烧结助剂对BaZr0.1Ce0.7Y0.2O3-δ电解质烧结行为及电导率的影响

doi:10.15541/jim20240328

无机材料学报 ›› 2025, Vol. 40 ›› Issue (1): 84-90.DOI: 10.15541/jim20240328 CSTR: 32189.14.10.15541/jim20240328

烧结助剂对BaZr_0.1Ce_0.7Y_0.2O_3-_δ电解质烧结行为及电导率的影响

张婧慧(), 陆晓彤, 毛海雁, 田亚州, 张山林()

中山大学化学工程与技术学院, 珠海 519082

收稿日期:2024-07-12 修回日期:2024-08-14 出版日期:2025-01-20 网络出版日期:2024-09-23
通讯作者: 张山林, 副教授. E-mail: zhangshlin@sysu.edu.cn
作者简介:张婧慧(1996-), 女, 博士研究生. E-mail: zhangjh67@mail2.sysu.edu.cn
基金资助:
国家重点研发计划(2021YFB4001402)

Effect of Sintering Additives on Sintering Behavior and Conductivity of BaZr_0.1Ce_0.7Y_0.2O_3-_δ Electrolytes

ZHANG Jinghui(), LU Xiaotong, MAO Haiyan, TIAN Yazhou, ZHANG Shanlin()

School of Chemical Engineering and Technology, Sun Yat-sen University, Zhuhai 519082, China

Received:2024-07-12 Revised:2024-08-14 Published:2025-01-20 Online:2024-09-23
Contact: ZHANG Shanlin, associate professor. E-mail: zhangshlin@sysu.edu.cn
About author:ZHANG Jinghui (1996-), female, PhD candidate. E-mail: zhangjh67@mail2.sysu.edu.cn
Supported by:
National Key Research and Development Program of China(2021YFB4001402)

摘要/Abstract

摘要：

BaZr_0.1Ce_0.7Y_0.2O_3-_δ(BZCY)作为质子导体型固体氧化物燃料电池的典型电解质材料之一, 具有高质子电导率及高稳定性等优点。然而, BZCY电解质的烧结活性较差, 通常需要较高的烧结温度来实现致密化, 而过高的烧结温度不利于电池的制备及应用。本研究旨在降低BZCY电解质的烧结温度, 通过引入NiO、Fe₂O₃、ZnO与CuO等烧结助剂, 探讨了烧结助剂对BZCY烧结行为的影响。结果表明, 除Fe₂O₃外, 其余氧化物均能有效促进BZCY烧结体的晶粒生长。其中, 添加CuO对BZCY烧结过程的促进作用最显著。在BZCY中添加质量分数2%的CuO(BZCY-2%CuO)后, 即使烧结温度降低至1250 ℃, 烧结体仍能保持高于98%的相对密度。此外, 在600 ℃的加湿H₂气氛下, BZCY-2%CuO的电导率高达2.7×10^-2 S·cm^-1, 且在加湿H₂下的电导率相较于加湿空气高出近5倍。更为关键的是, BZCY-2%CuO电解质在电池工作条件下的电子导电性可以忽略不计, 保持了优异的稳定性。

关键词: 质子导体型固体氧化物燃料电池, BaZr_0.1Ce_0.7Y_0.2O_3-_δ, 电解质, 烧结助剂, 烧结行为, 电导率

Abstract:

As one of the typical electrolyte materials for proton conducting solid oxide fuel cells, BaZr_0.1Ce_0.7Y_0.2O_3-_δ (BZCY) possesses advantages such as high proton conductivity and stability. However, sintering activity of BZCY electrolyte is poor, usually requiring high sintering temperature for densification, which is inconducive to the preparation and application in cells. This study aimed to reduce the sintering temperature of BZCY electrolyte and explore the influence of sintering additives such as NiO, Fe₂O₃, ZnO, and CuO on the sintering characteristics of BZCY in detail. The results indicate that the oxides except Fe₂O₃ can effectively promote the grain growth of BZCY sintered body. Among them, the addition of CuO has the most significant promoting effect on the sintering process of BZCY. After adding 2% (in mass) CuO into BZCY (BZCY-2%CuO), even if the sintering temperature was reduced to 1250 ℃, the relative density of the sintered body still maintained higher than 98%. Additionally, the conductivity of BZCY-2%CuO was up to 2.7×10^-2 S·cm^-1 at 600 ℃ in wet H₂ atmosphere, which was nearly 5 times higher than that in wet air. More importantly, BZCY-2%CuO electrolyte exhibits negligible electronic conductivity under cell operating conditions while maintaining excellent stability.

Key words: proton conducting solid oxide fuel cell, BaZr_0.1Ce_0.7Y_0.2O_3-_δ, electrolyte, sintering additive, sintering behavior, conductivity

中图分类号:

TQ174

张婧慧, 陆晓彤, 毛海雁, 田亚州, 张山林. 烧结助剂对BaZr_0.1Ce_0.7Y_0.2O_3-_δ电解质烧结行为及电导率的影响[J]. 无机材料学报, 2025, 40(1): 84-90.

ZHANG Jinghui, LU Xiaotong, MAO Haiyan, TIAN Yazhou, ZHANG Shanlin. Effect of Sintering Additives on Sintering Behavior and Conductivity of BaZr_0.1Ce_0.7Y_0.2O_3-_δ Electrolytes[J]. Journal of Inorganic Materials, 2025, 40(1): 84-90.

图/表 8

图1 添加不同烧结助剂的BZCY块体的XRD图谱

Fig. 1 XRD patterns of BZCY bulks with different sintering aids

图2 添加不同烧结助剂的BZCY样品的表面与断面形貌

Fig. 2 Surface and cross-section morphologies of BZCY samples with different sintering aids Surface: (a) BZCY-2%Fe2O3, (c) BZCY-2%ZnO, (e) BZCY-2%NiO, and (g) BZCY-2%CuO; Cross-section: (b) BZCY-2%Fe2O3, (d) BZCY-2%ZnO, (f) BZCY-2%NiO, and (h) BZCY-2%CuO

图3 添加不同烧结助剂的BZCY样品的相对密度

Fig. 3 Relative densities of BZCY samples with different sintering aids

图4 在1250 ℃烧结的BZCY-x%CuO(x=1, 2, 3)块体的表面及断面形貌

Fig. 4 Surface and cross-section morphologies of BZCY-x%CuO (x=1, 2, 3) bulks sintered at 1250 ℃ Surface: (a) BZCY, (c) BZCY-1%CuO, (e) BZCY-2%CuO, and (g) BZCY-3%CuO; Cross-section: (b) BZCY, (d) BZCY-1%CuO, (f) BZCY-2%CuO, and (h) BZCY-3%CuO

图5 在1250 ℃烧结的BZCY-x%CuO(x=1、2、3)块体的相对密度

Fig. 5 Relative densities of BZCY-x%CuO (x=1, 2, 3) bulks sintered at 1250 ℃

图6 BZCY-2%CuO样品的典型阻抗谱图

Fig. 6 Typical impedance spectra of BZCY-2%CuO (a) Full spectra; (b) Enlarged area in dotted frame of (a)

图7 BZCY-x%CuO样品在不同条件下的电导率

Fig. 7 Conductivities of BZCY-x%CuO samples under different conditions (a) Total conductivities of BZCY-x%CuO at 600 ℃; (b) Total conductivities at different temperatures in different atmospheres of BZCY-2%CuO; (c) Intracrystalline conductivities at low temperature of BZCY-2%CuO; (d) Grain boundary conductivities at low temperature of BZCY-2%CuO

图8 (a) 600 ℃下BZCY-2%CuO样品电导率的稳定性, (b) BZCY-2%CuO作为电解质的全电池的OCV

Fig. 8 (a) Stability of the conductivity of BZCY-2%CuO at 600 ℃ and (b) OCV of the full cell with BZCY-2%CuO as electrolyte

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烧结助剂对BaZr_0.1Ce_0.7Y_0.2O_3-_δ电解质烧结行为及电导率的影响

Effect of Sintering Additives on Sintering Behavior and Conductivity of BaZr_0.1Ce_0.7Y_0.2O_3-_δ Electrolytes

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