化学镀制备高温质子导体镍电极及其电化学性能

doi:10.15541/jim20170112

摘要/Abstract

摘要：

采用化学镀在高温质子导体CaZr_0.9In_0.1O_3-_δ (CZI)的电解质陶瓷表面沉积金属镍电极, 通过SEM显微结构分析比较了酸刻蚀和还原工艺对电极形貌以及电极-电解质界面的影响。结果表明, 使用HNO₃-HCl混合刻蚀液, 并以水合肼为还原剂的二次化学镀可获得颗粒均匀细小且界面结合良好的镍电极。通过电化学阻抗谱并结合浓差电池等方法研究比较了以化学镀镍电极和涂覆焙烧铂电极为电极, CZI为电解质的对称电池的电导率和质子迁移率。工作温度为800℃时, 镍电极高温质子导体的总电导率为4.131×10^-4S/cm, 并且工作温度在400℃以上时, 镍电极对称电池的质子迁移率均接近100%。这些结果表明, 二次化学镀制备的镍电极具有与铂电极相近的电化学性能, 而成本则更低, 可以取代Pt电极用于高温质子导体的电化学器件中。

关键词: 化学镀, 镍电极, 高温质子导体

Abstract:

Nickel layers were deposited on the surface of high-temperature proton-conducting CaZr_0.9In_0.1O_3-_δ (CZI) electrolytes by an electroless plating technique. Effects of acid etching and reduction processes on electrode surface morphology and electrolyte adherence to electrodes were investigated by SEM observation. The results showed that the electrodes prepared by a two-step electroless plating process in HNO₃-HCl etching solution with hydrazine reducing agent were uniform and well connected to the electrolyte surface. Conductivity and proton transport rate between Ni-CZI symmetric cell and Pt-CZI symmetric cell were compared by electrochemical impedance spectroscopy and concentration cell test. The total conductivity of the Ni-CZI symmetric cell was 4.131×10^-4 S/cm at 800℃, and the proton transport rates of the Ni-CZI symmetric cell were all almost 100% at the operating temperature higher than 400℃. The nickel electrode prepared by two-step electroless plating was achievable at low cost and had a comparable catalytic performance to that of platinum electrode, indicating it a promising candidate to replace athe noble platinum catalyst electrode.

Key words: electroless plating, nickel electrodes, high-temperature proton-conducting electrolytes

中图分类号:

O646

温亚兵, 张敬超, 叶晓峰, 王勇, 韩金铎, 罗文华, 谷穗, 孟建波, 温兆银. 化学镀制备高温质子导体镍电极及其电化学性能[J]. 无机材料学报, 2017, 32(12): 1250-1256.

WEN Ya-Bing, ZHANG Jing-Chao, YE Xiao-Feng, WANG Yong, HAN Jin-Duo, LUO Wen-Hua, GU Sui, MENG Jian-Bo, WEN Zhao-Yin. Nickle Electrodes for High-temperature Proton-conducting Electrolytes: Preparation by Electroless Plating and Electrochemical Performance[J]. Journal of Inorganic Materials, 2017, 32(12): 1250-1256.

图/表 9

图1 不同温度煅烧的CZI粉体和烧结后陶瓷表面的XRD图谱

Fig. 1 XRD patterns of CZI powders calcined at different temperatures and sintered CZI ceramic surface

图2 1550℃烧结的CZI陶瓷断面形貌

Fig. 2 Cross-sectional microstructure of CZI ceramic sintered at 1550℃

图3 HCl-HNO3刻蚀不同时间后CZI陶瓷的表面形貌

Fig. 3 Morphologies of the CZI surfaces etched for different time(a) Unetched; (b) HCl-HNO3 etched for 10 min; (c) HCl-HNO3 etched for 20 min

图4 经过不同阶段化学镀得到的电极断面和表面形貌

Fig. 4 Cross-section and surface morphology of electrodes after electroless plating for different periods(a) One-step, 1 h; (b) Two-step, 0 h; (c) Two-step, 0.5 h; (d) Two-step, 1 h; (e) Two-step, 1.5 h; (f) Two-step, 2 h

图5 镍电极的XRD图谱(a)和镍电极表面的EDS面扫描图(b)

Fig. 5 XRD pattern of Ni electrode (a) and EDS plane scan analysis of Ni electrode surface (b)

图6 湿氢气气氛中Pt-CZI和Ni-CZI在不同温度下的电化学阻抗谱

Fig. 6 Impedance spectra of Pt-CZI and Ni-CZI at different temperatures in wet H2

图7 以涂覆焙烧Pt和化学镀Ni为电极的高温质子导体在湿氢气气氛下总电导率的Arrhenius曲线

Fig. 7 Arrhenius curves of total conductivity of pasted Pt and electroless plated Ni electrode high-temperature proton conductor in wet H2

图8 浓差电池H2(PH2=105 Pa)/H2+N2(PH2=5×104 Pa), Ni | CZI | Ni, H2+Ar(PH2=5×103 Pa)的电动势、理论电动势和质子迁移率

Fig. 8 EMFs, theoretical electromotive force values and proton transport rates of hydrogen concentration cell: H2 (PH2=105 Pa)/ H2+N2 (PH2=5×104 Pa), Ni | CZI |Ni, H2+Ar (PH2=5×103 Pa)

图9 浓差电池(50%H2-5%H2)在800℃下, 运行不同时间的电解质/电极的界面形貌

Fig. 9 Interface morphology of electrolyte and electrode of concentration cell (50%H2-5%H2) with different run time at 800℃

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