Non-equilibrium kinetics for improving ionic conductivity in garnet solid electrolyte

doi:10.1039/d2mh01311h

2023-01-01

PRE

DOI：10.1039/d2mh01311h

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Solid-state electrolytes (SSEs), as an essential component of all solid-state batteries, exhibit limited ionic conductivity. The fractional occupancy of Li+ ions, regulated by the doping of hetero-valent transition metals, is an important characteristic to enable high Li+ conductivity. However, the structural and kinetic mechanism of this is still unclear, preventing the rational design of higher-conductivity SSEs. Here, taking the typical garnet SSE Li7-xLa3Zr2-xTaxO12 (0 <= x <= 0.625) as an example, we revealed that a Ta5+-doping concentration of x = 0.25 leads to a high amount of non-equilibrium Li+ configurations in the form of [LiO6]-[LiO4]-[VLiO6]. Non-equilibrium configurations induce high off-center shifts and high electrostatic energies of Li+ ions, reducing the activation energy of Li+-ionic transport. As a result, the doping of hetero-valent ions has a great effect on Li+-ionic conductivity through controlling the amount of non-equilibrium Li+ ions. These findings provide important insight into the understanding of ionic transport and pave the way towards optimizing Li+ distribution to improve ionic conductivity.

Keyword:

ULTRASOFT PSEUDOPOTENTIALS

LITHIUM DISTRIBUTION

MOLECULAR-DYNAMICS

OXIDES

期刊

Materials Horizons

IF:

10.7

论文数:

3.6K

被引数:

2.4W

机构

chinese academy of sciences

学者数:

56.7W

论文数: 45.0W

被引数: 704

引用论文

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