期刊
JOURNAL OF PHYSICAL CHEMISTRY C
卷 125, 期 30, 页码 16689-16699出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.1c03589
关键词
-
资金
- Swedish Research Council [2017-06345]
- US DOE Office of Energy Efficiency and Renewable Energy, Fuel Cell Technologies Office [DE-AC36-08GO28308]
- Center for High Resolution Neutron Scattering
- National Science Foundation [DMR-1508249, DMR-2010792]
- Barbro Osher Pro Suecia Foundation
- Russian Foundation for Basic Research [AAAA-A19-119012990095-0, 19-03-00133]
- U.S. Department of Energy's National Nuclear Security Administration [DE-NA-0003525]
- Swedish Research Council [2017-06345] Funding Source: Swedish Research Council
The study investigates the unique structural and ion dynamical properties of NaCB11H12 dispersed within high-surface-area silica through salt-solution infiltration, revealing the formation of a nanoconfined phase with superionic properties that persist at subambient temperatures. Fast-cation diffusion promoted by high anion mobilities leads to Na+ superionic conductivities of around 0.3 mS/cm at room temperature, indicating future potential for conductivity enhancement in related polyhedral (carba)borate-based salts as solid-state electrolytes in battery applications.
Superionic phases of bulk anhydrous salts based on large cluster-like polyhedral (carba)borate anions are generally stable only well above room temperature, rendering them unsuitable as solid-state electrolytes in energy-storage devices that typically operate at close to room temperature. To unlock their technological potential, strategies are needed to stabilize these superionic properties down to subambient temperatures. One such strategy involves altering the bulk properties by confinement within nanoporous insulators. In the current study, the unique structural and ion dynamical properties of an exemplary salt, NaCB11H12, nanodispersed within porous, high-surface-area silica via salt-solution infiltration were studied by differential scanning calorimetry, X-ray powder diffraction, neutron vibrational spectroscopy, nuclear magnetic resonance, quasielastic neutron scattering, and impedance spectroscopy. Combined results hint at the formation of a nanoconfined phase that is reminiscent of the high-temperature superionic phase of bulk NaCB11H12, with dynamically disordered CB11H12-anions exhibiting liquid-like reorientational mobilities. However, in contrast to this high-temperature bulk phase, the nanoconfined NaCB11H12 phase with rotationally fluid anions persists down to cryogenic temperatures. Moreover, the high anion mobilities promoted fast-cation diffusion, yielding Na+ superionic conductivities of similar to 0.3 mS/cm at room temperature, with higher values likely attainable via future optimization. It is expected that this successful strategy for conductivity enhancement could be applied as well to other related polyhedral (carba)borate-based salts. Thus, these results present a new route to effectively utilize these types of superionic salts as solid-state electrolytes in future battery applications.
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