Okura Toshinori, Matsuoka Naoki, Takahashi Yoshiko, Yoshida Naoya, Yamashita Kimihiro
Department of Applied Chemistry, School of Advanced Engineering, Kogakuin University, Nakano 2665-1, Hachioji, Tokyo 192-0015, Japan.
Graduate School of Medical and Dental Sciences, Tokyo Medical and Dental University, Yushima 1-5-45, Bunkyo, Tokyo 113-8501, Japan.
Materials (Basel). 2023 Mar 7;16(6):2155. doi: 10.3390/ma16062155.
We have developed 12-membered silica-tetrahedra-ringed NaYSiO-type sodium ion conducting glass-ceramics on the basis of the composition NaRPSiO (R: rare earth elements; denoted as Narpsio); especially, the material of NaYPSiO with the combined parameters of (x, y) = (0.4, 0.2) gives rise to the maximum conductivity of 1 × 10 Scm at 300 °C. Because glass-ceramics generally have the advantage of structural rigidity and chemical durability over sintered polycrystalline ceramics, the present study employed glass-ceramic Narpsio to perform chemically driven ion exchange of Na with protonated water molecules with an aim to produce a proton conductor. The ion exchange was carried out in a hydrochloric acid solution by changing immersion time, temperature, and acid concentration. The ion exchanged NaYPSiO-based glass-ceramics were analyzed by the complex impedance method, and the proton conductivity was found to exhibit 3 × 10 Scm at 300 °C with the activation energy of 59 kJ/mol. The dependence of humidity-sensitive conductivity of the ion exchanged bulk glass-ceramics was also examined; the conductivity increased almost linearly from 0.6 × 10 Scm in dry air to 1.5 × 10 Scm in 75% humid ambience at 300 °C. Thus, the ion exchanged glass-ceramics can be considered to be high temperature proton conductors as well as humidity sensors.
我们基于NaRPSiO（R：稀土元素；表示为Narpsio）的成分开发了具有12元硅四面体环的NaYSiO型钠离子传导玻璃陶瓷；特别是，(x, y) = (0.4, 0.2)组合参数的NaYPSiO材料在300°C时产生了1×10 S/cm的最大电导率。由于玻璃陶瓷通常比烧结多晶陶瓷具有结构刚性和化学耐久性的优势，本研究采用玻璃陶瓷Narpsio进行Na与质子化水分子的化学驱动离子交换，旨在制备质子导体。通过改变浸泡时间、温度和酸浓度在盐酸溶液中进行离子交换。采用复阻抗法对离子交换后的NaYPSiO基玻璃陶瓷进行分析，发现其在300°C时质子电导率为3×10 S/cm，活化能为59 kJ/mol。还研究了离子交换块状玻璃陶瓷的湿度敏感电导率的依赖性；在300°C时，电导率从干燥空气中的0.6×10 S/cm几乎线性增加到75%湿度环境中的1.5×10 S/cm。因此，离子交换后的玻璃陶瓷可被视为高温质子导体以及湿度传感器。
