Divalent Ni2+ cation conduction in NASICON-type solid
Divalent Ni2+ cation conduction in NASICON-type solid
复制标题
NASICON 型固体中二价 Ni2 阳离子的传导
DOI：
10.1016/j.matlet.2018.09.095
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发表时间：
2019
影响因子：
3
通讯作者：
Imanaka Nobuhito
中科院分区：
文献类型：
--
作者：
Lee Wonrak;Yamauchi Shota;Tamura Shinji;Imanaka Nobuhito
通过在具有三维NASICON型结构的HfNb（PO 4）3固体中引入Ni 2+阳离子，成功制备了二价Ni 2+阳离子导电固体电解质（NixHf 1 −x）4/（4−2x）Nb（PO 4）3。虽然HfNb（PO 4）3固体已被报道为纯粹的Hf 4+离子导体，但由于低价离子在刚性晶格中的容易迁移，在Ni 2+掺杂时，导电物种变为二价Ni 2+阳离子。此外，通过选择有序的NASICON型结构作为母晶，（NixHf 1 −x）4/（4−2x）Nb（PO 4）3固体电解质显示出比先前报道的具有β-Fe 2（SO 4）3型结构的NiZr 4（PO 4）6固体更低的活化能和更高的Ni 2+阳离子电导率。在（NixHf 1 −x）4/（4−2x）Nb（PO 4）3固体中，（Ni0.06Hf0.94）4/3.88Nb（PO 4）3（x= 0.06）显示出最高的Ni 2+离子电导率，在600 °C时为2.27 × 10−4S·cm− 1，约为2.27 × 10−4S·cm− 1。比NiZr_4（PO_4）_6固体高23倍。
Divalent Ni2+cation-conducting solid electrolytes, (NixHf1−x)4/(4−2x)Nb(PO4)3, were successfully developed by introducing Ni2+cations into a HfNb(PO4)3solid exhibiting a three-dimensional NASICON-type structure. Although the HfNb(PO4)3solid has been reported to be purely a Hf4+ion conductor, the conducting species was changed to the divalent Ni2+cation upon Ni2+doping, due to the facile migration of lower-valence ions in the rigid crystal lattice. In addition, by selecting the well-ordered NASICON-type structure as the mother crystal, the (NixHf1−x)4/(4−2x)Nb(PO4)3solid electrolytes exhibited lower activation energies and higher Ni2+cation conductivities than a previously reported NiZr4(PO4)6solid with the β-Fe2(SO4)3-type structure. Among the (NixHf1−x)4/(4−2x)Nb(PO4)3solids, (Ni0.06Hf0.94)4/3.88Nb(PO4)3(x= 0.06) showed the highest Ni2+ion conductivity, of 2.27 × 10−4S·cm−1at 600 °C, which is ca. 23 times higher than that of the NiZr4(PO4)6solid.