纳米ScSZ基电解质中低温导电性研究进展

doi:10.19964/j.issn.1006-4990.2020-0369

摘要/Abstract

摘要：

固体氧化物燃料电池（SOFC）适用于多种燃料气体,高效清洁,是最有前景的燃料电池之一。氧化钪（Sc₂O₃）掺杂二氧化锆（ZrO₂）系列（ScSZ）使氧化锆基电解质表现出优异的离子导电性。ScSZ基电解质晶粒纳米化呈现出了很好的电学性能而得到广泛深入的研究。但是ScSZ基电解质在中低温下会发生相变,产生低导电性的菱形相而影响其离子电导率。系统总结了单元或二元氧化物掺杂ScSZ电解质在中低温下的物相、晶体结构及电导率。多元氧化物复合掺杂ScSZ可有效防止在中低温下发生相变、稳定立方相ScSZ。采用不同方法制备纳米ScSZ基电解质,可很好地提高电解质的电导率。提出了ScSZ系列在中低温范围内（600~800 ℃）的发展方向：优化掺杂成分和掺杂量提高晶粒晶界电导率,使用不同工艺制备纳米电解质或不同制备方法制备新型结构电解质材料。

关键词: 精炼镁渣, 破碎风选, 镁珠, ScSZ基电解质, 氧化钪, 二氧化锆, 电导率

Abstract:

Solid oxide fuel cell（SOFC） is one of the most promising fuel cells,which is efficient and clean and suitable for a variety of fuel gases.Sc₂O₃ doped ZrO₂（ScSZ） series（including single or binary oxides doped ScSZ） makes zirconia-based electrolyte shows excellent ionic conductivity.The nano-crystallization of ScSZ-based electrolyte has been widely studied due to its excellent electrical properties.However,ScSZ-based electrolyte will undergo phase transition at medium and low tem-perature,resulting in rhombic phase with low conductivity,which affects its ionic conductivity.ScSZ electrolytes doped with single or binary oxides were systematically summarized.The results showed that multi-oxides doped ScSZ could effectively pre-vent from phase transformation at medium and low temperatures,stabilize cubic ScSZ.Nano-crystallization ScSZ based elec-trolytes prepared by different methods could improve the ionic conductivity very well.The development direction of ScSZ se-ries in medium and low temperature（600~800 ℃） was proposed：the conductivity of grain and grain boundary could be im-proved through optimizing the doped composition,nano-crystallization and electrolyte materials with novel structures could be prepared by different preparation methods and parameters.

Key words: refined magnesium slag, crushing and winnowing, magnesium beads, ScSZ-based electrolyte, Sc₂O₃, ZrO₂, conductivity

中图分类号:

梁天权,郭燕,陈锡勇,詹峰,张修海,曾建民. 纳米ScSZ基电解质中低温导电性研究进展[J]. 无机盐工业, 2021, 53(6): 87-94.

Liang Tianquan,Guo Yan,Chen Xiyong,Zhan Feng,Zhang Xiuhai,Zeng Jianmin. Research progress of conductivity of nano ScSZ-based electrolyte at medium and low temperature[J]. Inorganic Chemicals Industry, 2021, 53(6): 87-94.

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电解质	制备方法	测试温度/℃	电导率/ （S·cm^-1）
1Ce10ScSZ^[23]	固相合成：1 400 ℃烧结	600	0.046（高纯度） 0.033（低纯度）
1Ce10ScSZ^[24]	1 500 ℃烧结2 h,平均粒径为5.9 μm	800	0.140
1Ce10ScSZ^[25]	甘氨酸-硝酸盐法（MW- GNP）：微波中固溶燃烧合成,700 ℃煅烧2 h,1 300 ℃ 烧结5 h	500~ 800	0.033~ 0.184
1Ce9ScSZ^[12]	固相合成：1 335 ℃煅烧 6 h,1 550 ℃烧结10 h	700 600	0.032 0.018 8
1Ce10ScSZ^[26]	水热法：800 ℃煅烧2 h, 1 400 ℃烧结2 h,平均粒径为20.2 nm	800	0.131
1Ce10ScSZ^[11]	微波烧结法：在微波炉中1 335 ℃烧结15 min	800	0.280
1Ce10ScSZ^[27]	新型固液方法（SLM）： 1 000 ℃煅烧2 h,1 550 ℃煅烧5 h	800	0.140
1Ce10ScSZ^[28]	化学共沉淀法：1 500 ℃烧结5 h	800	0.040
1Ce10ScSZ^[29]	溶胶-凝胶法：600 ℃煅烧24 h,1 500 ℃烧结5 h	600	0.011 4
1Ce10ScSZ^[30]	沉淀-共沸蒸馏法：1 600 ℃ 烧结	800	0.084

电解质	制备方法	测试温度/℃	电导率/ （S·cm^-1）
4Y4ScSZ^[41]	溶胶凝胶-滴涂沉积法：1 000 ℃煅烧6 h,平均直径为144 nm,活化能为0.73 eV	700	0.120
1Eu10ScSZ^[10]	固相合成法：降低β→c转变温度,室温下为立方相	500	0.002
3Mg9ScSZ^[42]	尿素共沉淀合成法：1 200 ℃长时间处理不发生相变, 1 600 ℃ 3 h不影响致密性,相对密度约为97%	700 800	0.028 0.073
1Nb10ScSZ^[43]	固相合成法：1 300 ℃煅烧6 h,1 550 ℃烧结10 h,在650 ℃时比11ScSZ高80%	650 700	0.018 8 0.031 8
3LaScSZ^[44]	化学共沉淀法：800 ℃煅烧5 h, 1 550 ℃烧结6 h,室温下稳定立方相,晶粒为20~30 nm,晶界阻抗降低	500~ 660	0.021~ 0.024
1Mn10ScSZ^[45]	USP（超声喷雾热解）法：1 400 ℃煅烧10 h	800	0.112
1Hf10ScSZ^[46]	固相合成法：1 550 ℃烧结5 h	600	0.008 8

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