{"title":"An active and durable perovskite electrode with reversibly phase transition-induced exsolution for protonic ceramic cells","authors":"Zhen Wang, Guang Jiang, Ying Zhang, Yaowen Wang, Youcheng Xiao, Xiyang Wang, Yanxiang Zhang, Tong Liu, Fang Wang, Tianmin He","doi":"10.1016/j.cej.2024.157268","DOIUrl":null,"url":null,"abstract":"Protonic ceramic cells (PCCs) possess great application potential, attributed to their cleanliness and high energy conversion efficiency. However, designing active air electrodes with both high stability is challenging. Herein, we report a nanospinel-modified perovskite oxide, Nd<sub>0.5</sub>Ba<sub>0.5</sub>Mn<sub>0.7</sub>Co<sub>0.15</sub>Ni<sub>0.15</sub>O<sub>3−δ</sub>-(Co<sub>x</sub>Ni<sub>y</sub>)<sub>3</sub>O<sub>4</sub> (CNO@NBMCN), obtained by a reversibly phase transition-induced exsolution process, as a highly active and durable air electrode for PCCs. Phase-field simulations reveal the intrinsic mechanism of nanoparticles strongly pinning to the substrate in a high-temperature oxidizing environment. The CNO@NBMCN electrode exhibits remarkable low area specific resistance (0.38 Ω cm<sup>2</sup> at 600 °C) and exceptional stability (degradation rate 0.01 % h<sup>−1</sup>). It is confirmed by soft X-ray absorption spectroscopy that the construction of the heterostructure leads to more distortion in Mn–O octahedra and weaker metal–oxygen bonds, thereby contributing to the formation of oxygen vacancies. And the exceptionally high durability supported by both fast ion surface exchange and charge transfer at triple-phase boundaries. A single cell with the CNO@NBMCN air electrode achieves outstanding performances in the fuel cell (peak power density of 1.28 W cm<sup>−2</sup>) and electrolysis modes (current density of 2.14 A cm<sup>−2</sup> at 1.3 V), recorded at 700 °C. This work inspires innovative design concepts for robust heterogeneous electrocatalysts.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":null,"pages":null},"PeriodicalIF":13.3000,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Engineering Journal","FirstCategoryId":"5","ListUrlMain":"https://doi.org/10.1016/j.cej.2024.157268","RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"ENGINEERING, CHEMICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Protonic ceramic cells (PCCs) possess great application potential, attributed to their cleanliness and high energy conversion efficiency. However, designing active air electrodes with both high stability is challenging. Herein, we report a nanospinel-modified perovskite oxide, Nd0.5Ba0.5Mn0.7Co0.15Ni0.15O3−δ-(CoxNiy)3O4 (CNO@NBMCN), obtained by a reversibly phase transition-induced exsolution process, as a highly active and durable air electrode for PCCs. Phase-field simulations reveal the intrinsic mechanism of nanoparticles strongly pinning to the substrate in a high-temperature oxidizing environment. The CNO@NBMCN electrode exhibits remarkable low area specific resistance (0.38 Ω cm2 at 600 °C) and exceptional stability (degradation rate 0.01 % h−1). It is confirmed by soft X-ray absorption spectroscopy that the construction of the heterostructure leads to more distortion in Mn–O octahedra and weaker metal–oxygen bonds, thereby contributing to the formation of oxygen vacancies. And the exceptionally high durability supported by both fast ion surface exchange and charge transfer at triple-phase boundaries. A single cell with the CNO@NBMCN air electrode achieves outstanding performances in the fuel cell (peak power density of 1.28 W cm−2) and electrolysis modes (current density of 2.14 A cm−2 at 1.3 V), recorded at 700 °C. This work inspires innovative design concepts for robust heterogeneous electrocatalysts.
质子陶瓷电池(PCC)因其清洁和高能量转换效率而具有巨大的应用潜力。然而,设计具有高稳定性的活性空气电极是一项挑战。在此,我们报告了一种通过可逆相变诱导的溶出过程获得的纳米磷灰石改性包晶氧化物 Nd0.5Ba0.5Mn0.7Co0.15Ni0.15O3-δ-(CoxNiy)3O4(CNO@NBMCN),作为 PCC 的高活性和持久性空气电极。相场模拟揭示了纳米颗粒在高温氧化环境中与基底紧密结合的内在机制。CNO@NBMCN 电极具有显著的低面积比电阻(600 °C 时为 0.38 Ω cm2)和超高的稳定性(降解率为 0.01 % h-1)。软 X 射线吸收光谱证实,异质结构的构建导致 Mn-O 八面体发生更多畸变,金属-氧键更弱,从而促进了氧空位的形成。此外,三相边界的快速离子表面交换和电荷转移也支持了极高的耐用性。使用 CNO@NBMCN 空气电极的单个电池在 700 °C 下记录的燃料电池(峰值功率密度为 1.28 W cm-2)和电解模式(1.3 V 时的电流密度为 2.14 A cm-2)中均表现出色。这项工作启发了稳健型异质电催化剂的创新设计理念。
期刊介绍:
The Chemical Engineering Journal is an international research journal that invites contributions of original and novel fundamental research. It aims to provide an international platform for presenting original fundamental research, interpretative reviews, and discussions on new developments in chemical engineering. The journal welcomes papers that describe novel theory and its practical application, as well as those that demonstrate the transfer of techniques from other disciplines. It also welcomes reports on carefully conducted experimental work that is soundly interpreted. The main focus of the journal is on original and rigorous research results that have broad significance. The Catalysis section within the Chemical Engineering Journal focuses specifically on Experimental and Theoretical studies in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. These studies have industrial impact on various sectors such as chemicals, energy, materials, foods, healthcare, and environmental protection.