The Electronic Conductivity of Single Crystalline Ga‐Stabilized Cubic Li<sub>7</sub>La<sub>3</sub>Zr<sub>2</sub>O<sub>12</sub>: A Technologically Relevant Parameter for All‐Solid‐State Batteries
Martin Philipp, Bernhard Gadermaier, Patrick Posch, Ilie Hanzu, Steffen Ganschow, Martin Meven, Daniel Rettenwander, Günther J. Redhammer, Martin Wilkening
Abstract
Abstract The next‐generation of all‐solid‐state lithium batteries need ceramic electrolytes with very high ionic conductivities. At the same time a negligible electronic conductivity σ eon is required to eliminate self‐discharge in such systems. A non‐negligible electronic conductivity may also promote the unintentional formation of Li dendrites, being currently one of the key issues hindering the development of long‐lasting all‐solid‐state batteries. This interplay is suggested recently for garnet‐type Li 7 La 3 Zr 2 O 12 (LLZO). It is, however, well known that the overall macroscopic electronic conductivity may be governed by a range of extrinsic factors such as impurities, chemical inhomogeneities, grain boundaries, morphology, and size effects. Here, advantage of Czochralski‐grown single crystals, which offer the unique opportunity to evaluate intrinsic properties of a chemically homogeneous matrix, is taken to measure the electronic conductivity σ eon . Via long‐time, high‐precision potentiostatic polarization experiments an upper limit of σ eon in the order of 5 × 10 −10 S cm −1 (293 K) is estimated. This value is by six orders of magnitude lower than the corresponding total conductivity σ total = 10 −3 S cm −1 of Ga‐LLZO. Thus, it is concluded that the high values of σ eon recently reported for similar systems do not necessarily mirror intragrain bulk properties of chemically homogenous systems but may originate from chemically inhomogeneous interfacial areas.