CN111235589B - 一种高温电解池阴极材料及其制备和应用 - Google Patents

一种高温电解池阴极材料及其制备和应用 Download PDF

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CN111235589B
CN111235589B CN201811444589.9A CN201811444589A CN111235589B CN 111235589 B CN111235589 B CN 111235589B CN 201811444589 A CN201811444589 A CN 201811444589A CN 111235589 B CN111235589 B CN 111235589B
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程谟杰
赵哲
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Dalian Institute of Chemical Physics of CAS
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Abstract

本发明公开了一种高温电解池阴极材料及制备和应用，其特征在于所述阴极材料是钙钛矿氧化物Ln1‑xSrxAlyFe1‑yO3‑δ，Ln为La,Pr,Sm,Gd,Er,Yb,Y中一种或几种,0≤x≤1,0≤y﹤1，0.05≤δ≤0.5。本发明的该阴极材料作为高温电解池阴极，具有良好的电化学性能，显示出优异的水电解性能和稳定性。

Description

一种高温电解池阴极材料及其制备和应用
技术领域
本发明涉及燃料电池和电解池领域，具体涉及一种高温电解池阴极材料及其制备和应用。
背景技术
高温固体氧化物电解池(solid oxide electrolysis cell,SOEC)被认为是高效的能源转化和储存装置之一，它可利用风能、太阳能所产生的电，高效地电解水蒸气、二氧化碳或两者的混合物而得到氢气或合成气。这些产物既可以通过燃料电池发电以弥补电网高峰期的电力需求，又可以进一步转化为其他化工燃料，应用场景非常多元化。
SOEC的核心部件包括电解质、阴极(氢电极)与阳极(氧电极)，三者构成了三明治结构。SOEC的阴极起着催化H2O或CO2的电化学还原反应，并提供反应物与产物气体传输通道的作用，它必须具有良好的催化活性、电导率以及足够的孔隙率，还必须具备工作条件下的化学稳定性、热稳定性与机械强度。目前，高温电解池应用较多的是Ni-YSZ阴极。但是，由于SOEC工作在高温高湿条件下，Ni/YSZ的稳定性问题更为突出，是影响SOEC运行寿命的主要因素之一。Ni电极暴露在高湿度条件下，易发生显著的颗粒聚结现象，Ni覆盖率下降，极化阻抗增大，导致电化学性能明显下降。因此，具有高活性和高稳定性的阴极材料尚需开发。
发明内容
本发明公开了一种高温电解池阴极材料Ln1-xSrxAlyFe1-yO3-δ，Ln为La,Pr,Sm,Gd，Er，Yb，Y中一种或几种，0≤x≤1，0≤y﹤1，0.05≤δ≤0.5。本发明的该阴极材料作为高温固体氧化物燃料电池的阴极，具有良好的电化学性能，显示出优异的水电解性能和稳定性。
本发明解决上述问题所采用的技术方案为：一种高温电解池阴极材料，其特征在于：所述阴极材料是钙钛矿氧化物Ln1-xSrxAlyFe1-yO3-δ，Ln为La，Pr，Sm,Gd，Er，Yb，Y中一种或几种，0≤x≤1，0≤y﹤1，0.05≤δ≤0.5。
本发明公开一种固体氧化物电解池膜电极，其特征在于所述膜电极由阴极、隔层、电解质、隔层、阳极叠层组成，所述电解质两侧设置隔层，阳极和阴极相对设置电解质两侧的隔层上。所述阴极包含化学组成为Ln1-xSrxAlyFe1-yO3-δ的粉体，Ln为La，Pr，Sm，Gd，Er，Yb，Y中一种或几种，0≤x≤1,0≤y﹤1，0≤δ≤0.5，所述电解质包含化学组成为YnZr1-nO2的粉体，0≤n≤0.2，所述隔层包含化学组成为GdzCe1-zO2的粉体,0≤z≤0.2，所述阳极包含化学组成为A1-kSrkComFe1-mO3-β的粉体，0≤k≤1，0≤m≤1，0≤β≤0.5，A为La，Pr，Sm中一种。
所述膜电极的阴极Ln1-xSrxAlyFe1-yO3-δ，Ln优选La，Pr，Sm中一种或几种。
所述膜电极的阳极A1-kSrkComFe1-mO3-β，A优选La，Sm中一种。
所述阴极Ln1-xSrxAlyFe1-yO3-δ，优选0≤x≤0.5，0≤y﹤0.4。
所述阳极A1-kSrkComFe1-mO3-β，优选0≤k≤0.6，0≤m≤0.8。
所述阴极、隔层、电解质、隔层、阳极叠层厚度分别为10-50微米，0.03-3微米，150-500微米，0.03-3微米，10-50微米。
所述电解质由流延法、干压法制备，所述隔层由浆料涂覆法、丝网印刷法、磁控溅射法制备到电解质两侧，所述阳极可由浆料涂覆法、丝网印刷法制备到电解质一侧的隔层上，所述阴极可由浆料涂覆法、丝网印刷法制备到电解质另一侧的隔层上。
所述阴极和膜电极在高温固体氧化物电解池中的应用，可用于水蒸气电解。
本发明的优点在于：
本发明公开的高温电解池阴极材料，在还原气氛中具有较高的电导率和氧化/还原循环稳定性，解决了传统Ni阴极抗氧化/还原循环稳定性差的问题，在电解水方面显示出优异的电化学性能和较好的稳定性。该阴极材料制备简单，制备原材料价格相对较低，容易放大制备。
具体实施方式
下面通过实施例对本发明作进一步的阐述。
实施例1
固体氧化物电解池膜电极：阴极、隔层、电解质、隔层、阳极叠层厚度分别为20微米，0.05微米，200微米，0.05微米，20微米。其中，阴极为La0.8Sr0.2Al0.3Fe0.7O2.8，隔层为Gd0.1Ce0.9O2，电解质为Y0.15Zr0.85O2，阳极为La0.6Sr0.4Co0.2Fe0.8O2.7。制备方法如下，首先通过干压法制备电解质，然后通过浆料涂覆法在电解质两侧分别制备隔层，最后通过丝网印刷法分别在电解质两侧隔层上制备阴极和阳极。
膜电极电化学测试结果如下，测试温度800℃下，阴极测湿度45％，1.3V电解电压下，电流密度达到0.15A.cm-2，200h运行后无明显衰减。
实施例2
固体氧化物电解池膜电极：阴极、隔层、电解质、隔层、阳极叠层厚度分别为50微米，2微米，180微米，2微米，20微米。其中，阴极为Sm0.8Sr0.2Al0.3Fe0.7O2.85，隔层为Gd0.2Ce0.8O2，电解质为Y0.15Zr0.85O2，阳极为Sm0.6Sr0.4CoO2.65。制备方法如下，首先通过流延法制备电解质，然后通过磁控溅射法在电解质两侧分别制备隔层，最后通过丝网印刷法分别在电解质两侧隔层上制备阴极和阳极。
膜电极电化学测试结果如下，测试温度800℃下，阴极测湿度45％，1.3V电解电压下，电流密度达到0.35A.cm-2，200h运行后无明显衰减。
实施例3
固体氧化物电解池膜电极：阴极、隔层、电解质、隔层、阳极叠层厚度分别为30微米，1微米，250微米，1微米，40微米。其中，阴极为Sm0.6Sr0.4Al0.4Fe0.6O2.75，隔层为Gd0.2Ce0.8O2，电解质为Y0.15Zr0.85O2，阳极为Pr0.7Sr0.3CoO2.7。制备方法如下，首先通过流延法制备电解质，然后通过磁控溅射法在电解质两侧分别制备隔层，最后通过丝网印刷法分别在电解质两侧隔层上制备阴极和阳极。
膜电极电化学测试结果如下，测试温度800℃下，阴极测湿度45％，1.3V电解电压下，电流密度达到0.30A.cm-2，200h运行后无明显衰减。

Claims (7)

1.一种固体氧化物电解池膜电极，其特征在于：所述膜电极由阴极、隔层、电解质、隔层、阳极层叠组成，所述电解质两侧设置隔层，阳极和阴极相对设置电解质两侧的隔层上；所述阴极包含化学组成为Ln1-xSrxAlyFe1-yO3-δ的粉体，Ln为La，Pr，Sm，Gd，Er，Yb，Y 中一种或几种，0﹤x﹤1,0﹤y﹤1，0≤δ≤0.5，所述电解质包含化学组成为YnZr1-nO2的粉体，
0﹤n≤0.2，所述隔层包含化学组成为GdzCe1-zO2的粉体, 0﹤z﹤0.2，所述阳极包含化学组成为A1-kSrkComFe1-mO3-β的粉体，0﹤k﹤1，0≤m≤1，0≤β≤0.5，A为La，Pr，Sm中一种或二种以上。
2.按照权利要求1所述的固体氧化物电解池膜电极，其特征在于：所述膜电极的阴极Ln1-xSrxAlyFe1-yO3-δ，Ln为La，Pr，Sm中一种或几种。
3.按照权利要求1所述的 固体氧化物电解池膜电极，其特征在于：所述膜电极的阳极A1-kSrkComFe1-mO3-β，A为La，Sm中一种。
4.按照权利要求1或2所述的固体氧化物电解池膜电极，其特征在于：所述阴极Ln1- xSrxAlyFe1-yO3-δ， 0﹤x≤0.5，0﹤y﹤0.4。
5.按照权利要求1或3所述的固体氧化物电解池膜电极，其特征在于：所述阳极A1- kSrkComFe1-mO3-β， 0﹤k≤0.6， 0≤m≤0.8。
6.一种权利要求2-5任一项所述的固体氧化物电解池膜电极的制备方法，其特征在于：所述电解质由流延法或干压法制备，所述隔层由浆料涂覆法、丝网印刷法或磁控溅射法制备到电解质两侧，所述阳极可由浆料涂覆法或丝网印刷法制备到电解质一侧的隔层上，所述阴极可由浆料涂覆法或丝网印刷法制备到电解质另一侧的隔层上。
7.一种权利要求2-5任一所述的膜电极在高温固体氧化物电解池中的应用，可用于水蒸气电解。
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