Understanding the relationship between structure, ionic conductivity, and synthesis is the key to the development of superionic conductors. Here, a series of Li_3-3xM_1+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/Li_2.73Ho_1.09Cl₆/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.

In this study, the impact of water-to-cement (w/c) ratios of belite calcium sulfoaluminate cement (BCSA) on the hydration kinetics and the electrochemical impedance spectroscopy (EIS) parameters is studied. According to the analysis of classic hydration measurements, such as calorimetry tests, chemical shrinkage content, and chemically bound water content, it can be concluded that a higher w/c ratio clearly accelerates the hydration of BCSA cement paste. The electrical resistivity of BCSA0.35 cement paste is more than 4.5 times that of BCSA0.45 and BCSA0.5, due to the gradually densified micropore structure blocking the electrical signal transmission rather than the free charged-ion content. The porosity of BCSA0.5 is 27.5% higher than that of BCSA0.35 and 7.8% higher than that of BCSA0.45, which proves the resistivity is clearly related to the variation in microstructure, especially for the porosity and pore size distribution. The novelty of this study is the linear regression with logarithm terms of electrical resistivity and classic hydration parameters such as chemical shrinkage, cumulative hydration heat, and chemically bound water is established to extend the classical expression of cement hydration degree. It indicates that the electrochemical impedance spectroscopy can be taken as a nondestructive testing measurement to real-time monitor the cement hydration process of cement-based materials.