Correction to Untangling the Structure and Dynamics of Lithium-Rich Anti-Perovskites Envisaged as Solid Electrolytes for Batteries

The Batteries’ New Clothes: Li and H Dynamics in Poorly Conducting Li2OHCl Directly Probed by Nuclear Spin Relaxation

“…These measurements probe dynamic processes on the kHz rather than on the MHz time scale as it is the case with laboratory-frame SLR NMR. 48 It should be clearly stated that against some wishful thinking, our findings, 37 and those of others, 49 have shown that Li 2 (OH) Cl is a rather poor Li + -ion conductor. Li 2 (OH)Cl undergoes a first-order phase transformation at 35 °C and transforms from an orthorhombic from into the cubic counterpart, see Figure 1.…”

“…At 100 °C, the Li + jump rate might easily exceed 10 6 s −1 , thus the induced OH − (OD − ) reorientations could indeed lead to an averaging of the electric quadrupole interactions to which the 2 H spins are subjected. If the electric field gradient sensed by 2 H is mainly due to the local Li + distribution in the direct neighborhood of 2 H, sufficiently high Li + hopping would 37 Note that values of 0.57 eV include resistive effects from grain boundary regions. The barriers dictating long-range ion transport in the two structural modifications seem to be rather similar.…”

“…Despite the increasing number of investigations on Li 3−x OH x Cl, it remains, however, exceedingly difficult to reliably synthesize and to characterize the proton-free (x = 0) form "Li 3 OCl" because it is extremely hygroscopic. 37 In particular, Dawson et al point out its strongly exothermic hydration enthalpy. 38 Lithium hydroxychloride (Li 2 (OH)Cl) is, however, much easier accessible via different synthesis routes including even hydrothermal ones.…”

“…38 Lithium hydroxychloride (Li 2 (OH)Cl) is, however, much easier accessible via different synthesis routes including even hydrothermal ones. 37 Li 2 (OH)Cl is also being discussed as a very promising solid Li + electrolyte. As yet, we do, however, not fully understand the complete dynamic situation in Li 2 (OH)Cl, which might need to be described by both translational and rotational jump processes.…”

“…Figure 7. Temperature behavior of the direct current (d.c.) ionic conductivity σ d.c. plotted as log 10 (σ d.c. T) vs 1/T to extract activation energies for both the cubic and orthorhombic form of Li 2 OHCl; data taken from Hanghofer et al37 Note that values of 0.57 eV include resistive effects from grain boundary regions. The barriers dictating long-range ion transport in the two structural modifications seem to be rather similar.…”