期刊
CHEMISTRY OF MATERIALS
卷 27, 期 10, 页码 3658-3665出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.chemmater.5b00362
关键词
-
资金
- NSF CBET [1066406]
- Office of Naval Research through the Naval Research Laboratory's Basic Research Program
- Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy
- Revolutionary Materials for Solid State Energy Conversion, an Energy Frontier Research Center - US Department of Energy, Office of Science, Office of Basic Energy Science [DE-SC001054]
- U.S. Army Research Laboratory (ARL)
- Div Of Chem, Bioeng, Env, & Transp Sys
- Directorate For Engineering [1066406] Funding Source: National Science Foundation
The oxide garnet material L(i)7La(3)Zr(2)O(12) shows remarkably high ionic conductivity when doped with supervalent ions that are charge compensated by Li vacancies and is currently one of the best candidates for development of a technologically relevant solid electrolyte. Determination of optimal dopant concentration, however, has remained a persistent problem due to the extreme difficulty of establishing the actual (as compared to nominal) stoichiometry of intentionally doped materials and by the fact that it is still not entirely clear what level of lattice expansion/contraction best promotes. ionic diffusion. By combining careful synthesis, neutron diffraction, high-resolution X-ray diffraction (XRD), Raman measurements, and density functional theory calculations, we show that structure and stoichiometry are intimately related such that the former can in many cases be used as a gauge of the latter. We show that different Li-vacancy creating supervalent ions (Al3+ vs Ta5+) affect the structure very differently, both in terms of the lattice constant, which is easily measurable, and hi terms of the local structure, which can be difficult or impossible to access experimentally but may have important ramifications for conduction. We carefully correlate the lattice constant to dopant type/concentration via Vegard's law and then further correlate these quantities to relevant local structural parameters. Our work opens the possibility of developing a codopant scheme that optimizes the Li vacancy concentration and the lattice size simultaneously.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据