Jingrui Cao, Liyuan Liu, Bin Han, Zhiqiang Wang, Bin Li*, Muslum Demir and Pianpian Ma*,
{"title":"通过Ce取代和纳米纤维结构定制LaCoO3钙钛矿氧化物以增强电化学存储性能","authors":"Jingrui Cao, Liyuan Liu, Bin Han, Zhiqiang Wang, Bin Li*, Muslum Demir and Pianpian Ma*, ","doi":"10.1021/acsaem.5c01271","DOIUrl":null,"url":null,"abstract":"<p >Perovskite oxides offer great potential for supercapacitors thanks to their redox activity and structural tunability. However, their practical application is hindered by issues such as phase stability and low conductivity. Herein, La<sub>1–<i>x</i></sub>Ce<sub><i>x</i></sub>CoO<sub>3−δ</sub> (<i>x</i> = 0, 0.05, 0.1, 0.15, and 0.2) perovskite nanofibers were synthesized via the electrospinning–calcination method. As Ce substitution increased, the perovskite transitioned from a single hexagonal phase to a dual-phase (hexagonal and cubic) structure. Given that the as-constructed cubic phase and nanofiber morphology are more thermodynamically stable than the hexagonal phase in Co-based perovskites, Ce substitution was found to enhance the overall structural stability. Moreover, Ce substitution affected the oxygen vacancy concentration, with the highest concentration observed at <i>x</i> = 0.1, resulting in an optimal value of 267.9 F g<sup>–1</sup> at a current density of 1 A g<sup>–1</sup>. This was attributed to its relatively intact nanofiber structure providing abundant active sites and the lowest internal resistance. A supercapacitor device using La<sub>0.9</sub>Ce<sub>0.1</sub>CoO<sub>3</sub>@Ni-foam serving as the positive electrode and activated carbon (AC)@Ni-foam as the negative electrode achieved an energy density of 11.4 W h·kg<sup>–1</sup> at a power density of 775.1 W·kg<sup>–1</sup>. After 5000 charge–discharge cycles at 1 A g<sup>–1</sup>, the device retained 90.42% of its initial capacitance. These results demonstrate that Ce substitution significantly improves the electrochemical and cycling performance of LaCoO<sub>3</sub>, offering a viable strategy for designing stable and high-performance supercapacitor electrodes.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"8 17","pages":"12543–12552"},"PeriodicalIF":5.5000,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Tailoring LaCoO3 Perovskite Oxides via Ce Substitution and Nanofiber Architecture for Enhanced Electrochemical Storage Performance\",\"authors\":\"Jingrui Cao, Liyuan Liu, Bin Han, Zhiqiang Wang, Bin Li*, Muslum Demir and Pianpian Ma*, \",\"doi\":\"10.1021/acsaem.5c01271\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Perovskite oxides offer great potential for supercapacitors thanks to their redox activity and structural tunability. However, their practical application is hindered by issues such as phase stability and low conductivity. Herein, La<sub>1–<i>x</i></sub>Ce<sub><i>x</i></sub>CoO<sub>3−δ</sub> (<i>x</i> = 0, 0.05, 0.1, 0.15, and 0.2) perovskite nanofibers were synthesized via the electrospinning–calcination method. As Ce substitution increased, the perovskite transitioned from a single hexagonal phase to a dual-phase (hexagonal and cubic) structure. Given that the as-constructed cubic phase and nanofiber morphology are more thermodynamically stable than the hexagonal phase in Co-based perovskites, Ce substitution was found to enhance the overall structural stability. Moreover, Ce substitution affected the oxygen vacancy concentration, with the highest concentration observed at <i>x</i> = 0.1, resulting in an optimal value of 267.9 F g<sup>–1</sup> at a current density of 1 A g<sup>–1</sup>. This was attributed to its relatively intact nanofiber structure providing abundant active sites and the lowest internal resistance. A supercapacitor device using La<sub>0.9</sub>Ce<sub>0.1</sub>CoO<sub>3</sub>@Ni-foam serving as the positive electrode and activated carbon (AC)@Ni-foam as the negative electrode achieved an energy density of 11.4 W h·kg<sup>–1</sup> at a power density of 775.1 W·kg<sup>–1</sup>. After 5000 charge–discharge cycles at 1 A g<sup>–1</sup>, the device retained 90.42% of its initial capacitance. These results demonstrate that Ce substitution significantly improves the electrochemical and cycling performance of LaCoO<sub>3</sub>, offering a viable strategy for designing stable and high-performance supercapacitor electrodes.</p>\",\"PeriodicalId\":4,\"journal\":{\"name\":\"ACS Applied Energy Materials\",\"volume\":\"8 17\",\"pages\":\"12543–12552\"},\"PeriodicalIF\":5.5000,\"publicationDate\":\"2025-08-26\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Applied Energy Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acsaem.5c01271\",\"RegionNum\":3,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Applied Energy Materials","FirstCategoryId":"88","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsaem.5c01271","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
钙钛矿氧化物由于其氧化还原活性和结构可调性,为超级电容器提供了巨大的潜力。然而,它们的实际应用受到相稳定性和低电导率等问题的阻碍。采用电纺丝-煅烧法制备了La1-xCexCoO3−δ (x = 0、0.05、0.1、0.15和0.2)钙钛矿纳米纤维。随着Ce取代量的增加,钙钛矿从单一的六方相转变为双相(六方和立方)结构。考虑到钴基钙钛矿的立方相和纳米纤维形态比六方相更具有热力学稳定性,Ce取代增强了整体结构的稳定性。此外,Ce取代影响氧空位浓度,在x = 0.1时观察到的氧空位浓度最高,导致电流密度为1 a g-1时的最佳值为267.9 F g-1。这是由于其相对完整的纳米纤维结构提供了丰富的活性位点和最低的内阻。以La0.9Ce0.1CoO3@Ni-foam为正极,活性炭(AC)@泡沫镍为负极的超级电容器器件,在775.1 W·kg-1的功率密度下,实现了11.4 W h·kg-1的能量密度。在1 A g-1条件下充放电5000次后,器件保持了90.42%的初始电容。这些结果表明,Ce取代显著提高了LaCoO3的电化学和循环性能,为设计稳定、高性能的超级电容器电极提供了可行的策略。
Tailoring LaCoO3 Perovskite Oxides via Ce Substitution and Nanofiber Architecture for Enhanced Electrochemical Storage Performance
Perovskite oxides offer great potential for supercapacitors thanks to their redox activity and structural tunability. However, their practical application is hindered by issues such as phase stability and low conductivity. Herein, La1–xCexCoO3−δ (x = 0, 0.05, 0.1, 0.15, and 0.2) perovskite nanofibers were synthesized via the electrospinning–calcination method. As Ce substitution increased, the perovskite transitioned from a single hexagonal phase to a dual-phase (hexagonal and cubic) structure. Given that the as-constructed cubic phase and nanofiber morphology are more thermodynamically stable than the hexagonal phase in Co-based perovskites, Ce substitution was found to enhance the overall structural stability. Moreover, Ce substitution affected the oxygen vacancy concentration, with the highest concentration observed at x = 0.1, resulting in an optimal value of 267.9 F g–1 at a current density of 1 A g–1. This was attributed to its relatively intact nanofiber structure providing abundant active sites and the lowest internal resistance. A supercapacitor device using La0.9Ce0.1CoO3@Ni-foam serving as the positive electrode and activated carbon (AC)@Ni-foam as the negative electrode achieved an energy density of 11.4 W h·kg–1 at a power density of 775.1 W·kg–1. After 5000 charge–discharge cycles at 1 A g–1, the device retained 90.42% of its initial capacitance. These results demonstrate that Ce substitution significantly improves the electrochemical and cycling performance of LaCoO3, offering a viable strategy for designing stable and high-performance supercapacitor electrodes.
期刊介绍:
ACS Applied Energy Materials is an interdisciplinary journal publishing original research covering all aspects of materials, engineering, chemistry, physics and biology relevant to energy conversion and storage. The journal is devoted to reports of new and original experimental and theoretical research of an applied nature that integrate knowledge in the areas of materials, engineering, physics, bioscience, and chemistry into important energy applications.