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La0.6Sr0.4CoO3–δ(LSC)材料是现在固体氧化物燃料电池(SOFC)空气极材料的主流研究方向之一，有着极佳的电化学性能，而其最大的短处就是热膨胀系数过大。负热膨胀材料因为特定温度区间内会呈现出热收缩的特性而被命名，复合后在理论上可以显著降低材料的热膨胀系数，更容易使SOFC空气极材料与电解质材料实现热匹配。本工作以LSC材料为基体，选择负热膨胀特性较为突出的Sm0.85Zn0.15Mn O3(SZM)材料作为复合相，研究了复合料的电化学性能。通过固–液复合法合成了负热膨胀(NTE)氧化物SZM，将之与La0.6Sr0.4CoO3–δ(LSC)机械混合形成LSC–x SZM(x=0～40%)系列复合空气极材料。XRD结果显示SZM与LSC二者化学相容性良好。热膨胀测试表明，SZM有着优秀的热补偿能力，x=30%时，复合材料在室温至800℃的平均热膨胀系数为13×10–6 K–1，与阻隔层材料相近。LSC–30%SZM复合材料在800～550℃的面比电阻由LSC的0.012～1.240Ω·cm2降至0.008～0.620Ω·cm2，展现良好的界面接触。纽扣电池在750℃的功率密度为1 702 mW·cm–2，而同温的纯相LSC为1 209 mW·cm–2，实现41%的提升；同步的极化电阻Rp由0.65Ω·cm2降至0.50Ω·cm2。热循环和恒流放电的电压降幅均在1%以下，测试后的电池截面SEM照片均未发生分层现象。由于复合材料良好的热匹配，界面接触更好，最终实现电池的功率密度和稳定性的同时提升。
Abstract：Introduction Solid oxide fuel cell (SOFC) is one of the strong competitors of energy technology.SOFC has the characteristics of wide fuel selection,less pollution emission,high safety,and low noise as an excellent energy conversion and utilization device.However,the existing commercial SOFC still has some problems like high working temperature and large attenuation rate due to the limitation of material performance,restricting the application.Among the components of SOFC,the performance of air pole material is a key factor affecting SOFC.LSC material is one of the main research directions of solid oxide fuel cells (SOFC) air polar materials with the superior electrochemical properties,but its major disadvantage is a great thermal expansion coefficient (TEC).The negative thermal expansion (NTE) material provides an effective way to reduce the TEC of the SOFC air pole material.NTE material is named because of the characteristics of thermal contraction in the specific temperature interval.Theoretically,it can reduce the TEC of composite material and facilitate the thermal match between SOFC air electrode material and electrolyte material.Some NTE materials are a perovskite structure with a higher conductivity than Gd0.2Ce0.8O2–δ (GDC) of fluorite structure.These advantages make the theoretical cell power density of NTE composite air electrode material above the GDC composite cathode In this paper,La0.6Sr0.4CoO3–δ (LSC) material was used as a matrix,Sm0.85Zn0.15MnO3 (SZM) material with the superior negative thermal expansion characteristics was selected as a composite phase,and a series of LS–x SZM (x=0–40%) materials were designed to achieve the thermal matching of composite materials.Methods LSC and SZM powders were synthesized by a solid–liquid composite method.First,the corresponding quality of acetate raw materials was accurately weighed according to the stoichiometric ratio,and then the appropriate citric acid (CA) was weighed as a complexing agent according to the total metal particle weight and citric acid (CA) amount of 5:1.All the raw materials were mixed with an appropriate amount of deionized water and ground in a ball mill at a speed of 300 r/min for more than 12 h.The turbid liquid in the ball mill was taken out and placed in a beaker,and the precursor powder was obtained after drying in the oven at 250℃for 6 h,and then the LSC powder was obtained via calcination in a muffle furnace at 950℃ for 2 h,and the SZM powder was obtained via calcination at 1 300℃ for 2 h.The two powders were mixed with ethanol and ground in the ball mill for 6 h.The cathode slurry was prepared by mixing powders,and then full cells and symmetrical cells were made by screen printing for subsequent tests.Results and discussion The X-ray diffraction patterns show that the SZM is chemically compatible with LSC.The thermal expansion test indicates that SZM has an excellent thermal offset ability,and the average thermal expansion coefficient of the composite material from room temperature to 800℃ at x of 30%is 13×10–6 K–1,which is similar to that of the barrier material.The area specific resistance of the LSC–30%SZM composite material at 800–500℃decreases from 0.012–1.240Ω·cm2 in the case of LSC to 0.008–0.620Ω·cm2,indicating a good interfacial contact.The power density of the button cell at 750℃is 1 702 m W·cm–2,while the pure phase LSC at the same temperature is 1 209 m W·cm–2,which is increased by 41%.The polarization resistance Rp reduces from 0.65Ω·cm2 to 0.50Ω·cm2.The voltage drop of thermal cycling and constant current discharge is below 1%.In the 200 h constant current discharge test at 300 m A·cm–2,the voltage of the battery remains stable after the initial increase,and the whole process only reduces to 10 mV,which is decreased by 1.2%,showing a good long-term stability.No delamination occurs in the SEM images of the battery cross-section after the test.The comprehensive analysis of a better interfacial contact due to a good thermal matching of the composites ultimately achieves a simultaneous increase in the power density and stability of the cell.Conclusions A perovskite structural oxide material of Sm0.85Zn0.15MnO3 (SZM) with negative thermal expansion characteristics was synthesized by a solid–liquid recombination method.The XRD analysis indicated that SZM was chemical compatible with LSC.The pure phase SZM had special thermal shrinkage characteristics,while the thermal expansion characteristics of the composite materials decreased.The TEC of the pure phase LSC was 20×10–6 K–1,while the TEC of the 30%SZM composite LSC was only 13×10–6 K–1.The ASR of the composite material at 750℃decreased from 0.02Ω·cm2 to 0.013Ω·cm2,while that at 550℃decreased from 1.2Ω·cm2 to 0.6Ω·cm2,having an excellent performance.The battery of LSC–30% SZM material was improved at 750℃ from 1 209 m W·cm–2 of pure phase LSC to 1 702 m W·cm–2 of LSC–30%SZM,which was increased by 41%.In the thermal cycle test,the variation of battery OCV was within 1%,and the voltage decay rate of long-term constant current discharge at 200 h was 1.2%.The microscopic section analysis indicated that there was little interface stratification phenomenon.LSC–30%SZM composite material had good long-term thermal stability and structural stability.
[1] YUN S N, ZHANG Y W, XU Q, et al. Recent advance in new-generation integrated devices for energy harvesting and storage[J].Nano Energy, 2019, 60:600–619.
[2] STAMBOULI A B, TRAVERSA E. Solid oxide fuel cells(SOFCs):A review of an environmentally clean and efficient source of energy[J].Renew Sustain Energy Rev, 2002, 6(5):433–455.
[3]汝艳雷,王建新,李卓斌,等.基于对称双阴极结构固体氧化物燃料电池乙醇燃料内直接重整的电化学性能[J].硅酸盐学报, 2020,48(3):442–446.RU Yanlei, WANG Jianxin, LI Zhuobin, et al. J Chin Ceram Soc, 2020,48(3):442–446.
[4] RU Y L, SANG J K, XIA C R, et al. Durability of direct internal reforming of methanol as fuel for solid oxide fuel cell with double-sided cathodes[J]. Int J Hydrog Energy, 2020, 45(11):7069–7076.
[5] NDUBUISI A, ABOUALI S, SINGH K, et al. Recent advances,practical challenges, and perspectives of intermediate temperature solid oxide fuel cell cathodes[J]. J Mater Chem A, 2022, 10(5):2196–2227.
[6]邹志文,刘武,蒋龙,等.中空对称双阴极结构电池的高温抗氧化还原特性[J].硅酸盐学报, 2019, 47(3):308–312.ZOU Zhiwen, LIU Wu, JIANG Long, et al. J Chin Ceram Soc, 2019,47(3):308–312.
[7]杜志广，张华，蒋龙，等.基于对称双阴极结构固体氧化物燃料电池的快速热稳定性[J].硅酸盐学报, 2020, 48:423–427.DU Zhiguang, ZHANG Hua, JIANG Long, et al. J Chin Ceram Soc,2020, 48:423–427.
[8] MINH N. Solid oxide fuel cell technology? features and applications[J].Solid State Ion, 2004, 174(1/4):271–277.
[9] TAHIR N N M, BAHARUDDIN N A, SAMAT A A, et al. A review on cathode materials for conventional and proton-conducting solid oxide fuel cells[J]. J Alloys Compd, 2022, 894:162458.
[10] FAN L D, ZHU B, SU P C, et al. Nanomaterials and technologies for low temperature solid oxide fuel cells:Recent advances, challenges and opportunities[J]. Nano Energy, 2017, 45(Part 1):148–176.
[11] XIE M Y, CAI C K, LIU X J, et al. Improved durability of high-performance intermediate-temperature solid oxide fuel cells with a Ba-doped La0.6Sr0.4Co0.2Fe0.8O3–δ cathode[J]. ACS Appl Mater Interfaces, 2022:33052–33064.
[12] YANG J, CHEN L, CAI D M, et al. Study on the strontium segregation behavior of lanthanum strontium cobalt ferrite electrode under compression[J]. Int J Hydrog Energy, 2021, 46(15):9730–9740.
[13] DEVELOS-BAGARINAO K, ISHIYAMA T, KISHIMOTO H, et al.Nanoengineering of cathode layers for solid oxide fuel cells to achieve superior power densities[J]. Nat Commun, 2021, 12(1):3979.
[14] SOLOVYEV A A, KUTERBEKOV K A, NURKENOV S A, et al.Anode-supported solid oxide fuel cells with multilayer LSC/CGO/LSC cathode[J]. Fuel Cells, 2021, 21(4):408–412.
[15] ZENG R, HUANG Y H. Enhancing surface activity of La0.6Sr0.4CoO3–δcathode by a simple infiltration process[J]. Int J Hydrog Energy, 2017,42(10):7220–7225.
[16] MATSUI T, KOMOTO M, MUROYAMA H, et al. Degradation factors in(La, Sr)(Co, Fe)O3–δ cathode/Sm2O3–CeO2 interlayer/Y2O3–ZrO2electrolyte system during operation of solid oxide fuel cells[J]. J Power Sources, 2016, 312:80–85.
[17]常晓辉,段香梅,王琴,等.钐钕共掺杂氧化铈纳米粉体的制备及烧结行为[J].硅酸盐学报, 2018, 46(6):873–879.CHANG Xiaohui, DUAN Xiangmei, WANG Qin, et al. J Chin Ceram Soc, 2018, 46(6):873–879.
[18] ZHANG Y, CHEN B, GUAN D Q, et al. Thermal-expansion offset for high-performance fuel cell cathodes[J]. Nature, 2021, 591(7849):246–251.
[19] ATTFIELD J P. Mechanisms and materials for NTE[J]. Front Chem,2018, 6:371.
[20] LI Q, LIN K, LIU Z N, et al. Chemical diversity for tailoring negative thermal expansion[J]. Chem Rev, 2022, 122(9):8438–8486.
[21] LU F, YANG M J, SHI Y J, et al. Application of a negative thermal expansion oxide in SOFC cathode[J]. Ceram Int, 2021, 47(1):1095–1100.
[22] WANG H R, LEI Z, JIANG W W, et al. A novel composite oxygen electrode:PrBaCo2O5+δ combined with negative thermal expansion oxide applied to reversible solid oxide cells[J]. Int J Hydrog Energy,2022, 47(90):38327–38333.
[23] LIU K, LU F, JIA X S, et al. A high performance thermal expansion offset composite cathode for IT-SOFCs[J]. J Mater Chem A, 2022,10(45):24410–24421.
[24] WANG H, LEI Z, JING J, et al. Evaluation of NdBaCo2O5+δ oxygen electrode combined with negative expansion material for reversible solid oxide cells[J]. J Eur Ceram Soc, 2022, 42(10):4259–4265.
[25] TANG X B, JIAO Y J, YANG M J, et al. Anomalous thermal expansion properties in perovskite Sm0.85Zn0.15MnO3[J]. Solid State Ion, 2020, 344:115139.
[26] HUANG P N, HORKY A, PETRIC A. Interfacial reaction between nickel oxide and lanthanum gallate during sintering and its effect on conductivity[J]. J Am Ceram Soc, 1999, 82(9):2402–2406.
[27] YANG J, ZOU Z W, ZHANG H, et al. Study on the long-term discharge and redox stability of symmetric flat-tube solid oxide fuel cells[J]. Int J Hydrog Energy, 2021, 46(15):9741–9748.
[28]殷超凡,刘峥嵘,孙跃跃,等.质子导体型可逆固体氧化物电池材料的研究进展[J].硅酸盐学报, 2023, 51(10):2700–2711YIN Chaofan, LIU Zhenrong, SUN Yueyue, et al. J Chin Ceram Soc,2023, 51(10):2700–2711
[29]司运祥,潘尚可,任海深,等.用于中温固体氧化物燃料电池的Al2O3/微晶玻璃复合密封材料的制备与性能[J].硅酸盐学报, 2023,51(10):2653–2661.SI Yunxiang, PAN Shangke, REN Haishen, et al. J Chin Ceram Soc,2023, 51(10):2653–2661.
基本信息:
DOI：10.14062/j.issn.0454-5648.20240261
中图分类号:TB332;TM911.4
引用信息:
[1]司宇,高铭泽,李世清等.用负热膨胀氧化物Sm_(0.85)Zn_(0.15)MnO_3复合La_(0.6)Sr_(0.4)CoO_(3–δ)材料制备中温固体氧化物燃料电池空气极[J].硅酸盐学报,2024,52(12):3772-3780.DOI:10.14062/j.issn.0454-5648.20240261.
基金信息:
国家自然科学基金(22209191,11932005,U20A20251)