Analysis Of Neutron Diffraction Data Research Articles

Role of Crystal Structure on the Ionic Conduction and Electrical Properties of Germanate Compounds A2Cu3Ge4O12 (A = Na, K)

Crystal structure and electrical properties of A2Cu3Ge4O12 (where A = Na, K) have been investigated by neutron diffraction and electrical impedance spectroscopy (EIS). The real and imaginary parts of the impedance, dielectric constant, and electrical modulus have been studied as a function of frequency and temperature. The crystal structures of the compounds K2Cu3Ge4O12 (KCGO) and Na2Cu3Ge4O12 (NCGO) are made of perfect 2D and quasi-2D alkali metal ion layers, respectively. The dc conductivity occurs due to small polaron hopping for both compounds with single activation energy over the entire experimentally available temperature range. The values of activation energies are 0.90(3) and 1.22(6) eV for KCGO and NCGO, respectively, as determined from dc conductivity and relaxation time analysis. The frequency dependent ac conductivity curves for both compounds follow a universal Jonscher’s power law. Soft bond valence sum analysis of neutron diffraction data reveals that the conduction pathways are confined within a plane in KCGO, whereas they form a one-dimensional channel in NCGO. The bottlenecks for ionic conduction and the role of crystal structure on them are discussed. The scaling behavior of electrical modulus indicates that the relaxation process does not change with temperature; however, a sharp decrease in the time constant has been observed. The present comprehensive study facilitates the understanding of the role of crystal structure on the microscopic mechanism of ionic conduction in both battery materials, which would be useful in designing sodium and potassium based ionic conductors. Further, the constant value of activation energy over the kHz frequency range is suitable for potential applications of the studied materials in avalanche beacons and amateur and geophysical sensors.

Lone Pair Rotation and Bond Heterogeneity Leading to Ultralow Thermal Conductivity in Aikinite.

Understanding the relationship between the crystal structure, chemical bonding, and lattice dynamics is crucial for the design of materials with low thermal conductivities, which are essential in fields as diverse as thermoelectrics, thermal barrier coatings, and optoelectronics. The bismuthinite-aikinite series, Cu1-x□xPb1-xBi1+xS3 (0 ≤ x ≤ 1, where □ represents a vacancy), has recently emerged as a family of n-type semiconductors with exceptionally low lattice thermal conductivities. We present a detailed investigation of the structure, electronic properties, and the vibrational spectrum of aikinite, CuPbBiS3 (x = 0), in order to elucidate the origin of its ultralow thermal conductivity (0.48 W m-1 K-1 at 573 K), which is close to the calculated minimum for amorphous and disordered materials, despite its polycrystalline nature. Inelastic neutron scattering data reveal an anharmonic optical phonon mode at ca. 30 cm-1, attributed mainly to the motion of Pb2+ cations. Analysis of neutron diffraction data, together with ab-initio molecular dynamics simulations, shows that the Pb2+ lone pairs are rotating and that, with increasing temperature, Cu+ and Pb2+ cations, which are separated at distances of ca. 3.3 Å, exhibit significantly larger displacements from their equilibrium positions than Bi3+ cations. In addition to bond heterogeneity, a temperature-dependent interaction between Cu+ and the rotating Pb2+ lone pair is a key contributor to the scattering effects that lower the thermal conductivity in aikinite. This work demonstrates that coupling of rotating lone pairs and the vibrational motion is an effective mechanism to achieve ultralow thermal conductivity in crystalline materials.

Interplay of spin, phonon, and lattice degrees in a hole-doped double perovskite: Observation of spin–phonon coupling and magnetostriction effect

Unlike a typical spin–phonon coupling, an exhibition of unconventional spin–phonon coupling, which is mediated via magnetostriction effect, is reported in a hole-doped double perovskite Pr1.5Sr0.5CoMnO6. Various investigations including electronic and crystal structures, spin structure, transport property, lattice dynamics, and theoretical density of states analysis by density-functional theory (DFT) have been performed. A substantial increase in the mean oxidation states of Co ions and a concurrent abrupt decrease in the resistivity upon Sr doping is observed, thus altering its underlying transport mechanism. An insulating and ferromagnetic (FM) ground state is predicted by DFT calculations. The neutron diffraction data analysis reveals a complex crystal structure of Pr1.5Sr0.5CoMnO6, which consists of B-site disordered monoclinic (P21/n) and orthorhombic (Pnma) structures, highlighting the presence of an anti-site disorder in the system. The analysis also suggests an overall FM ordering of Co/Mn spins below 150 K for the monoclinic phase, whereas no such magnetic ordering is found for the orthorhombic phase. More interestingly, the neutron powder diffraction study perceives the presence of a strong magnetostriction effect in the system. Raman spectroscopy unravels the presence of a spin–phonon coupling, which is essentially mediated by the magnetostriction effect.

To grind or not to grind? The influence of mechanical and thermal treatments on the Cu/Zn disorder in Cu2ZnSn(SxSe1-x)4 monograins

Kesterite-type based thin film solar cell technologies are mainly based on polycrystalline absorber layers. A promising low cost alternative technology uses Cu 2 ZnSn(S x Se 1-x ) 4 (CZTSSe) monograins (single crystals of 20–100 μm size) which are fixed in a polymer matrix to form a flexible solar cell. The Cu/Zn disorder is discussed as a possible reason for band tailing causing voltage losses limiting the efficiency of CZTSSe-based devices. The experimental determination of the order parameter Q which is a quantitative measure of Cu/Zn disorder, requires a differentiation between the isoelectronic cations Cu + and Zn 2+ . An in-depth analysis of neutron diffraction data allows the determination of type and concentration of intrinsic point defects including a distinction between Cu and Zn. Neutron diffraction requires large sample volumes, thus monograins offer the unique possibility to correlate structural disorder in CZTSSe with device performance parameters. In this study we tackle the influence of grinding the monograins on stoichiometry deviations, the Cu/Zn disorder as well as intrinsic point defects and optoelectronic properties of CZTSSe monograins. Moreover, an easy methodology based on Raman scattering spectroscopy is proposed for the assessment of Cu/Zn disorder in the CZTSSe compounds. • a significant impact on the order parameter Q in CZTSSe monograins from the “ordering” and “disordering” procedures. • The possibility to develop a fast and easy methodology to estimate the level of Cu/Zn disorder from Raman measurements. • Clear independence of the main structural, compositional and optoelectronic properties from the mechanical treatment.

Formation of the structure-II gas hydrate from low-concentration propane mixed with methane

It has been recognized that a small amount of propane mixed with methane can change greatly in not only the thermodynamics but also the structural properties of gas hydrate. However, its mechanism is still not well understood yet. In this research, structure-II (sII) hydrate is synthesized using a methane-propane gas mixture with an initial mole ratio of 99:1, and it is found that large (51264) cages are co-occupied by multiple gases based on the rigid structure analysis of neutron diffraction data. The first principles calculation and molecular dynamics simulation are conducted to uncover the molecular mechanism for sII methane-propane hydrate formation, revealing that the presence of propane inhibits the formation of structure-I (sI) hydrate but promotes sII hydrate formation. The results help to understand the accumulation mechanism of natural gas hydrate and benefit to optimize the condition for gas storage and transportation in hydrate form.

Simultaneous Reduction of Proton Conductivity and Enhancement of Oxide-Ion Conductivity by Aliovalent Doping in Ba7Nb4MoO20.

Hexagonal perovskite-related oxides have garnered a great deal of research interest because of their high oxide-ion conductivity at intermediate temperatures, with Ba7Nb4MoO20 being a notable example. However, concomitant proton conduction in Ba7Nb4MoO20 may cause a decrease in power efficiency when used as the electrolyte in conventional solid oxide fuel cells. Here, through investigations of the transport and structural properties of Ba7Nb4-xWxMoO20+x/2 (x = 0-0.25), we show that the aliovalent substitution of Nb5+ by W6+ not only increases the oxide-ion conductivity but also dramatically lowers proton conductivity. The highest conductivity is achieved for x = 0.15 composition, with 2.2 × 10-2 S cm-1 at 600 °C, 2.2 times higher than that of pristine Ba7Nb4MoO20. The proton transport number of Ba7Nb3.85W0.15MoO20.075 is smaller compared with Ba7Nb4MoO20, Ba7Nb3.9Mo1.1O20.05, and Ba7Ta3.7Mo1.3O20.15. The structure analyses of neutron diffraction data of Ba7Nb3.85W0.15MoO20.075 at 25 and 800 °C reveal that the aliovalent W6+ doping introduces interstitial oxide ions in the intrinsically oxygen-deficient c' layers, thereby simultaneously increasing the carrier concentration for oxide-ion conduction and decreasing oxygen vacancies responsible for dissociative absorption of water. Neutron scattering length density distribution was examined using the maximum-entropy method and neutron diffraction data at 800 °C, which indicates the interstitialcy oxide-ion diffusion in the c' layers of Ba7Nb3.85W0.15MoO20.075. Ba7Nb3.85W0.15MoO20.075 exhibits extremely high chemical and electrical stability in the wide oxygen partial pressure P(O2) region [ex. 10-23 ≤ P(O2) ≤ 1 atm at 903 °C]. The present results offer a strategy for developing pure oxide-ion conducting hexagonal perovskite-related oxides for possible industrial applications.

PyRS: a user-friendly package for the reduction and analysis of neutron diffraction data measured at the High Intensity Diffractometer for Residual Stress Analysis

The pyRS (Python residual stress) analysis software was designed to address the data reduction and analysis needs of the High Intensity Diffractometer for Residual Stress Analysis (HIDRA) user community. pyRS implements frameworks for the calibration and reduction of measured 2D data into intensity versus scattering vector magnitude and subsequent single-peak-fitting analysis to facilitate texture and residual strain/stress analysis. pyRS components are accessible as standalone user interfaces for peak-fitting and stress/strain analysis or as Python scripts. The scripting interface facilitates automated data reduction and peak-fitting analysis using an autoreduction protocol. Details of the implemented functionality are discussed.

Visualizing lithium ions in the crystal structure of Li3PO4 by in situ neutron diffraction

Li3PO4 is known to demonstrate Li+ ionic conductivity, making it a good candidate for solid electrolytes in all-solid batteries. Understanding the crystal structure and its connection to Li+ diffusion is essential for further rational doping to improve the ionic transport mechanism. The purpose of this study is to investigate this mechanism using anisotropic displacement parameters (ADPs), nuclear density distribution and bond valence mapping. In situ neutron powder diffraction experiments have been performed using the high-resolution powder diffractometer ECHIDNA at the OPAL reactor, Australian Centre for Neutron Scattering, Australian Nuclear Science and Technology Organisation, NSW, Australia. The ADPs and nuclear density distribution were determined from the analysis of neutron diffraction data using the Rietveld method, whereas the bond valence map was calculated from the refined structure. The crystal structure remained unchanged as the temperature was increased (3, 100, 300 and 400 K). However, the ADPs show a greater increase in anisotropy in the a and b axes compared with the c axis, indicating the tendency of the ionic movement. By combining nuclear density distribution and bond valence mapping, the most likely lithium-ion diffusion in the crystal structure can be visualized.

Magnetic structure, excitations and short-range order in honeycomb Na2Ni2TeO6

Na2Ni2TeO6 has a layered hexagonal structure with a honeycomb lattice constituted by Ni2+ and a chiral charge distribution of Na+ that resides between the Ni layers. In the present work, the antiferromagnetic (AFM) transition temperature of Na2Ni2TeO6 is confirmed at T N ≈ 27 K, and further, it is found to be robust up to 8 T magnetic field and 1.2 GPa external pressure; and, without any frequency-dependence. Slight deviations from nominal Na-content (up to 5%) does not seem to influence the magnetic transition temperature, T N. Isothermal magnetization curves remain almost linear up to 13 T. Our analysis of neutron diffraction data shows that the magnetic structure of Na2Ni2TeO6 is faithfully described by a model consisting of two phases described by the commensurate wave vectors , and , with an additional short-range order component incorporated in to the latter phase. Consequently, a zig-zag long-range ordered magnetic phase of Ni2+ results in the compound, mixed with a short-range ordered phase, which is supported by our specific heat data. Theoretical computations based on density functional theory predict predominantly in-plane magnetic exchange interactions that conform to a J 1–J 2–J 3 model with a strong J 3 term. The computationally predicted parameters lead to a reliable estimate for T N and the experimentally observed zig-zag magnetic structure. A spin wave excitation in Na2Ni2TeO6 at E ≈ 5 meV at T = 5 K is mapped out through inelastic neutron scattering experiments, which is reproduced by linear spin wave theory calculations using the J values from our computations. Our specific heat data and inelastic neutron scattering data strongly indicate the presence of short-range spin correlations, at T > T N, stemming from incipient AFM clusters.

On the Lithium Distribution in Halide Superionic Argyrodites by Halide Incorporation in Li7–xPS6–xClx

Superionic lithium argyrodites are attractive as solid electrolytes for all-solid-state-batteries. These materials of composition Li6PS5X (X = Cl, Br, and I) exhibit structural disorder between the X−/S2− positions, with higher disorder realizing better Li+ transport. Further replacement of the sulfide by chloride anions (for the series Li7−xPS6−xClx) has been shown to increase the ionic conductivity. However, the underlying changes to the lithium substructure are still relatively unknown. Here we explore a larger range of nominal halide compositions in this material from x = 0.25 to x = 1.5 and explore the changes with neutron diffraction and impedance spectroscopy. The replacement of S2− by Cl−causes a lowered average charge in the center of the prevalent Li+ “cages”, which in turn causes weaker interactions with Li+ ions. Analysis of neutron diffraction data reveals that the increased Cl− content causes these clustered Li+ “cages” to become more interconnected, thereby increasing Li+ conductivity through the structure. This study explores the understanding of the fundamental structure–transport correlations in the argyrodites, specifically structural changes withinthe Li+ ion substructure upon changing anionic charge distribution.

Electrical Properties, Defect Structures, and Ionic Conducting Mechanisms in Alkali Tungstate Li2W2O7.

Discovery of new high-conductivity solid-state ionic conductors has been a long-lasting interest in the field of solid-state ionics for their important applications in solid-state electrochemical devices. Here, we report the mixed oxide-ion and Li-ion conductions, together with their conducting mechanisms in the Li2W2O7 material with triclinic symmetry. The process for the ionic identity is supported by several electrochemical measurements including electrochemical impedance spectroscopy, DC polarization, oxygen concentration cell, and theoretical analysis of neutron diffraction data and bond-valence-based energy landscape calculations. We show from electrochemical measurements strong evidences of the predominating oxide-ion conducting and minor Li-ion chemistry in Li2W2O7 at high temperatures, while the bond-valence-based energy landscape analysis reveals possible multidimensional ionic migration pathways for both oxide-ions and Li-ions. Thus, the presented results provide fundamental insights into new mixed ionic conduction mechanisms in low-symmetry materials and have implications for discoveries of new ionic conductors in years to come.

Emergence of metamagnetic transition, re-entrant cluster glass and spin phonon coupling in Tb2CoMnO6

The double perovskite compound Tb2CoMnO6 has been investigated using x-ray absorption spectroscopy (XAS), Raman spectroscopy, magnetic measurements and ab initio band structure calculations. It is observed that both anti-ferromagnetic (AFM) and ferromagnetic (FM) phase coexist in this material. The presence of anti-site disorder (ASD) has been established from the analysis of neutron diffraction data. Moreover, a prominent metamagnetic transition is observed in the M(H) behavior that has been explained with the drastic reorientation of the pinned domain which are aligned antiparallel by the antiphase boundaries (APBs) at zero field. The ASD further gives rise to spin frustration at low temperature which leads to the re-entrant cluster glass ∼33 K. The coupling between phononic degree of freedom and spin in the system has also been demonstrated. It is observed that the theoretical calculation is consistent with that of the experimentally observed behavior.

Neutronography of Irradiated Reactor Austenitic Steels

The neutron diffracttion studies of the samples of fuel element claddings made of EK-164 and ChS-600 austenitic steels in the initial state and after operation in a BN-600 fast neutron reactor are reviewed. The samples were investigated in a wide range of fast neutron doses and irradiation temperatures, up to ∼80 displacements per atoms (dpa) and 628°C, respectively. Various microstructural characteristics, such as microstresses, dislocation density, and crystallographic texture are determined using full-profile analysis of neutron diffraction data. At high doses studied in this work, the irradiation temperature is the dominant factor responsible for the dislocation density. The procedures of analyzing and revealing defect types were preliminary developed on specially prepared nickel samples and austenitic alloys upon irradiation in the IVV-2M reactor core at a temperature near 80°С, which provided a low thermal mobility of lattice defects. The results obtained in some first diffraction studies on samples after their operation in the reactor core show that neutron data can be used to characterize the microstructures formed due to irradiation and, at least, estimate the mechanical properties of irradiated materials without their destruction and with no radiation risk for personnel.

High Proton Conductivity in Ba5Er2Al2ZrO13, a Hexagonal Perovskite-Related Oxide with Intrinsically Oxygen-Deficient Layers.

For the development of proton-based electrolytes, high proton conductivity at intermediate temperatures (300-600 °C) is crucial, but the available materials have been confined to a limited number of the structure families, such as cubic perovskites. Herein, we report Ba5Er2Al2ZrO13, a hexagonal perovskite-related oxide, as a new class of proton conductors exhibiting higher conductivities than 10-3 S cm-1 between 300 and 1200 °C. The protons as charge carriers are found to exist in the inherently oxygen-deficient h' layer of Ba5Er2Al2ZrO13, which are supported by Rietveld analysis of neutron-diffraction data, bond-valence-based energy calculations, and thermogravimetric analysis. Our discovery of a new structure family of proton conductors with the inherently oxygen-deficient h' layer offers a strategy in designing superior proton conductors based on hexagonal perovskite-related oxides.

Magnetodielectricity induced by coexisting incommensurate conical magnetic structure and cluster glass-like states in polycrystalline BaFe10In2O19

Indium doped barium hexaferrite BaFe10In2O19 is shown to exhibit complex magnetic behaviour below 110 K wherein there is a coexistence of a long-range conical magnetic order along with a cluster spin-glass-like state. Temperature dependent dc magnetization measurements reveal that the system exhibits an anomaly around 110 K. Temperature dependent neutron diffraction (ND) measurements measured in the Q-range 0.28–7.35 Å−1 characterize this anomaly as a transition to a longitudinal conical magnetic state from the ferrimagnetic state at room temperature. Ac susceptibility and thermoremanent magnetization relaxation measurements also reveal the existence of cluster spin-glass like behavior below 110 K, indicating coexistence with conical magnetic order. The lattice parameters determined from the analysis of ND data show a sharp change at ∼110 K which is also reflected in the anomalous changes seen in the temperature dependent Raman phonon modes around this temperature. This gives a clear indication of spin lattice coupling in the system. Finally, temperature and magnetic field dependent dielectric constant measurements reveal the occurrence of large magnetodielectric effect (MDE) near 110 K. This intriguing intrinsic magnetodielectric feature can be explained in terms of spin lattice coupling.

Spin phonon coupling in Mn doped HoFeO3 compounds exhibiting spin reorientation behaviour

An investigation has been carried out on the spin phonon coupling in a series of isostructural polycrystalline orthorhombic (Space group Pnma) compounds HoFe1−XMnXO3 (x ⩽ 0.6) exhibiting spin reorientation below Néel temperature (TN), using magnetization, neutron diffraction, and Raman scattering techniques. Mn doping leads to an anomalous increase in the spin reorientation temperature (TSR), shifting it close to room temperature from TSR ~ 60 K for x = 0 sample, and concomitant lowering of TN. The TSR is absent in samples for x ⩾ 0.5. The magnetic structure undergoes a transition at TSR from Γ4 → Γ1 in the Mn doped compounds as against Γ4 → Γ2 observed in HoFeO3 sample. In the region T < TN an anomalous softening of Raman phonon modes viz., B2g(5) and B3g(3), identified with the stretching motion and breathing mode, respectively, of Fe/Mn–O6 octahedra, is observed in compounds exhibiting spin-reorientation behaviour, indicating a spin-phonon coupling in these compounds. A quadratic correlation between the deviation of phonon frequency and variation of antiferromagnetic moment (Δω M2) is observed in these compounds. The temperature evolution of the M2+ mode obtained from the analysis of neutron diffraction data based on symmetry adapted mode decomposition of the Pnma structure further corroborates the mode softening observation.

Realization of spin-canted magnetism from lattice site specific spin structure in the double perovskite Nd2CoTiO6

Abstract The magnetic, dielectric and structural properties of a double perovskite oxide Nd2CoTiO6 (NCTO), synthesized by solid state reaction method, have been studied. The Rietveld refinement of the room temperature neutron diffraction (ND) pattern specifies that the crystal structure of NCTO is monoclinic with space group P21/n, which contains an ordered array of alternate CoO6 and TiO6 octahedra. Magnetization measurements, carried out from room temperature to 2 K indicate a transition at ∼17 K. The rise of magnetization sharply below ∼17 K is attributed to the magnetic ordering of Nd3+ ions. Ac susceptibility data recorded in the range 70 K–5 K ruled out the presence of spin glass behavior in NCTO. To confirm the nature of magnetic ordering, temperature-dependent ND measurements were carried out and the analysis of ND data recorded at 15 K and 3 K shows the presence of canted antiferromagnetic spin structure of NCTO at low temperatures. Thermal variation of dielectric permittivity shows an anomaly at ∼720 K. First principles density functional theory (DFT) has been invoked to determine the band structure of the sample. The electronic structure has also been extensively investigated to correlate different observed properties of the sample.

Defect structure in δ-Bi5PbY2O11.5.

A detailed study of the defect structure in a di-substituted δ-Bi2O3 type phase, δ-Bi5PbY2O11.5, is presented. Using a combination of conventional Rietveld analysis of neutron diffraction data, reverse Monte Carlo (RMC) analysis of total neutron scattering data and ab initio molecular dynamics (MD) simulations, both average and local structures have been characterized. δ-Bi5PbY2O11.5 represents a model system for the highly conducting δ-Bi2O3 type phases, in which there is a higher nominal vacancy concentration than in the unsubstituted parent compound. Uniquely, the methodology developed in this study has afforded the opportunity to study both oxide-ion vacancy ordering as well as specific cation–cation interactions. Oxide-ion vacancies in this system have been found to show a preference for association with Pb2+ cations, with some evidence for clustering of these cations. The system shows a non-random distribution of vacancy pair alignments, with a preference for 〈100〉 ordering, the extent of which shows thermal variation. MD simulations indicate a predominance of oxide-ion jumps in the 〈100〉 direction.

Structural study of amorphous and nanocrystalline Mg-based metallic glass examined by neutron diffraction, X-ray photoelectron spectroscopy, Reverse Monte Carlo calculations and high-resolution electron microscopy

The microstructure of amorphous and nanocrystalline Mg65Cu20Y10Zn5 alloy in as-quenched and post-annealed state was examined using neutron diffraction (ND), Reverse Monte Carlo modeling (RMC) and high-resolution transmission electron microscopy (HRTEM). The surface characteristic of Mg-based glass was investigated by X-ray photoelectron spectroscopy (XPS) method. The corrosion activity of alloy in glassy and nanocrystalline state was determined by electrochemical polarization measurements conducted in 3.5% NaCl solution. It was found that the structure of the melt-spun glass is homogeneous, but some medium-range order (MRO) regions as small as 1–2 nm were observed. The RMC analysis of ND data was used for local atomic structure and coordination numbers of the Mg65Cu20Y10Zn5 alloy in as-quenched state. The three-dimensional model representing a simulation box with atomic arrangements was also proposed. An average coordination number for Mg-Mg and Mg-Cu atoms is 8.1 and 2.5, adequately. The formation of nanocrystalline structure after annealing was confirmed by X-ray diffraction (XRD) and HRTEM observations. The TEM and HRTEM techniques allowed to observe regions containing very small particles in the amorphous matrix with size of 4–10 nm. The selected area electron diffraction (SAED) patterns allowed to identified hexagonal Mg and orthorhombic Mg2Cu phases. XPS results indicated the co-existence of MgO and Mg(OH)2 on the surface film formed on glassy ribbon in as-quenched state. The electrochemical polarization measurements revealed that the glassy ribbon exhibited lower corrosion current density than nanocrystalline sample.

Competing Structural Influences in the Li Superionic Conducting Argyrodites Li6PS5- xSe xBr (0 ≤ x ≤ 1) upon Se Substitution.

Lithium-ion conducting argyrodites have recently attracted significant interest as solid electrolytes for solid-state battery applications. In order to enhance the utility of materials in this class, a deeper understanding of the fundamental structure-property relationships is still required. Using Rietveld refinements of X-ray diffraction data and pair distribution function analysis of neutron diffraction data, coupled with electrochemical impedance spectroscopy and speed of sound measurements, the structure and transport properties within Li6PS5- xSe xBr (0 ≤ x ≤ 1) have been monitored with increasing Se content. While it has been previously suggested that the incorporation of larger, more polarizable anions within the argyrodite lattice should lead to enhancements in the ionic conductivity, the Li6PS5- xSe xBr transport behavior was found to be largely unaffected by the incorporation of Se2- due to significant structural modifications to the anion sublattice. This work affirms the notion that, when optimizing the ionic conductivity of solid ion conductors, local structural influences cannot be ignored and the idea of "the softer the lattice, the better" does not always hold true.