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Understanding the relationship between structure, ionic conductivity, and synthesis is the key to the development of superionic conductors. Here, a series of Li3-3xM1+xCl6 (−0.14 < x ≤ 0.5, M = Tb, Dy, Ho, Y, Er, Tm) solid electrolytes with orthorhombic and trigonal structures are reported. The orthorhombic phase of Li–M–Cl shows an approximately one order of magnitude increase in ionic conductivities when compared to their trigonal phase. Using the Li–Ho–Cl components as an example, their structures, phase transition, ionic conductivity, and electrochemical stability are studied. Molecular dynamics simulations reveal the facile diffusion in the z-direction in the orthorhombic structure, rationalizing the improved ionic conductivities. All-solid-state batteries of NMC811/Li2.73Ho1.09Cl6/In demonstrate excellent electrochemical performance at both 25 and −10 °C. As relevant to the vast number of isostructural halide electrolytes, the present structure control strategy guides the design of halide superionic conductors., Green Open Access added to TU Delft Institutional Repository 'You share, we take care!' - Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public., RST/Storage of Electrochemical Energy, Photovoltaic Materials and Devices, RID/TS/Instrumenten groep

The ultrafast ionic conductivity of Li 6 PS 5 Br, which is higher than 1 mS cm -1 at room temperature, makes it an attractive candidate electrolyte for the all-solid-state Li-S battery. A simple synthesis route with an easy scale up process is critical for practical applications. In this work, the highest room temperature ionic conductivity (2.58 × 10 -3 S cm -1 ) of Li 6 PS 5 Br is obtained by an optimal annealing temperature in a simple solid-state reaction method. Neutron diffraction and XRD show that the origin of the highest ionic conductivity is due to the higher purity, smaller mean lithium ion jumps and the optimal Br ordering over 4a and 4c sites. All-solid-state Li-S batteries using a S-C composite cathode in combination with the optimized Li 6 PS 5 Br electrolyte and Li-In anode show high (dis)charge capacities. Different cycling modes (charge-discharge and discharge-charge) reveal that the capacity of the S-C-Li 6 PS 5 Br/Li 6 PS 5 Br/Li-In battery arises from both the active S-C composite and the Li 6 PS 5 Br in the cathode mixture. The contribution of the latter is verified from all-solid-state batteries using Li 6 PS 5 Br and its analogues as active materials. Ex situ XRD and electrochemical performance results show that the contribution of capacity from Li 6 PS 5 Br in the cathode mixture may be associated with the decomposition product Li 2 S, while the Li 6 PS 5 Br in the bulk solid electrolyte layer is stable during cycling., Accepted Author Manuscript, RST/Storage of Electrochemical Energy, RST/Neutron and Positron Methods in Materials