Chihiro Hiraiwa

Origins of structural and electrochemical influence on Y-doped BaZrO3 heat-treated with NiO additive

Nickel (Ni) is expected to be an attractive anode material for protonic ceramic fuel cells using Y-doped BaZrO3 (BZY) as an electrolyte, since Ni shows good catalytic properties for the anode reaction, and NiO is a sintering aid for BZY. In this work, a systematic investigation has been performed to reveal the influence of Ni incorporation on structural and electrochemical properties of BZY. Then, some new knowledge was obtained; the important point is that Ni cations occupy the interstitial position of (1/2, 0, 0) in the lattice of BZY, with a greatly Ba-deficient environment. As a result, Ba cations were possibly driven to the grain boundary and induced the formation of a liquid phase, which promoted the sintering process. However, the occupation of Ni on this (1/2, 0, 0) position also resulted in a negative influence on conductivity. A careful processing is required to apply Ni as the electrode in BZY based fuel cells.

A high temperature reduction cleaning (HTRC) process: a novel method for conductivity recovery of yttrium-doped barium zirconate electrolytes

Proton conducting Y-doped BaZrO3 (BZY) and nickel oxide (NiO) are currently the most promising electrolyte and anode catalyst for protonic ceramic fuel cells, respectively. However, during the co-sintering process to fabricate the fuel cells, Ni cations diffuse from the anode into the lattice of the BZY electrolyte, resulting in significant degradation of the electrolyte conductivity and fuel cell performance. With the aim to solve such a problem, in this work, we report a novel method, named as high temperature reduction cleaning (HTRC) process, which is composed of several sequential heat-treatments in controlled atmospheres. The most interesting point is that after heat-treating the NiO-contaminated BZY at 1400 °C in a Ti-deoxidized Ar atmosphere for 100 h, Ni cations were observed to be expulsed from the BZY lattice and segregated at the grain boundary as Ni metal particles. And the conductivity of the BZY electrolyte was recovered. However, delamination along the grain boundary of the BZY electrolyte was introduced when the segregated Ni metal particles were oxidized to NiO particles in an oxygen atmosphere. And a series of sequential heat-treatments were designed to solve such a problem.

Detrimental Effect of Sintering Additives on Conducting Ceramics: Yttrium‐Doped Barium Zirconate

Y-doped BaZrO3 (BZY) is currently the most promising proton-conductive ceramic-type electrolyte for application in electrochemical devices, including fuel cells and electrolyzer cells. However, owing to its refractory nature, sintering additives, such as NiO, CuO, or ZnO are commonly added to reduce its high sintering temperature from 1600 °C to approximately 1400 °C. Even without deliberately adding a sintering additive, the NiO anode substrate provides another source of the sintering additive; during the co-sintering process, NiO diffuses from the anode into the BZY electrolyte layer. In this work, a systematic study of the effect of NiO, CuO, and ZnO on the electroconductive properties of BaZr0.8 Y0.2 O3-δ (BZY20) is conducted. The results revealed that the addition of NiO, CuO, or ZnO into BZY20 not only degraded the electrical conductivity but also resulted in enhancement of the hole conduction. Removal of these sintering additives can be realized by post-annealing in hydrogen at a mild temperature of 700 °C, but it is kinetically very slow. Therefore, the addition of NiO, CuO, and ZnO is detrimental to the electroconductive properties of BZY20, and significantly restrict its application as an electrolyte. The development of new sintering additives, new anode catalysts, or new methods for preparing BZY electrolyte-based cells is urgently needed.