Sn掺杂CeO2中Ce3+的形成机制及其对质子交换膜燃料电池耐久性的影响

摘要/Abstract

摘要： 在质子交换膜燃料电池(PEMFC)运行过程中,产生的自由基会攻击质子交换膜,使其开裂或形成孔洞,导致电池失效。常见的改性方法是在质子交换膜(PEM)中添加自由基清除剂材料。基于此,本文合成了Sn掺杂CeO₂自由基清除剂,通过提高Ce³⁺浓度来增强其在PEMFC中自由基清除性能,避免PEM厚度迅速减薄,从而提高质子PEMFC的耐久性。密度泛函理论计算和试验结果表明,Sn掺杂会引起CeO₂产生晶格畸变,降低氧空位形成能,促进CeO₂中Ce³⁺的形成。同时,Sn²⁺的加入可将CeO₂-Sn样品中的Ce⁴⁺还原为Ce³⁺,提升Ce³⁺的浓度,从而提高PEM的耐久性。单电池测试结果表明,经70 h的开路电压衰减测试,CeO₂-Sn-5%改性后的质子交换膜组装的单电池电压衰减率最低(18%),且功率保留率(56%)比其他样品更高,表明该样品具有更优异的耐久性。

关键词: CeO₂, Sn掺杂, 密度泛函理论计算, 氧空位, 质子交换膜燃料电池, 耐久性

Abstract: During the operation of a proton exchange membrane fuel cell (PEMFC), free radicals generated by PEMFC usually attack proton exchange membrane (PEM), causing the formation of crack or holes, which make the cell failure. Adding free radical scavenger material into PEM is regarded as a commonly modification method. Here, a Sn-doped CeO₂ free radical scavenger was synthesized. By increasing the concentration of Ce³⁺, the free radical scavenging performance of CeO₂ in PEMFC could be enhanced, which could avoid PEM thickness to decrease rapidly, and the durability of PEMFC could be improved. Density functional theory calculation and experimental results show that Sn-doping can cause lattice distortion of CeO₂, reduce the formation energy of oxygen vacancy, and improve the formation of Ce³⁺ in CeO₂. At the same time, the addition of Sn²⁺ can reduce Ce⁴⁺ in CeO₂-Sn to form Ce³⁺, which is conducive to increasing the concentration of Ce³⁺ and thus improving the durability of PEM. The results of single cell test show that the voltage attenuation rate of the single cell assembled with CeO₂-Sn-5% modified is the lowest (18%) and the power retention rate (56%) of the single cell is higher than that of other PEM after 70 h open circuit voltage decay test, which indicates that the sample has better durability.

Key words: CeO₂, Sn-doping, density functional theory calculation, oxygen vacancy, PEMFC, durability

中图分类号:

TK91

涂自强, 何漩, 杜星, 陈辉, 赵雷, 张海军, 王诚. Sn掺杂CeO₂中Ce³⁺的形成机制及其对质子交换膜燃料电池耐久性的影响[J]. 硅酸盐通报, 2023, 42(5): 1841-1851.

TU Ziqiang, HE Xuan, DU Xing, CHEN Hui, ZHAO Lei, ZHANG Haijun, WANG Cheng. Formation Mechanism of Ce³⁺ in Sn-Doped CeO₂ and Its Effect on Durability of Proton Exchange Membrane Fuel Cells[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2023, 42(5): 1841-1851.

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Sn掺杂CeO₂中Ce³⁺的形成机制及其对质子交换膜燃料电池耐久性的影响

Formation Mechanism of Ce³⁺ in Sn-Doped CeO₂ and Its Effect on Durability of Proton Exchange Membrane Fuel Cells

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