Preparation of CeO2@La0.6Sr0.4Co0.2Fe0.8O3-δ electrolyte and its property in semiconductor ionic fuel cells performance

doi:10.11949/0438-1157.20240845

CIESC Journal ›› 2025, Vol. 76 ›› Issue (3): 1353-1362.DOI: 10.11949/0438-1157.20240845

• Material science and engineering, nanotechnology • Previous Articles Next Articles

Preparation of CeO₂@La_0.6Sr_0.4Co_0.2Fe_0.8O_3-_δ electrolyte and its property in semiconductor ionic fuel cells performance

Yanbei LIU¹(), Ruoming WANG¹, Juan LIU¹, Taimoor Raza¹, Yuzheng LU², Rizwan Raza³, Bin ZHU⁴, Songbo LI⁵, Shengli AN⁶, Sining YUN¹()

^1.School of Materials Science and Engineering, Xi’an University of Architecture and Technology, Xi’an 710055, Shaanxi, China
^2.School of Electronic Engineering, Nanjing Xiaozhuang University, Nanjing 211171, Jiangsu, China
^3.Department of Physics, COMSATS University Islamabad, Lahore 54000, Pakistan
^4.School of Energy and Environment, Southeast University, Nanjing 210096, Jiangsu, China
^5.School of Chemistry and Chemical Engineering, Inner Mongolia University of Science and Technology, Baotou 014010, Inner Mongolia, China
^6.School of Materials Science and Engineering, Inner Mongolia University of Science and Technology, Baotou 014010, Inner Mongolia, China

Received:2024-07-25 Revised:2024-09-25 Online:2025-03-28 Published:2025-03-25
Contact: Sining YUN

CeO₂@La_0.6Sr_0.4Co_0.2Fe_0.8O_3-_δ 电解质的制备及半导体离子燃料电池性能研究

刘彦贝¹(), 王若名¹, 刘娟¹, Raza Taimoor¹, 陆玉正², Raza Rizwan³, 朱斌⁴, 李松波⁵, 安胜利⁶, 云斯宁¹()

^1.西安建筑科技大学材料科学与工程学院，陕西西安 710055
^2.南京晓庄学院电子工程学院，江苏南京 211171
^3.伊斯兰堡COMSATS大学物理系，巴基斯坦拉合尔 54000
^4.东南大学能源与环境学院，江苏南京 210096
^5.内蒙古科技大学化学与化工学院，内蒙古包头 014010
^6.内蒙古科技大学材料科学与工程学院，内蒙古包头 014010

通讯作者: 云斯宁
作者简介:刘彦贝(2000—)，女，硕士研究生，yanbei@xauat.edu.cn
基金资助:
国家自然科学基金项目(51672208);陕西省自然科学基金重点项目(2019JZ?20);陕西省重点研发计划国际合作重点项目(2019KWZ?03);陕西省重点科技创新团队(2022TD?34);国家自然科学基金面上项目(51772080)

Abstract

Abstract:

Developing electrolytes with high ionic conductivity is crucial to improve the electrochemical performance of semiconductor ion fuel cells (SIFC) at medium and low temperatures. In this study, a solvothermal method was employed to synthesize a core-shell structured CeO₂@La_0.6Sr_0.4Co_0.2Fe_0.8O_3-_δ (CeO₂@LSCF) composite electrolyte material. The phase information, microstructure, and valence state evolution of the material were analyzed. Moreover, its electrochemical performance and fuel cell properties were systematically investigated when used as an electrolyte in SIFCs. The charge transfer mechanism and the role of the built-in electric field at the core-shell heterojunction interface were also examined. The experimental results demonstrated that at 550℃, the CeO₂@LSCF electrolyte exhibited a maximum power density of 942.2 mW·cm^-2 at an open circuit voltage of 1.08 V. As a mixed ion and electron conductor in SIFC electrolyte materials, the core-shell structured CeO₂@LSCF holds great potential for future applications.

Key words: composites, fuel cells, electrolytes, core-shell structure, built-in field, heterojunction

摘要：

开发高离子电导率的电解质对于提升半导体离子燃料电池（SIFC）在中低温下的电化学性能至关重要。为此，采用溶剂热法制备核-壳结构CeO₂@La_0.6Sr_0.4Co_0.2Fe_0.8O_3-_δ （CeO₂@LSCF）复合电解质材料，通过对其物相信息、微观形貌及价态演变进行分析，进一步将其作为SIFC电解质测试其电化学性能和燃料电池性能，研究核-壳结构异质界面电荷传输及内建电场作用机理。结果表明：550℃时，CeO₂@LSCF作为燃料电池的电解质，在1.08 V开路电压下，获得942.2 mW·cm^-2的最大输出功率密度。作为混合离子和电子导体的SIFC电解质材料，核-壳结构CeO₂@LSCF具有潜在的应用前景。

关键词: 复合材料, 燃料电池, 电解质, 核-壳结构, 内建电场, 异质结

CLC Number:

O 611.62

Yanbei LIU, Ruoming WANG, Juan LIU, Taimoor Raza, Yuzheng LU, Rizwan Raza, Bin ZHU, Songbo LI, Shengli AN, Sining YUN. Preparation of CeO₂@La_0.6Sr_0.4Co_0.2Fe_0.8O_3-_δ electrolyte and its property in semiconductor ionic fuel cells performance[J]. CIESC Journal, 2025, 76(3): 1353-1362.

刘彦贝, 王若名, 刘娟, Raza Taimoor, 陆玉正, Raza Rizwan, 朱斌, 李松波, 安胜利, 云斯宁. CeO₂@La_0.6Sr_0.4Co_0.2Fe_0.8O_3-_δ 电解质的制备及半导体离子燃料电池性能研究[J]. 化工学报, 2025, 76(3): 1353-1362.

Figures/Tables 8

Fig.1 Schematic diagram of SIFC structure

Fig.2 The structure and microstructure of CeO2@LSCF

Fig.3 The XPS spectra of CeO2@LSCF and CeO2

Fig.4 CeO2@LSCF related test results

Table 1 CeO2@LSCF-SIFC open circuit voltage and maximum power density at different temperatures

Temperature/℃	Open-circuit voltage (OCV)/V	Maximum power density (P_max)/(mW·cm^-2)
450	1.204	312.5
475	1.190	428.1
500	1.109	603.1
525	1.108	745.3
550	1.080	942.2

Table 2 Ohmic resistance and total conductivity of CeO2@LSCF electrolyte at 450—550℃

Temperature/℃	R₀/Ω	R₁/Ω	σ_t/(S·cm^-1)
450	0.133	1.915	0.357
475	0.111	0.342	0.428
500	0.093	0.189	0.511
525	0.0793	0.062	0.599
550	0.0723	0.035	0.656

Fig. 5 UV-visible absorption spectra and UV photoelectron spectra of CeO2 and LSCF

Fig.6 Schematic illustration of the band structure of the composite electrolyte material CeO2@LSCF

References 43

1	Paydar S, Zhu B, Shi J, et al. Surfacial proton conducting CeO₂ nanosheets[J]. Ceramics International, 2023, 49(6): 9138-9146.
2	Zhu B, Fan L D, Deng H, et al. LiNiFe-based layered structure oxide and composite for advanced single layer fuel cells[J]. Journal of Power Sources, 2016, 316: 37-43.
3	Zhang W W, Wang H C, Guan K, et al. La_0.6Sr_0.4Co_0.2Fe_0.8O_3- _δ /CeO₂ heterostructured composite nanofibers as a highly active and robust cathode catalyst for solid oxide fuel cells[J]. ACS Applied Materials & Interfaces, 2019, 11(30): 26830-26841.
4	Mansilla Y, Arce M, Gonzalez Oliver C, et al. Synthesis and characterization of ZrO₂ and YSZ thin films[J]. Materials Today: Proceedings, 2019, 14: 92-95.
5	Han M F, Tang X L, Yin H Y, et al. Fabrication, microstructure and properties of a YSZ electrolyte for SOFCs[J]. Journal of Power Sources, 2007, 165(2): 757-763.
6	Chen Y, Wei W C J. Processing and characterization of ultra-thin yttria-stabilized zirconia (YSZ) electrolytic films for SOFC[J]. Solid State Ionics, 2006, 177(3): 351-357.
7	Butz B, Kruse P, Störmer H, et al. Correlation between microstructure and degradation in conductivity for cubic Y₂O₃-doped ZrO₂ [J]. Solid State Ionics, 2006, 177(37): 3275-3284.
8	Liu K, Ganesh K S, Nie J J, et al. Characterizing the blocking electron ability of the schottky junction in SnO₂-SDC semiconductor-ionic membrane fuel cells[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(28): 10357-10368.
9	Xia C, Mi Y Q, Wang B Y, et al. Shaping triple-conducting semiconductor BaCo_0.4Fe_0.4Zr_0.1Y_0.1O_3- _δ into an electrolyte for low-temperature solid oxide fuel cells[J]. Nature Communications, 2019, 10: 1707.
10	Liu Z, Liu M F, Yang L, et al. LSM-infiltrated LSCF cathodes for solid oxide fuel cells[J]. Journal of Energy Chemistry, 2013, 22(4): 555-559.
11	Wang L, Wang P P, Geng C L, et al. A novel core-shell LSCF perovskite structured electrocatalyst with local hetero-interface for solid oxide fuel cells[J]. International Journal of Hydrogen Energy, 2020, 45(20): 11824-11833.
12	Cai H D, Zheng D, Xia C, et al. Improving the electrochemical energy conversion of solid oxide fuel cells through the interface effect in La_0.6Sr_0.4Co_0.2Fe_0.8O_3- _δ -BaTiO_3- _δ electrolyte[J]. Journal of Colloid and Interface Science, 2023, 641: 70-81.
13	王天闻, 闫肃, 赵梦园,等. Co掺杂SrTi_0.3Fe_0.7O_3- _δ 阳极SOFC在化工副产气燃料下的性能及稳定性[J]. 化工学报, 2022, 73(9): 4079-4086.
	Wang T W, Yan S, Zhao M Y, et al. Performance and durability of cobalt doped SrTi_0.3Fe_0.7O_3- _δ anode SOFC fueled with by-product gas from chemical industry[J]. CIESC Journal, 2022, 73(9): 4079-4086.
14	肖扬, 徐春明, 杨晓霞, 等. NiMn₂O₄尖晶石氧化物阴极的制备及电化学性能研究[J]. 化工学报, 2020, 71(9): 4292-4302.
	Xiao Y, Xu C M, Yang X X, et al. Preparation and electrochemical properties of NiMn₂O₄ spinel oxide cathode[J]. CIESC Journal, 2020, 71(9): 4292-4302.
15	Tariq S, Marium A, Raza R, et al. Comparative study of Ce_0.80Sm_0.20 Ba_0.80Y_0.20O_3- _δ (YB-SDC) electrolyte by various chemical synthesis routes[J]. Results in Physics, 2018, 8: 780-784.
16	Lu Y Z, Mushtaq N, Shah M A K Y, et al. Proton transport controlled at surface layer of CeO₂ by gradient-doping with a built-in-field effect[J]. Journal of Rare Earths, 2023, 41(12): 2025-2032.
17	Namai Y, Fukui K I, Iwasawa Y. Atom-resolved noncontact atomic force microscopic and scanning tunneling microscopic observations of the structure and dynamic behavior of CeO₂(111) surfaces[J]. Catalysis Today, 2003, 85(2/3/4): 79-91.
18	Fu Y P, Wen S B, Lu C H. Preparation and characterization of samaria-doped ceria electrolyte materials for solid oxide fuel cells[J]. Journal of the American Ceramic Society, 2008, 91(1): 127-131.
19	Pikalova E Y, Maragou V I, Demina A N, et al. The effect of co-dopant addition on the properties of Ln_0.2Ce_0.8O_2- _δ (Ln=Gd, Sm, La) solid-state electrolyte[J]. Journal of Power Sources, 2008, 181(2): 199-206.
20	Feng B, Sugiyama I, Hojo H, et al. Atomic structures and oxygen dynamics of CeO₂ grain boundaries[J]. Scientific Reports, 2016, 6: 20288.
21	Montini T, Melchionna M, Monai M, et al. Fundamentals and catalytic applications of CeO₂-based materials[J]. Chemical Reviews, 2016, 116(10): 5987-6041.
22	Cai H D, Zhang L L, Xu J S, et al. Cobalt-free La_0.5Sr_0.5Fe_0.9Mo_0.1O_3- _δ electrode for symmetrical SOFC running on H₂ and CO fuels[J]. Electrochimica Acta, 2019, 320: 134642.
23	Xing Y M, Wu Y, Li L Y, et al. Proton shuttles in CeO₂/CeO_2- _δ core-shell structure[J]. ACS Energy Letters, 2019, 4(11): 2601-2607.
24	Zhu B, Lund P, Raza R, et al. A new energy conversion technology based on nano-redox and nano-device processes[J]. Nano Energy, 2013, 2(6): 1179-1185.
25	Campbell C T, Peden C H F. Oxygen vacancies and catalysis on ceria surfaces[J]. Science, 2005, 309(5735): 713-714.
26	Zhu B, Lund P D, Raza R, et al. Schottky junction effect on high performance fuel cells based on nanocomposite materials[J]. Advanced Energy Materials, 2015, 5(8): 1401895.
27	Jaiswal S K, Hong J, Yoon K J, et al. Optical absorption and XPS studies of (Ba_1- _x Sr _x )(Ce_0.75Zr_0.10Y_0.15)O_3- _δ electrolytes for protonic ceramic fuel cells[J]. Ceramics International, 2016, 42(8): 10366-10372.
28	He J J, Xu Y H, Shao P H, et al. Modulation of coordinative unsaturation degree and valence state for cerium-based adsorbent to boost phosphate adsorption[J]. Chemical Engineering Journal, 2020, 394: 124912.
29	Ali Abdelkareem M, Sayed E T, Mohamed H O, et al. Nonprecious anodic catalysts for low-molecular-hydrocarbon fuel cells: theoretical consideration and current progress[J]. Progress in Energy and Combustion Science, 2020, 77: 100805.
30	Sebastián D, Serov A, Matanovic I, et al. Insights on the extraordinary tolerance to alcohols of Fe-N-C cathode catalysts in highly performing direct alcohol fuel cells[J]. Nano Energy, 2017, 34: 195-204.
31	Shimada H, Yamaguchi T, Sumi H, et al. Improved transport property of proton-conducting solid oxide fuel cell with multi-layered electrolyte structure[J]. Journal of Power Sources, 2017, 364: 458-464.
32	Xian C N, Wang S F, Sun C W, et al. Effect of Ni doping on the catalytic properties of nanostructured peony-like CeO₂ [J]. Chinese Journal of Catalysis, 2013, 34(2): 305-312.
33	Yang D, Chen G, Liu H L, et al. Electrochemical performance of a Ni_0.8Co_0.15Al_0.05LiO₂ cathode for a low temperature solid oxide fuel cell[J]. International Journal of Hydrogen Energy, 2021, 46(17): 10438-10447.
34	Chen G, Luo Y D, Sun W K, et al. Electrochemical performance of a new structured low temperature SOFC with BZY electrolyte[J]. International Journal of Hydrogen Energy, 2018, 43(28): 12765-12772.
35	Vafaeenezhad S, Hanifi A R, Laguna-Bercero M A, et al. Microstructure and long-term stability of Ni-YSZ anode supported fuel cells: a review[J]. Materials Futures, 2022, 1(4): 042101.
36	Ni M, Shao Z P. Fuel cells that operate at 300℃ to 500℃[J]. Science, 2020, 369(6500): 138-139.
37	Dong W J, Tong Y Z, Zhu B, et al. Semiconductor TiO₂ thin film as an electrolyte for fuel cells[J]. Journal of Materials Chemistry A, 2019, 7(28): 16728-16734.
38	Shah M A K Y, Lu Y Z, Mushtaq N, et al. Showcasing the potential of iron-doped electrolytes to enhance the ionic conduction for a low-temperature ceramics fuel cell[J]. ACS Applied Energy Materials, 2023, 6(21): 10829-10841.
39	Cain T, Lai B K, Sankaranarayanan S, et al. Photo-excitation enhanced high temperature conductivity and crystallization kinetics in ultra-thin La_0.6Sr_0.4Co_0.8Fe_0.2O_3- _δ films[J]. Journal of Power Sources, 2010, 195(10): 3145-3148.
40	Li F F, Tang J, Ke Q P, et al. Investigation into enhanced catalytic performance for epoxidation of styrene over LaSrCo _x Fe_2- _x O₆ double perovskites: the role of singlet oxygen species promoted by the photothermal effect[J]. ACS Catalysis, 2021, 11(19): 11855-11866.
41	Tayyab Z, Rauf S, Bilal Hanif M, et al. Theoretical and experimental explored tailored hybrid H⁺/O^2–ions conduction: bridged for high performance fuel cell and water electrolysis[J]. Chemical Engineering Journal, 2024, 482: 148750.
42	Hu M S, Chen M R, Wang Y C, et al. A p-n heterostructure composite of NaCrO₂ and CeO₂ for intermediate temperature solid oxide fuel cells[J]. Journal of Alloys and Compounds, 2023, 962: 171169.
43	Huang Q A, Liu M F, Liu M L. Impedance spectroscopy study of an SDC-based SOFC with high open circuit voltage[J]. Electrochimica Acta, 2015, 177: 227-236.

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Preparation of CeO₂@La_0.6Sr_0.4Co_0.2Fe_0.8O_3-_δ electrolyte and its property in semiconductor ionic fuel cells performance

CeO₂@La_0.6Sr_0.4Co_0.2Fe_0.8O_3-_δ 电解质的制备及半导体离子燃料电池性能研究

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