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.

In situ Raman analysis of gas formation in NiMH batteries.

In this paper Raman spectrometry is introduced in the field of sealed battery research for in situ gas-phase analysis and for longterm measurements. For this purpose, a new method was successfully applied in order to model battery behavior without interfering with operation. It is shown that oxygen, hydrogen, and nitrogen are responsible for the pressure increase that occurs during overcharging. The relative contribution of the different gases depends on the current imposed on the battery as well as the operating temperature. Reproducible and stable signals could be obtained even under severe conditions such as high pressure and elevated temperature. Oxygen and hydrogen are produced in side reactions taking place during battery operation. However, as nitrogen is unlikely to be a reacting gas inside the battery, the change in its partial pressure can be attributed to electrode expansion and a change in the electrolyte volume.