃)才能获得高致密度，过程繁琐。
发明内容
为了使隔离层GDC能够在低温下致密化，本发明提供了一种固体氧化物电池阻隔层致密化的方法，采用GDC同组分的硝酸水合物溶液，通过水热法以原位析出的方式在多孔的GDC表面上析出晶体，使GDC阻隔层致密化。
本发明解决现有技术问题所提出来的技术方案如下：
首先在致密YSZ(8％molY2O3稳定ZrO2，化学式为：Zr0.84Y0.16O2-x)电解质片上丝网印刷上隔离层GDC，之后在马弗炉中1250℃下煅烧3h。
然后配置水热溶液，在100ml反应釜中加入60ml去离子水，再加入0.1354gGe(NO3)3·6H2O(0.005mol/L)和1.1724g Ce(NO3)3·6H2O(0.045mol/L)晶体，连同反应釜一起超声溶解几分钟。
之后将丝网印刷上GDC的电解质片用酒精浸泡十分钟，之后擦拭干净。电解质片放入加了水热溶液的反应釜中，将反应釜放在烘箱中，180℃下反应24h。
最后将电解质片取出，在电解质片的GDC上丝网印刷上LSCF，面积为0.5cm，在1075℃下煅烧2h。之后在两侧加上银网和银丝集电，做成对称电池。
该方法与传统氧化铈基隔离层(GDC)的制备相比，其优势是：
(1)采用水热法将电池在反应釜中高压反应，使水热溶质原位析出在隔离层GDC的多孔处，再通过1075℃的煅烧形成致密的隔离层。有效降低了隔离层致密化煅烧温度。
(2)该方法在较低温度下获得致密的氧化铈基隔离层，避免了氧化锆基电解质与氧化铈基隔离层之间的相互反应，从而提高了电池性能。
附图说明
图1是本发明的工作流程图。
图2是水热反应后对称电池的断面扫描图，a图为GDC未水热处理的断面扫描电镜图，b图为GDC水热24h处理的断面扫描电镜图。
图3是水热反应后对称电池的断面扫描图，a图为GDC水热处理的断面扫描电镜图，b图为GDC醇热处理的断面扫描电镜图。
具体实施方式
实施例1
不同溶质比使电池阻隔层致密化的差异
首先在致密YSZ电解质片上丝网印刷上隔离层GDC，之后在马弗炉中1250℃下煅烧3h。
然后配置两份水热溶液，在100ml反应釜中加入60ml去离子水，再把Ge(NO3)3·6H2O与Ce(NO3)3·6H2O按0.1:0.9的摩尔比例(Ce0.9Gd0.1O2-m)配成的溶液，即与GDC同组分的硝酸水合物溶液晶体；第二份水热溶液Ge(NO3)3·6H2O与Ce(NO3)3·6H2O按0.1:1的摩尔比例(CeGd0.1O2-m)配成的溶液。电池片分别在两份水热溶液中反应24h。
之后将丝网印刷上GDC的电解质片用酒精浸泡十分钟，之后擦拭干净。电解质片放入加了水热溶液的反应釜中，将反应釜放在烘箱中，180℃下反应24h。
最后将电解质片取出，在电解质片的GDC上丝网印刷上LSCF，面积为0.5cm，在1075℃下煅烧2h。之后在两侧加上银网和银丝集电，做成对称电池。
0.1:0.9的摩尔比例的水热溶液反应过的电池在750℃下的欧姆阻抗为0.55Ω·cm2，0.1:0.9的摩尔比例的水热溶液反应过的电池在750℃下的欧姆阻抗为0.9Ω·cm2，欧姆阻抗越小，表明阻隔层GDC越致密，说明0.1:0.9的摩尔比例是最适合的水热比例。
实施例2
不同水热溶剂对电池致密化的影响
Ge(NO3)3·6H2O与Ce(NO3)3·6H2O按0.1:0.9的摩尔比例(Ce0.9Gd0.1O2-m)，分别以去离子水和无水乙醇为溶剂，即与GDC同组分的硝酸水合物溶液晶体。电解质片放入加了水热溶液的反应釜中，将反应釜放在烘箱中，180℃下反应24h。
最后将电解质片取出，在电解质片的GDC上丝网印刷上LSCF，面积为0.5cm，在1075℃下煅烧2h。之后在两侧加上银网和银丝集电，做成对称电池。
最终结果如图3可以看出，以乙醇为溶剂的电池，其隔离层的致密度更高，相比较水热反应，醇热反应的孔隙更小。

Claims (4)

1.一种固体氧化物电池阻隔层致密化的方法，其特征在于，将阻隔层为GDC，为Gd2O3掺杂CeO2，通式为Ce0.9Gd0.1O2-m，0﹤m≤0.5；
加入用于水热的溶质为Gd(NO3)3·6H2O与Ce(NO3)3·6H2O按0.1:0.9的摩尔比例配成的溶液，即与GDC同组分的硝酸水合物溶液，将丝网印刷的多孔隔离层通过水热法以原位析出的形式在具有多孔的GDC表面上析出晶体，水热条件为在 180℃下反应24h，使GDC阻隔层致密化。
2.根据权利要求1所述的固体氧化物电池阻隔层致密化的方法，其特征在于，通过丝网印刷在致密YSZ电解质片上丝网印刷上隔离层GDC，丝网印刷的隔离层为多孔结构。
3.根据权利要求1所述的固体氧化物电池阻隔层致密化的方法，其特征在于，丝网印刷的多孔隔离层在1250℃下煅烧3h。
4.根据权利要求1所述的固体氧化物电池阻隔层致密化的方法，其特征在于，水热后致密的隔离层GDC上丝网印刷上LSCF，面积为0.5cm，在1075℃下煅烧2h，之后在两侧加上银网和银丝集电，做成对称电池。
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