{"title":"B 位变化对用于锌-空气电池的 LaFexCo1-xO3 双功能性能的影响","authors":"","doi":"10.1016/j.electacta.2024.144711","DOIUrl":null,"url":null,"abstract":"<div><p>Perovskites offer great promise as bifunctional catalyst in Zn-air batteries or reversible fuel cells. While there are optimization efforts for either oxygen reduction reaction (ORR) or oxygen evolution reaction (OER), there is a lack of information on the interplay between bifunctional performance and structural and electronic properties.</p><p>We investigated the influence of metal variation at the B-site in LaFe<sub>x</sub>Co<sub>1-x</sub>O<sub>3</sub> (<em>x</em> = 0, 0.2, 0.4, 0.6, 0.8 and 1) on it's structural, magnetic and bifunctional electrocatalytic properties for sol-gel based materials. Characterization was carried out by X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FT-IR), <sup>57</sup>Fe Mössbauer spectroscopy and superconducting quantum interference device (SQUID) magnetometry. Rotating ring disc electrode (RRDE) experiments and Zn-air battery measurements in single cells were made to explore the bifunctional catalytic characteristics. On the basis of the data, we were able to identify structural changes that could be linked with variations of the electronic properties. An average e<sub>g</sub> orbital filling was determined and correlated to the ORR and OER performance data. The optimum e<sub>g</sub> filling was reached at the transition point between orthorhombic and rhombohedral structure. Moreover, in the orthorhombic structure cobalt remained always in the low spin state, whereas its spin state changed much easier with B-site occupancy for the rhombohedral environment. LaFe<sub>0.4</sub>Co<sub>0.6</sub>O<sub>3</sub> was found to have the best bifunctional activity with a potential gap of 0.93 V, reaching a peak power density of 55 mW cm<sup>−2</sup> in a Zn-air battery single cell.</p><p>While these findings indicated that the electronic state might be more easily tuned in the rhombohedral structure types, for future application the synthesis route should be changed to enable significantly larger electrochemical active surface areas.</p></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":null,"pages":null},"PeriodicalIF":5.5000,"publicationDate":"2024-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0013468624009514/pdfft?md5=f2791dca8a45bb1c4b2a4c2fc096ee8e&pid=1-s2.0-S0013468624009514-main.pdf","citationCount":"0","resultStr":"{\"title\":\"Influence of B-site variation on the bifunctional performance of LaFexCo1-xO3 for Zn-air battery\",\"authors\":\"\",\"doi\":\"10.1016/j.electacta.2024.144711\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Perovskites offer great promise as bifunctional catalyst in Zn-air batteries or reversible fuel cells. While there are optimization efforts for either oxygen reduction reaction (ORR) or oxygen evolution reaction (OER), there is a lack of information on the interplay between bifunctional performance and structural and electronic properties.</p><p>We investigated the influence of metal variation at the B-site in LaFe<sub>x</sub>Co<sub>1-x</sub>O<sub>3</sub> (<em>x</em> = 0, 0.2, 0.4, 0.6, 0.8 and 1) on it's structural, magnetic and bifunctional electrocatalytic properties for sol-gel based materials. Characterization was carried out by X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FT-IR), <sup>57</sup>Fe Mössbauer spectroscopy and superconducting quantum interference device (SQUID) magnetometry. Rotating ring disc electrode (RRDE) experiments and Zn-air battery measurements in single cells were made to explore the bifunctional catalytic characteristics. On the basis of the data, we were able to identify structural changes that could be linked with variations of the electronic properties. An average e<sub>g</sub> orbital filling was determined and correlated to the ORR and OER performance data. The optimum e<sub>g</sub> filling was reached at the transition point between orthorhombic and rhombohedral structure. Moreover, in the orthorhombic structure cobalt remained always in the low spin state, whereas its spin state changed much easier with B-site occupancy for the rhombohedral environment. LaFe<sub>0.4</sub>Co<sub>0.6</sub>O<sub>3</sub> was found to have the best bifunctional activity with a potential gap of 0.93 V, reaching a peak power density of 55 mW cm<sup>−2</sup> in a Zn-air battery single cell.</p><p>While these findings indicated that the electronic state might be more easily tuned in the rhombohedral structure types, for future application the synthesis route should be changed to enable significantly larger electrochemical active surface areas.</p></div>\",\"PeriodicalId\":305,\"journal\":{\"name\":\"Electrochimica Acta\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.5000,\"publicationDate\":\"2024-07-14\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.sciencedirect.com/science/article/pii/S0013468624009514/pdfft?md5=f2791dca8a45bb1c4b2a4c2fc096ee8e&pid=1-s2.0-S0013468624009514-main.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Electrochimica Acta\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0013468624009514\",\"RegionNum\":3,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"ELECTROCHEMISTRY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Electrochimica Acta","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0013468624009514","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"ELECTROCHEMISTRY","Score":null,"Total":0}
引用次数: 0
摘要
作为锌-空气电池或可逆燃料电池中的双功能催化剂,透镜石前景广阔。我们研究了基于溶胶凝胶材料的 LaFexCo1-xO3(x = 0、0.2、0.4、0.6、0.8 和 1)中 B 位金属变化对其结构、磁性和双功能电催化性能的影响。表征方法包括 X 射线衍射(XRD)、傅立叶变换红外光谱(FT-IR)、57Fe 莫斯鲍尔光谱和超导量子干涉装置(SQUID)磁力测定法。为了探索双功能催化特性,我们还进行了旋转环盘电极(RRDE)实验和单电池锌-空气电池测量。根据这些数据,我们能够确定与电子特性变化相关的结构变化。我们确定了平均 eg 轨道填充度,并将其与 ORR 和 OER 性能数据相关联。在正方体结构和斜方体结构之间的过渡点达到了最佳eg填充。此外,在正方体结构中,钴始终处于低自旋状态,而在斜方体环境中,钴的自旋状态则更容易随着 B 位占有率的变化而变化。研究发现,LaFe0.4Co0.6O3 具有最佳的双功能活性,其电位差为 0.93 V,在锌-空气电池单电池中的峰值功率密度为 55 mW cm-2。
Influence of B-site variation on the bifunctional performance of LaFexCo1-xO3 for Zn-air battery
Perovskites offer great promise as bifunctional catalyst in Zn-air batteries or reversible fuel cells. While there are optimization efforts for either oxygen reduction reaction (ORR) or oxygen evolution reaction (OER), there is a lack of information on the interplay between bifunctional performance and structural and electronic properties.
We investigated the influence of metal variation at the B-site in LaFexCo1-xO3 (x = 0, 0.2, 0.4, 0.6, 0.8 and 1) on it's structural, magnetic and bifunctional electrocatalytic properties for sol-gel based materials. Characterization was carried out by X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FT-IR), 57Fe Mössbauer spectroscopy and superconducting quantum interference device (SQUID) magnetometry. Rotating ring disc electrode (RRDE) experiments and Zn-air battery measurements in single cells were made to explore the bifunctional catalytic characteristics. On the basis of the data, we were able to identify structural changes that could be linked with variations of the electronic properties. An average eg orbital filling was determined and correlated to the ORR and OER performance data. The optimum eg filling was reached at the transition point between orthorhombic and rhombohedral structure. Moreover, in the orthorhombic structure cobalt remained always in the low spin state, whereas its spin state changed much easier with B-site occupancy for the rhombohedral environment. LaFe0.4Co0.6O3 was found to have the best bifunctional activity with a potential gap of 0.93 V, reaching a peak power density of 55 mW cm−2 in a Zn-air battery single cell.
While these findings indicated that the electronic state might be more easily tuned in the rhombohedral structure types, for future application the synthesis route should be changed to enable significantly larger electrochemical active surface areas.
期刊介绍:
Electrochimica Acta is an international journal. It is intended for the publication of both original work and reviews in the field of electrochemistry. Electrochemistry should be interpreted to mean any of the research fields covered by the Divisions of the International Society of Electrochemistry listed below, as well as emerging scientific domains covered by ISE New Topics Committee.