CN110563455A - 一种利用改进的液相辅助烧结机制来制备sofc陶瓷连接体的方法 - Google Patents

一种利用改进的液相辅助烧结机制来制备sofc陶瓷连接体的方法 Download PDF

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CN110563455A
CN110563455A CN201910988744.1A CN201910988744A CN110563455A CN 110563455 A CN110563455 A CN 110563455A CN 201910988744 A CN201910988744 A CN 201910988744A CN 110563455 A CN110563455 A CN 110563455A
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魏涛
叶钰盛
卓怀芃
张早红
王志孟
杨兴林
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Jiangsu University of Science and Technology
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Abstract

本发明公开了一种利用改进的液相辅助烧结机制来制备SOFC陶瓷连接体的方法，固体氧化物燃料电池用陶瓷连接体组成为镧锶铬铁氧化物，其化学式为LaxSr1‑xCryFe1‑yO3‑σ，其中x=0.5～1;y=0.1～0.5，厚度为10～20μm；具体制备方法如下步骤：1）镧锶铬铁氧化物粉体的制备；2）提拉法制备连接体并实现与阳极的共烧。本发明利用一种改进的液相辅助烧结机制，从材料本身的性能入手，利用简单的提拉制备法即可使得连接体烧结致密，同时实现SOFC的Ni‑YSZ阳极与陶瓷连接体共烧，大大节省了制备陶瓷连接体的成本。

Description

一种利用改进的液相辅助烧结机制来制备SOFC陶瓷连接体的 方法
技术领域
本发明涉及属于电池领域，具体的说是一种利用改进的液相辅助烧结机制来制备SOFC陶瓷连接体的方法。
背景技术
固体氧化物燃料电池(SOFC)是将燃料中的化学能直接转化为电能的一种电化学装置，具有高效、清洁、能量转换效率高、对环境友好、燃料适应性强及寿命长等优点，被公认为21世纪的绿色能源转化装置。目前国际国内主流的SOFC结构主要分为平板式和管式两种，而由于管式结构相较于平板式结构具有易于封装，耐久性更强以及制作成本低等优势，得到世界各机构的广泛关注，如美国的西门子-西屋公司以及日本的三菱重工均采用管式结构。
但是SOFC单电池工作电压只有0.8 V左右，要达到能够实际应用的千瓦乃至兆瓦级发电机功率范围，需将很多单电池按照串联和并联方式组装。连接体就是将电池组装成电池堆的关键部件，它不仅为相邻电池的阴极和阳极提供电子通道，而且起着隔离相邻阳极和阴极的不同气氛的作用。因此连接体必须具备高的电子电导率、低的氧离子电导率，同时其在800℃左右的工作环境下，最重要的一个作用是隔离阴极的O2和阳极的H2，因此连接体必须是致密的，而且需在氧化和还原气氛下都具备良好的化学和物理稳定性，是SOFC所有组件中对材料性能要求最为苛刻的。而且管式SOFC只能采用陶瓷材料作为连接体。目前，常用的材料是铬酸镧（LaCrO3），它因具备良好的电子电导和化学稳定性而被用作SOFC连接体达数十年，比如：西门子-西屋公司采用等离子喷涂法，沿管轴线方向制备了宽11mm、厚100μm的掺杂LaCrO3连接体条，但是由于工艺复杂，成本很高。这是由于LaCrO3基陶瓷材料的烧结性能不佳，使得该类材料很难在NiO-YSZ阳极上通过共烧而达到致密，因此不得不采用电化学气相沉积、等离子喷涂以及磁控溅射等方法，对设备要求高，导致SOFC连接体的制造成本往往占到整个电堆的60 %，这严重阻碍了SOFC的商业化进展。
除了采用高精尖的制备技术，另一种提高LaCrO3烧结性能的方法是“液相辅助烧结机制”在LaCrO3粉末中加入少量的烧结助剂，比如添加CaCrO4，该材料熔点较低，在烧结过程中会变成液体，从而填补在LaCrO3的缝隙中，进而提升连接体的致密度，但是这种方法不仅在连接体材料中引入了CaCrO4杂质，该杂质还会与SOFC的电解质（YSZ，氧化钇稳定的氧化锆）发生反应生成绝缘的CaZrO3，造成连接体的导电性能变差。
发明内容
为了解决上述问题，本发明提供了一种利用改进的液相辅助烧结机制来制备SOFC陶瓷连接体的方法，利用一种改进的液相辅助烧结机制，从材料本身的性能入手，利用简单的提拉制备法即可使得连接体烧结致密，同时实现SOFC的Ni-YSZ阳极与陶瓷连接体共烧。
为了达到上述目的，本发明通过以下技术方案来实现的：
本发明是一种利用改进的液相辅助烧结机制来制备SOFC陶瓷连接体的方法，其特征在于：固体氧化物燃料电池用陶瓷连接体组成为镧锶铬铁氧化物，其化学式为LaxSr1-xCryFe1- yO3-σ，其中x=0.5～1; y=0.1～0.5，厚度为10～20μm；具体制备方法如下步骤：
1）镧锶铬铁氧化物粉体的制备：
a、采用均为分析纯的La2O3, SrCO3, Fe(NO3)3·9H2O和 Cr(NO3)3·9H2O为初始原料，根据各组分的元素化学计量比，将La2O3，SrCO3溶于50~100ml浓度为1mol/L稀硝酸，配制成溶液1；Fe(NO3)3·9H2O 和Cr(NO3)3·9H2O溶于50~100ml去离子水，配制成溶液2，然后将上述溶液1和溶液2混合，搅拌均匀得到混合溶液；
b、往步骤a中得到的混合溶液中加入柠檬酸和乙二醇作为络合剂，在80 ℃的水浴中不停地搅拌，直至形成暗黑色胶状物；
c、将步骤b中得到的暗黑色胶状物转移至烘箱中以200 ℃烘干，待胶状物变成蓬松的泡沫状后取出；
d、将步骤三中的泡沫状LaxSr1-xCryFe1-yO3-σ前驱体研磨成粉末后置于马弗炉中，采用程序升温法烧结，烧结温度为700～1100 ℃，升温速率为3~5 ℃/min，保温4～8小时，除去中间残留的有机物以及碳，形成所需的含有SrCrO4的LaxSr1-xCryFe1-yO3-σ粉体；
2）提拉法制备连接体并实现与阳极的共烧：
e、取LaxSr1-xCryFe1-yO3-σ粉体20克，酒精40克，分散剂TEA 0.6克，粘结剂PVB 0.4克，加入60克氧化锆研磨球，在行星球磨机上研磨4小时，然后抽真空处理2～3分钟，除去浆料中的空气，得到LaxSr1-xCryFe1-yO3-σ浆料；
f、将阳极支撑管素坯浸入e中的浆料中，放入10~20s，待管子上的LaxSr1-xCryFe1-yO3-σ浆料干燥后，继续提拉一次，然后放入烘箱干燥。最后将上述提拉两次后的带有连接体的素胚管放入马弗炉中在1400℃共烧4个小时，厚度为10～20μm。
本发明的进一步改进在于：所述LaxSr1-xCryFe1-yO3-σ为La0.8Sr0.2Cr0.5Fe0.5O3-σ。
本发明的进一步改进在于：所述步骤1的b步骤中向混合溶液中加入的柠檬酸与乙二醇 与溶液中的金属离子之和的摩尔比为1∶1∶1。
本发明的进一步改进在于：步骤1中的d步骤中烧结的温度为800-1100℃。
本发明的进一步改进在于：步骤1中的b步骤中搅拌时间为8-12h。
本发明的进一步改进在于：步骤1中的a步骤中的La2O3、SrCO3、Fe(NO3)3·9H2O 和Cr(NO3)3·9H2O的量均为0.01~0.03mol。
在我们前期的研究中，我们发现掺杂一定量Sr和Fe的LaCrO3即LaxSr1-xCryFe1- yO3-σ，其中x=0.5～1; y=0.1～0.5，在800 ℃时，电导率在空气中达21.88 S cm-1，在5 % H2/Ar中达6.45 S cm-1，且在还原和氧化气氛中都能保持稳定，同时热膨胀系数为11.47×10-6 K-1，同YSZ 的膨胀系数10.95×10-6 K-1基本保持一致。只要烧结致密后，便非常适合作为SOFC的陶瓷连接体材料。
但是采用传统的方法很难将这种材料烧结致密。通过研究发现，在800-1100 ℃时会有SrCrO4析出，但是到1200℃以后，SrCrO4又会重新融入到LaxSr1-xCryFe1-yO3-σ当中，形成完整的纯相结构，见图1，即在1200℃以上，Sr、Fe掺杂的LaCrO3中并没有其他杂相生成，可以形成纯相物质。我们还发现SrCrO4的熔点也比较低，在800~1000 ℃以下也会以液体形式存在，这让我们联想到“液相辅助烧结机制”中烧结助剂的作用。因此我们直接利用这一现象，即采用800~1000℃煅烧的粉体（会有析出的SrCrO4）作为制作连接体的材料，而不是采用1200℃煅烧的粉体。这样当连接体制备好后，在1400℃煅烧4h后，原来的SrCrO4又会重新融入到LaxSr1-xCryFe1-yO3-σ材料当中，形成纯相的LaxSr1-xCryFe1-yO3-σ，既没有引入杂质，保持了原材料的性能，同时利用了“液相辅助烧结”的原理，使得连接体致密，在此，我们称之为“改进的液相辅助烧结机制”。
本发明的有益效果是：本发明工艺简单，通过上述提拉的办法可以很方便地在管式SOFC电池上制备连接体，连接体面积可控，通过改变涂覆面积的大小，可以很容易地控制连接体面积。采用与阳极支撑管共烧结的办法，经济、简单且方便，减少制备步骤及成本，有利于管式SOFC商业化。由于是通过共烧制备，连接体与阳极烧结在一起，结构牢固，结合性好，有利于提高电池热循环性能。此外，陶瓷连接体不会生氧化，在氧化和还原气氛中稳定性好。
附图说明
图1是图1 900~1200℃煅烧的粉体的XRD图。
图2是在NiO-YSZ阳极素胚上用提拉法制备LSCrF连接体薄膜的示意图。
图3 共烧后的电池阳极与连接体接触情况。其中a为还原前；b为还原后。
具体实施方式
为了加强对本发明的理解，下面将结合附图和实施例对本发明作进一步描述，以下实施例进一步说明本发明的内容，但不应理解为对本发明的限制，在不背离本发明实质的情况下，对本发明方法、步骤或条件所作的修改和替换，均属于本发明的范围。
本发明是一种利用改进的液相辅助烧结机制来制备SOFC陶瓷连接体的方法，固体氧化物燃料电池用陶瓷连接体组成为镧锶铬铁氧化物，其化学式为LaxSr1-xCryFe1-yO3-σ其中x=0.5～1; y=0.1～0.5，厚度为10～20μm；本发明的镧锶铬铁氧化物组成为La0.8Sr0.2Cr0.5Fe0.5O3-σ具体制备方法如下步骤：
1）镧锶铬铁氧化物粉体的制备：
a、采用均为分析纯的La2O3, SrCO3, Fe(NO3)3·9H2O和 Cr(NO3)3·9H2O为初始原料，根据各组分的元素化学计量比，将0.01~0.03mol La2O3，0.01~0.03mol SrCO3溶于50~100ml浓度为1mol/L稀硝酸，配制成溶液1；0.01~0.03mol Fe(NO3)3·9H2O 和0.01~0.03mol Cr(NO3)3·9H2O溶于50~100ml去离子水，配制成溶液2，然后将上述溶液1和溶液2混合，搅拌均匀得到混合溶液；
b、往步骤a中得到的混合溶液中加入柠檬酸和乙二醇作为络合剂，在80 ℃的水浴中不停地搅拌8-12h，直至形成暗黑色胶状物；
c、将步骤b中得到的暗黑色胶状物转移至烘箱中以200 ℃烘干，待胶状物变成蓬松的泡沫状后取出；
d、将步骤三中的泡沫状La0.8Sr0.2Cr0.5Fe0.5O3-σ前驱体研磨成粉末后置于马弗炉中，采用程序升温法烧结，烧结温度为700～1100 ℃，升温速率为3~5 ℃/min，保温4～8小时，除去中间残留的有机物以及碳，形成所需的含有SrCrO4的La0.8Sr0.2Cr0.5Fe0.5O3-σ粉体；
2）提拉法制备连接体并实现与阳极的共烧：
e、取La0.8Sr0.2Cr0.5Fe0.5O3-σ粉体20克，酒精40克，分散剂TEA 0.6克，粘结剂PVB 0.4克，加入60克氧化锆研磨球，在行星球磨机上研磨4小时，然后抽真空处理2～3分钟，除去浆料中的空气，得到La0.8Sr0.2Cr0.5Fe0.5O3-σ浆料；
f、将阳极支撑管素坯浸入e中的浆料中，放入10~20s，待管子上的La0.8Sr0.2Cr0.5Fe0.5O3-σ浆料干燥后，继续提拉一次，然后放入烘箱干燥，最后将上述提拉两次后的带有连接体的素胚管放入马弗炉中在1400℃共烧4个小时，厚度为10～20μm。
图3a为共烧4h后的电池阳极与连接体接触的情况，连接体与阳极可以紧密的结合在一起，同时连接体表面呈现光亮，说明非常致密。图2可以看出即使经过H2还原之后，即模拟SOFC真实工作环境，连接体与阳极支撑体之间依然结合紧密且致密性良好，说明该连接体与阳极支撑管素坯共烧的办法是可行的。

Claims (7)

1.一种利用改进的液相辅助烧结机制来制备SOFC陶瓷连接体的方法，其特征在于：固体氧化物燃料电池用陶瓷连接体组成为镧锶铬铁氧化物，其化学式为LaxSr1-xCryFe1-yO3-σ，其中x=0.5～1; y=0.1～0.5，厚度为10～20μm；具体制备方法如下步骤：
1）镧锶铬铁氧化物粉体的制备：
a、采用均为分析纯的La2O3, SrCO3, Fe(NO3)3·9H2O和 Cr(NO3)3·9H2O为初始原料，根据各组分的元素化学计量比，将La2O3，SrCO3溶于50~100ml浓度为1mol/L稀硝酸，配制成溶液1；Fe(NO3)3·9H2O 和Cr(NO3)3·9H2O溶于50~100ml去离子水，配制成溶液2，然后将上述溶液1和溶液2混合，搅拌均匀得到混合溶液；
b、往步骤a中得到的混合溶液中加入柠檬酸和乙二醇作为络合剂，在80 ℃的水浴中不停地搅拌，直至形成暗黑色胶状物；
c、将步骤b中得到的暗黑色胶状物转移至烘箱中以200 ℃烘干，待胶状物变成蓬松的泡沫状后取出；
d、将步骤三中的泡沫状LaxSr1-xCryFe1-yO3-σ前驱体研磨成粉末后置于马弗炉中，采用程序升温法烧结，烧结温度为700～1100 ℃，升温速率为3~5 ℃/min，保温4～8小时，除去中间残留的有机物以及碳，形成所需的含有SrCrO4的LaxSr1-xCryFe1-yO3-σ粉体；
2）提拉法制备连接体并实现与阳极的共烧：
e、取LaxSr1-xCryFe1-yO3-σ粉体20克，酒精40克，分散剂TEA 0.6克，粘结剂PVB 0.4克，加入60克氧化锆研磨球，在行星球磨机上研磨4小时，然后抽真空处理2～3分钟，除去浆料中的空气，得到LaxSr1-xCryFe1-yO3-σ浆料；
f、将阳极支撑管素坯浸入e中的浆料中，放入10~20s，待管子上的LaxSr1-xCryFe1-yO3-σ浆料干燥后，继续提拉一次，然后放入烘箱干燥。
2.最后将上述提拉两次后的带有连接体的素胚管放入马弗炉中在1400℃共烧4个小时，厚度为10～20μm。
3.根据权利要求1所述一种利用改进的液相辅助烧结机制来制备SOFC陶瓷连接体的方法，其特征在于：所述LaxSr1-xCryFe1-yO3-σ为La0.8Sr0.2Cr0.5Fe0.5O3-σ。
4.根据权利要求2所述一种利用改进的液相辅助烧结机制来制备SOFC陶瓷连接体的方法，其特征在于：所述步骤1的b步骤中向混合溶液中加入的柠檬酸与乙二醇 与溶液中的金属离子之和的摩尔比为1∶1∶1。
5.根据权利要求1所述一种利用改进的液相辅助烧结机制来制备SOFC陶瓷连接体的方法，其特征在于：步骤1中的d步骤中烧结的温度为800-1100℃。
6.根据权利要求1所述一种利用改进的液相辅助烧结机制来制备SOFC陶瓷连接体的方法，其特征在于：步骤1中的b步骤中搅拌时间为8-12h。
7.根据权利要求3-5任意一项所述一种利用改进的液相辅助烧结机制来制备SOFC陶瓷连接体的方法，其特征在于：步骤1中的a步骤中的La2O3、SrCO3、Fe(NO3)3·9H2O 和Cr(NO3)3·9H2O的量均为0.01~0.03mol。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111484329A (zh) * 2020-05-20 2020-08-04 中国科学院重庆绿色智能技术研究院 一种液相合成LaxSr1-xCoO3-δ复合氧化物的方法

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050022883A1 (en) * 2003-07-29 2005-02-03 Paul Adams Fuel cartridge with connecting valve
US20050084733A1 (en) * 2003-10-21 2005-04-21 Tarver Gary D. Fuel cell assembly and method of making the same
US20070190393A1 (en) * 2006-02-14 2007-08-16 Markoski Larry J System for flexible in situ control of water in fuel cells
US20070290384A1 (en) * 2004-08-07 2007-12-20 Cabot Corporation Gas dispersion manufacture of nanoparticulates, and nanoparticulate-containing products and processing thereof
CN101148322A (zh) * 2007-06-29 2008-03-26 清华大学 固体氧化物燃料电池用微晶玻璃封接材料及其封接方法
US20080274393A1 (en) * 2007-04-17 2008-11-06 Markoski Larry J Hydrogel barrier for fuel cells
CN102888599A (zh) * 2012-11-01 2013-01-23 哈尔滨工业大学 在多孔基底材料上制备高致密度金属氧化物薄膜的方法
US20170069917A1 (en) * 2015-09-08 2017-03-09 Institute Of Nuclear Energy Research, Atomic Energy Council, Executive Yuan Growing method of layers for protecting metal interconnects of solid oxide fuel cells
CN107200575A (zh) * 2017-06-08 2017-09-26 江苏师范大学 一种Ca助剂体系YAG基透明陶瓷的制备方法
CN107721424A (zh) * 2017-09-30 2018-02-23 江苏师范大学 一种凝胶注模成型制备yag透明陶瓷的方法
CN109704765A (zh) * 2019-03-07 2019-05-03 哈尔滨工业大学 具有准同型晶相结构的高致密化铁电陶瓷及其制备方法

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050022883A1 (en) * 2003-07-29 2005-02-03 Paul Adams Fuel cartridge with connecting valve
US20050084733A1 (en) * 2003-10-21 2005-04-21 Tarver Gary D. Fuel cell assembly and method of making the same
US20070290384A1 (en) * 2004-08-07 2007-12-20 Cabot Corporation Gas dispersion manufacture of nanoparticulates, and nanoparticulate-containing products and processing thereof
US20070190393A1 (en) * 2006-02-14 2007-08-16 Markoski Larry J System for flexible in situ control of water in fuel cells
US20080274393A1 (en) * 2007-04-17 2008-11-06 Markoski Larry J Hydrogel barrier for fuel cells
CN101148322A (zh) * 2007-06-29 2008-03-26 清华大学 固体氧化物燃料电池用微晶玻璃封接材料及其封接方法
CN102888599A (zh) * 2012-11-01 2013-01-23 哈尔滨工业大学 在多孔基底材料上制备高致密度金属氧化物薄膜的方法
US20170069917A1 (en) * 2015-09-08 2017-03-09 Institute Of Nuclear Energy Research, Atomic Energy Council, Executive Yuan Growing method of layers for protecting metal interconnects of solid oxide fuel cells
CN107200575A (zh) * 2017-06-08 2017-09-26 江苏师范大学 一种Ca助剂体系YAG基透明陶瓷的制备方法
CN107721424A (zh) * 2017-09-30 2018-02-23 江苏师范大学 一种凝胶注模成型制备yag透明陶瓷的方法
CN109704765A (zh) * 2019-03-07 2019-05-03 哈尔滨工业大学 具有准同型晶相结构的高致密化铁电陶瓷及其制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111484329A (zh) * 2020-05-20 2020-08-04 中国科学院重庆绿色智能技术研究院 一种液相合成LaxSr1-xCoO3-δ复合氧化物的方法

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