Lithium deposition in single ion conducting polymer electrolytes

Lithium Li metal is considered as promising anode material for high energy density rechargeable batteries, although its application is hampered by inhomogeneous Li deposition and dendritic Li morphologies that could eventually result in contact losses of bulk and deposited Li as well as cell short circuits. Based on theoretical investigations, recent works on polymer electrolytes particularly focus on the design of single ion conducting electrolytes and improvement of bulk Li transport properties, including enhanced Li transference numbers, ionic conductivity, and mechanical stability, thereby affording safer and potentially dendrite free cycling of Li metal batteries. In the present work, it is revealed that the spatial microstructures, localized chemistry, and corresponding distributions of properties within the electrolyte are also decisive for achieving superior cell performances. Thus, targeted modification of the electrolyte microstructures should be considered as further critical design parameters for future electrolyte development and to actually control Li deposition behavior and longevity of Li metal batterie

Investigation of the Li-ion conduction behavior in the Li10GeP2S12 solid electrolyte by two-dimensional T1-spin alignment echo correlation NMR

Li10GeP2S12 (LGPS) is the fastest known Li-ion conductor to date due to the formation of one-dimensional channels with a very high Li mobility. A knowledge-based optimization of such materials for use, for example, as solid electrolyte in all-solid-state batteries requires, however, a more comprehensive understanding of Li ion conduction that considers mobility in all three dimensions, mobility between crystallites and different phases, as well as their distributions within the material. The spin alignment echo (SAE) nuclear magnetic resonance (NMR) technique is suitable to directly probe slow Li ion hops with correlation times down to about 10−5 s, but distinction between hopping time constants and relaxation processes may be ambiguous. This contribution presents the correlation of the 7Li spin lattice relaxation (SLR) time constants (T1) with the SAE decay time constant τc to distinguish between hopping time constants and signal decay limited by relaxation in the τc distribution. A pulse sequence was employed with two independently varied mixing times. The obtained multidimensional time domain data was processed with an algorithm for discrete Laplace inversion that does not use a non-negativity constraint to deliver 2D SLR–SAE correlation maps. Using the full echo transient, it was also possible to estimate the NMR spectrum of the Li ions responsible for each point in the correlation map. The signal components were assigned to different environments in the LGPS structure

Complexions at the Electrolyte Electrode Interface in Solid Oxide Cells

Rapid deactivation presently limits a wide spread use of high temperature solid oxide cells SOCs as otherwise highly efficient chemical energy converters. With deactivation triggered by the ongoing conversion reactions, an atomic scale understanding of the active triple phase boundary between electrolyte, electrode, and gas phase is essential to increase cell performance. Here, a multi method approach is used comprising transmission electron microscopy and first principles calculations and molecular simulations to untangle the atomic arrangement of the prototypical SOC interface between a lanthanum strontium manganite LSM anode and a yttria stabilized zirconia YSZ electrolyte in the as prepared state after sintering. An interlayer of self limited width with partial amorphization and strong compositional gradient is identified, thus exhibiting the characteristics of a complexion that is stabilized by the confinement between two bulk phases. This offers a new perspective to understand the function of SOCs at the atomic scale. Moreover, it opens up a hitherto unrealized design space to tune the conversion efficienc