Formation of Amorphous H3Zr2Si2PO12 by Electrochemical Substitution of Sodium Ions in Na3Zr2Si2PO12 with Protons
Formation of Amorphous H3Zr2Si2PO12 by Electrochemical Substitution of Sodium Ions in Na3Zr2Si2PO12 with Protons
复制标题
质子电化学取代 Na3Zr2Si2PO12 中的钠离子形成非晶态 H3Zr2Si2PO12
DOI：
10.1021/acs.inorgchem.7b02060
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发表时间：
2017
影响因子：
4.6
通讯作者：
T. Omata
中科院分区：
文献类型：
--
作者：
S. Tsukuda;K. Miyake;T. Yamaguchi;M. Kita;T. Ishiyama;J. Nishii;T. Yamashita;H. Kawazoe;T. Omata
在400 °C下，在5%H2/95%N2气氛下，使用电化学碱-质子取代（APS）技术用质子取代Na 3 Zr 2Si 2 PO 12（NASICON）中的钠离子。NASICON中的钠离子成功地被质子取代，深度<400 μm。完全质子化NASICON，即，H_3Zr_2Si_2PO_1_2在离阳极<40 μm的深度处得到，尽管NASICON的完全质子化不能通过在含水酸中的离子交换实现。H3 Zr 2Si 2 PO 12是非晶态的，而部分质子化的NASICON是晶态的，其晶胞体积随着取代度的增加而减小.通过压力诱导NASICON骨架的非晶化制备了非晶H3 Zr 2Si 2 PO 12，其中在400 °C的APS过程中，通过用小质子取代大钠离子来诱导约3.5 GPa的内压。
The sodium ions in Na3Zr2Si2PO12(NASICON) were substituted with protons using an electrochemical alkali–proton substitution (APS) technique at 400 °C under a 5% H2/95% N2atmosphere. The sodium ions in NASICON were successfully substituted with protons to a depth of <400 μm from the anode. Completely protonated NASICON, i.e., H3Zr2Si2PO12, was obtained to a depth <40 μm from the anode, although complete protonation of NASICON cannot be achieved by ion exchange in aqueous acid. H3Zr2Si2PO12was amorphous, whereas the partially protonated NASICON was crystalline, and its unit cell volume decreased with an increase in the extent of substitution. Amorphous H3Zr2Si2PO12was prepared by pressure-induced amorphization of the NASICON framework, in which an internal pressure of ∼3.5 GPa was induced by the substitution of large sodium ions with small protons during APS at 400 °C.