Subtle Local Structural Details Influence Ion Transport in Glassy Li+ Thiophosphate Solid Electrolytes.

Many of the promising, high-performing solid electrolytes for lithium-ion batteries are amorphous or contain an amorphous component, particularly in the Li thiophosphate Li2S-P2S5 (LPS) compositional series. An explicit study of the local structure in four samples of ostensibly identically prepared 70Li2S-30P2S5 glass reveals substantial variation in the ratio between the two main local structural units in this system: PS43- tetrahedra and P2S74- corner-sharing tetrahedral pairs. Local structural and compositional probes including Raman spectroscopy, X-ray photoelectron spectroscopy, and X-ray pair distribution function analysis are employed here to arrive at a consistent description of the relative amounts of isolated tetrahedral units, which vary by 13% across the samples measured. This local structure variation translates to differences in the activation energies measured by electrochemical impedance spectroscopy in these samples, such that the higher concentration of isolated tetrahedra corresponds to a lower activation energy. The measured temperature-dependent ionic conductivity data are compared to conductivity results across the literature reported on the same compositions, highlighting the variation in the measured activation energy for nominally identical samples. These findings have implications for the critical need to play close attention to the local structure in solid electrolytes, particularly in systems that are glasses or glass ceramics, or those that comprise any amorphous contribution.

Chemical Control of Spin-Orbit Coupling and Charge Transfer in Vacancy-Ordered Ruthenium(IV) Halide Perovskites.

Vacancy-ordered double perovskites are attracting significant attention due to their chemical diversity and interesting optoelectronic properties. With a view to understanding both the optical and magnetic properties of these compounds, two series of RuIV halides are presented; A2 RuCl6 and A2 RuBr6 , where A is K, NH4 , Rb or Cs. We show that the optical properties and spin-orbit coupling (SOC) behavior can be tuned through changing the A cation and the halide. Within a series, the energy of the ligand-to-metal charge transfer increases as the unit cell expands with the larger A cation, and the band gaps are higher for the respective chlorides than for the bromides. The magnetic moments of the systems are temperature dependent due to a non-magnetic ground state with Jeff =0 caused by SOC. Ru-X covalency, and consequently, the delocalization of metal d-electrons, result in systematic trends of the SOC constants due to variations in the A cation and the halide anion.

Rapid and Tunable Assisted-Microwave Preparation of Glass and Glass-Ceramic Thiophosphate "Li7P3S11" Li-Ion Conductors.

Glass and glass-ceramic samples of metastable lithium thiophosphates with compositions of 70Li2S-30P2S5 and Li7P3S11 were controllably prepared by using a rapid assisted-microwave procedure in under 30 min. The rapid preparation times and weak coupling of the evacuated silica ampules with microwave radiation ensure minimal reactivity of the reactants and the container. The microwave-prepared samples display comparable conductivity values with more conventionally prepared (melt quenched) glass and glass-ceramic samples, on the order of 0.1 and 1 mS cm-1 at room temperature, respectively. Rietveld analysis of synchrotron X-ray diffraction data acquired with an internal standard quantitatively yields phase amounts of the glassy and amorphous components, establishing the tunable nature of the microwave preparation. X-ray photoelectron spectroscopy and Raman spectroscopy confirm the composition and the appropriate ratios of isolated and corner-sharing tetrahedra in these semicrystalline systems. Solid-state 7Li nuclear magnetic resonance (NMR) spectroscopy resolves the seven crystallographic Li sites in the crystalline compound into three main environments. The diffusion behavior of these Li environments as obtained from pulsed-field gradient NMR methods can be separated into one slow and one fast component. The rapid and tunable approach to the preparation of high quality "Li7P3S11" samples presented here coupled with detailed structural and compositional analysis opens the door to new and promising metastable solid electrolytes.

Ab initio computation for solid-state 31P NMR of inorganic phosphates: revisiting X-ray structures.

The complete 31P NMR chemical shift tensors for 22 inorganic phosphates obtained from ab initio computation are found to correspond closely to experimentally obtained parameters. Further improvement was found when structures determined by diffraction were geometry optimized. Besides aiding in spectral assignment, the cases where correspondence is significantly improved upon geometry optimization point to the crystal structures requiring correction.

Synthesis, Characterization, and Low Temperature Transport Properties of Eu11-xYbxCd6Sb12 Solid-Solution Zintl Phases.

Eu11-xYbxCd6Sb12 Zintl solid solutions have been prepared by tin flux reaction by employing the elements Eu/Yb/Cd/Sb/Sn in the ratio 11 - xp:xp:6:12:30, where xp is an integer less than 11 representing the preparative amount of Eu (11 - xp) and Yb (xp). Efforts to make the Yb compositions for x exceeding ∼3 resulted in structures other than the Sr11Cd6Sb12 structure type. The crystal structures and compositions were determined by single-crystal and powder X-ray diffraction and wavelength-dispersive X-ray analysis measurements. The title solid-solution Zintl compounds crystallize in the centrosymmetric monoclinic space group C2/m (no. 12, Z = 2) as the Sr11Cd6Sb12 structure type (Pearson symbol mC58), and the lattice parameters decrease with increasing ytterbium content. Single crystal X-ray diffraction shows that Yb atoms are not randomly distributed in the Eu sites but have a site preference which can be attributed to size effects. The influence of the rare earth (RE) metal sites on thermal and electronic properties of RE11Cd6Sb12 solid solutions has been studied by measuring their thermoelectric properties from 5 to 300 K after consolidation by either spark plasma sintering (SPS) or hot pressing (HP). Electron microprobe analysis reveals that some of the rare earth metal is lost during SPS; as a result pellets formed through SPS have lower electrical resistivity by an order of magnitude due to increased hole-charge carrier concentrations. While the carrier concentration increases, the mobility decreases due to deficiencies in Eu content. Refinement of powder X-ray diffraction shows that Eu loss is mainly from the Eu1 crystallographic site, which has a unique coordination suggesting that this site plays a key role in the transport properties of RE11Cd6Sb12.

Effect of Isovalent Substitution on the Structure and Properties of the Zintl Phase Solid Solution Eu7Cd4Sb8-xAsx (2 ≤ x ≤ 5).

A novel Zintl phase structure type, Eu7Cd4Sb8-xAsx (x = 2, 3, 4, and 5), with the general formula Eu7Cd4Pn8 (Pn = mixed occupancy Sb and As), was synthesized by molten tin flux reaction. Its structure was determined using single-crystal X-ray diffraction methods. This structure type is only preserved for 2 ≤ x ≤ 5 under our experimental conditions, and efforts to synthesize samples with x < 2 or x > 5 resulted in other structure types. The mixed occupancy Sb and As can be thought of as a pseudoatom whose ideal size, in this range of Sb/As ratios, fits the structure. The title phase crystallizes in the I-centered monoclinic space group I2/m (No. 12, Z = 4) with unit cell parameters ranging as follows: a = 19.7116(17)-19.4546(13) Å, b = 4.6751(4)-4.6149(3) Å, c = 24.157(2)-23.871(15) Å, and ß = 95.8798(1)-96.016(5)°, depending on the Sb/As ratio. The structure can be described as parallel double pentagonal tubes resulting from Cd-Pn and Pn-Pn bonding. These double pentagons are formed through corner sharing of the Cd-centered CdPn4 tetrahedra and a Pn-Pn interaction from two adjacent CdPn4 tetrahedra. This structure type is closely related to the Sr11Cd6Sb12 structure type as both share the same bonding features of Pn-Pn bonding and double pentagonal tubes. Electron microprobe analysis confirms the composition of these new Zintl solid solution phases. The As exhibits preferential substitution on specific sites, and site specificity trends are supported by lowest energy models from theoretical calculations. Theoretical calculations also predict that Sb-rich compounds should be metallic or semimetallic and that they should become more insulating as As content increases. Members of the solid-solution order ferromagnetically between 5 and 6 K and exhibit relatively low electrical resistivity between 50 and 300 K, ranging from ∼0.57 to ∼26 mΩ·cm, increasing with increasing As content.