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钙钛矿结构出溶材料的研究进展

盛彬 梅杰 孟则达 甘甜

盛彬, 梅杰, 孟则达, 等. 钙钛矿结构出溶材料的研究进展[J]. 复合材料学报, 2024, 41(1): 50-59. doi: 10.13801/j.cnki.fhclxb.20230731.004
引用本文: 盛彬, 梅杰, 孟则达, 等. 钙钛矿结构出溶材料的研究进展[J]. 复合材料学报, 2024, 41(1): 50-59. doi: 10.13801/j.cnki.fhclxb.20230731.004
SHENG Bin, MEI Jie, MENG Zeda, et al. Research progress for perovskite-structure exsolution materials[J]. Acta Materiae Compositae Sinica, 2024, 41(1): 50-59. doi: 10.13801/j.cnki.fhclxb.20230731.004
Citation: SHENG Bin, MEI Jie, MENG Zeda, et al. Research progress for perovskite-structure exsolution materials[J]. Acta Materiae Compositae Sinica, 2024, 41(1): 50-59. doi: 10.13801/j.cnki.fhclxb.20230731.004

钙钛矿结构出溶材料的研究进展

doi: 10.13801/j.cnki.fhclxb.20230731.004
基金项目: 苏州科技大学科研启动经费(332114509)
详细信息
    通讯作者:

    甘甜,博士,讲师,研究方向为固体氧化物燃料电池、能量转换与储存 E-mail: gantiantg@usts.edu.cn

  • 中图分类号: TM911.4;TB333

Research progress for perovskite-structure exsolution materials

Funds: Start-up Fund of Suzhou University of Science and Technology (332114509)
  • 摘要: 纳米结构催化材料被认为是各种能量转换和存储系统的有利设计理念。负载在氧化物载体上的纳米金属催化剂已被应用于燃料电池、气体传感器和化学重整装置等众多领域。然而,纳米金属催化剂经常存在耐久性问题。尽管表面修饰的纳米金属催化剂可以提供足够的催化活性,但其在恶劣的操作环境中的耐久性问题仍然存在。最近,原位出溶产生的纳米催化剂已被证明可以克服传统纳米金属催化剂的应用局限。出溶被定义为钙钛矿氧化物中具有催化活性的掺杂剂作为高度分散的纳米金属催化剂在其表面上出溶的过程。特别地,嵌入钙钛矿氧化物的出溶纳米催化剂比传统的纳米金属催化剂表现出更高的纳米颗粒密度和更强的抗烧结能力。本文概述了用于能源应用中出溶材料的最新进展,包括基本机制、主体氧化物的设计策略和实际应用。还讨论了这些材料的未来前景和进一步优化的途径。

     

  • 图  1  促进钙钛矿氧化物B位阳离子出溶的各种效应及其多功能应用示意图[1]

    Figure  1.  Schematic of various effects in facilitating the exsolution of B-site cations for perovskite oxides and its multifunctional applications[1]

    SOFC—Solid oxide fuel cells; SOEC—Solid oxide electrolysis cells; CB—Conduction band; VB—Valence band; hv—Photon energy; HER—Hydrogen evolution reaction; OER—Oxygen evolution reaction; PO2—Oxygen partial pressure

    图  2  (a) 在还原-煅烧条件下,A位缺陷钙钛矿氧化物的B位出溶过程示意图[14];(b) 非化学计量在出溶中的作用[20]

    Figure  2.  (a) Schematic of the B-site ex-solution process from A-site-deficient perovskite oxides under a reducing-annealing condition[14]; (b) Role of nonstoichiometry in exsolution[20]

    图  3  在出溶过程中同时形成B位金属相和Ruddlesden-Popper相的示意图[31]

    Figure  3.  Illustration of the simultaneous formation of B-site metal phase and a Ruddlesden-Popper phase during the exsolution process[31]

    图  4  压缩应变和拉伸应变薄膜中还原过程的示意图[33]

    Figure  4.  Schematic representation of the reduction process in compressive- and tensile-strained thin films[33]

    c/a—Tetragonality

    图  5  (a) 在纯H2 (左)和20% H2 (右)中还原5、10、15、20和30 h颗粒的SEM图像;(b) 不同氧分压(PO2)下平均粒径和还原时间之间的关系[34]

    Figure  5.  (a) SEM images of the particles reduced in pure H2 (left) and 20% H2 (right) for 5, 10, 15, 20, and 30 h; (b) Relationship between average particle size and reduction time under different oxygen partial pressure (PO2) conditions[34]

    图  6  Srx(Ti, Fe, Ni)O3−δ在氧化还原循环期间气-固界面和深度方向的示意图[37]

    Figure  6.  Schematic depiction of the suggested Srx(Ti, Fe, Ni)O3−δ surface reorganization during the atmospheric redox cycle at the solid-gas interface and in depth[37]

    图  7  电化学转换和触发效应:(a) 电化学转换方法的示意图;(b) TGA曲线和施加电势下的电池电流;(c) 气体还原和电化学转换的特性[39]

    Figure  7.  Electrochemical switching and triggering effects: (a) Schematic illustration of the electrochemical swit ching method; (b) TGA curve and cell current under an applied potential; (c) Properties of gas reduction and electrochemical switching[39]

    表  1  还原气氛处理的出溶钙钛矿在电催化领域的应用

    Table  1.   Summary on the exsolution on perovskites under reducing gas for electrocatalysis

    CatalystsAtmosphereExsolved metalApplicationRef.
    La0.43Sr0.37Cu0.12Ti0.88O3–δPure H2 at 400-700℃CuSOFC[41]
    La0.65Sr0.3Cr0.85Ni0.15O3−δ5% H2-Ar at 1200℃NiSOFC[45]
    Sm0.80-xSr0.20Fe0.80Ti0.15Ru0·05O3−δ5% H2/Ar at 900℃RuSOFC[46]
    La0.4Sr0.6Co0.2Fe0.7Mo0.1O3–δ5% H2/Ar at 700℃Co-FeSOEC[47]
    Pr0.8Sr1.2(Fe, Ni)0.8Nb0.2O4–δ20% H2/Ar at 850℃Ni-FeSOEC[48]
    La0.43Ca0.37Ni0.06Ti0.94O3–δ10% H2/N2 at 900℃NiSOEC[49]
    Sr2Fe1.3Ni0.2Mo0.5O6–δH2 (3% H2O) at 800℃Ni-FeSOFC/SOEC[50]
    La0.9Mn0.6Ni0.4O3−δ5% H2/Ar at 650℃NiLi-O2 batteries[51]
    LaMn0.75Co0.25O3−δ5% H2/Ar at 830℃CoZi-air batteries[52]
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  • 收稿日期:  2023-05-15
  • 修回日期:  2023-06-28
  • 录用日期:  2023-07-07
  • 网络出版日期:  2023-08-01
  • 刊出日期:  2024-01-01

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