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Computationally Guided Discovery of the Sulfide Li3AlS3 in the Li–Al–S Phase Field: Structure and Lithium Conductivity
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Computationally Guided Discovery of the Sulfide Li3AlS3 in the Li–Al–S Phase Field: Structure and Lithium Conductivity
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Chemistry of Materials

Cite this: Chem. Mater. 2019, 31, 23, 9699–9714
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https://doi.org/10.1021/acs.chemmater.9b03230
Published October 23, 2019

Copyright © 2019 American Chemical Society. This publication is licensed under CC-BY.

Abstract

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With the goal of finding new lithium solid electrolytes by a combined computational–experimental method, the exploration of the Li–Al–O–S phase field resulted in the discovery of a new sulfide Li3AlS3. The structure of the new phase was determined through an approach combining synchrotron X-ray and neutron diffraction with 6Li and 27Al magic-angle spinning nuclear magnetic resonance spectroscopy and revealed to be a highly ordered cationic polyhedral network within a sulfide anion hcp-type sublattice. The originality of the structure relies on the presence of Al2S6 repeating dimer units consisting of two edge-shared Al tetrahedra. We find that, in this structure type consisting of alternating tetrahedral layers with Li-only polyhedra layers, the formation of these dimers is constrained by the Al/S ratio of 1/3. Moreover, by comparing this structure to similar phases such as Li5AlS4 and Li4.4Al0.2Ge0.3S4 ((Al + Ge)/S = 1/4), we discovered that the AlS4 dimers not only influence atomic displacements and Li polyhedral distortions but also determine the overall Li polyhedral arrangement within the hcp lattice, leading to the presence of highly ordered vacancies in both the tetrahedral and Li-only layer. AC impedance measurements revealed a low lithium mobility, which is strongly impacted by the presence of ordered vacancies. Finally, a composition–structure–property relationship understanding was developed to explain the extent of lithium mobility in this structure type.

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This paper was published ASAP on November 22, 2019, with an error in Figure 3. The corrected version was reposted on November 26, 2019.

1. Introduction

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All solid-state batteries (ASSBs) are of considerable current interest because they are a potential route to the use of lithium metal anodes while avoiding dendrite formation. (1,2) Solid-state electrolytes (SSEs) offer advantages over liquid electrolytes, such as large electrochemical stability windows and better thermal stability, (3,4) and have a lithium transport number of unity. Moreover, inorganic crystalline lithium ion conductors have superior ionic conductivity compared to organic polymers. (5) Recent reviews compared the different families of Li electrolytes, (5−9) and sulfides have the highest Li ion conductivity. For instance, members of the thio-LISICON family (10−14) such as the Li7P3S11 crystalline phase discovered in the Li2S–P2S5 system (15,16) and the Li–argyrodites Li6PS5X (X = Cl, Br, I) (17,18) have superior ionic conductivities, σ, ∼1 to 20mScm–1 at room temperature (RT) and low activation energies, Ea, ∼0.20 eV. These values are competitive with those of liquid electrolytes and make them promising candidates for integration in ASSBs. The sulfide anion is larger than oxide and more polarizable and affords lower frequency lattice vibrations, all favoring higher lithium mobility, (19−21) while superior mechanical properties offer lower grain boundary resistance (6) and allow easier processing into dense pellets. While these characteristics indicate superiority of sulfides over oxides, the usually narrower electrochemical stability window of the former can lead to parasitic reactions at the electrodes and considerably limit the performance and life cycle of ASSBs containing sulfide electrolytes. (5,11,22) Moreover, sulfide materials are often not stable in air, which makes them more difficult to handle. Further improvement of SSEs is needed for their commercialization, which implies finding materials showing good ionic conductivity as well as being able to form stable and conducting interfaces at the cathode and anode sides. (8,14,23)
Given the large number of candidate material compositions for potential new SSEs, computation has been extensively used to guide experimental work. On the one hand, some studies focus on currently known materials in order to produce an understanding of the underlying mechanisms for ion transport thanks to density functional theory (DFT) energy landscape methods and molecular dynamics. (20,24,25) The need for higher throughput screening methods led to database-driven approaches where models of ion transport, such as the development of predictive performance metrics, (26) are used to prioritize existing materials for evaluation as SSE. This can be done for example through the use of machine learning algorithms combined with first-principles calculations (27,28) or with bond valence mapping analysis. (18,29−31) On the other hand, the discovery of new materials with unique compositions and/or structures can be accelerated by predicting the most stable compounds within a chosen phase field prior to experimentation. The crystal structure for which the energy is calculated can be either thought to be isostructural to a known material in which original substitutions are performed (32−34) or can be determined through crystal structure prediction techniques. (35−37)
A relatively few mixed anion systems have been studied as SSE. Such materials can combine the advantages of each individual anion and may also offer new structure types for ion transport. The good performance of argyrodite sulfide halide materials demonstrates the potential of such mixed anion systems. (18,38) Oxysulfide phases, especially for lithium solid electrolyte applications, however remain less explored (39−42) and could be a promising approach to yield new materials. In particular, the oxygen for sulfur substitution in LGPS structures has been an area of investigation. (40,42) For instance, Kim et al. (42) reported the study of the Li10SiP2S12–xOx (0 < x < 1.75) solid solution, which resulted in an optimal conductivity for x = 0.7. Another interesting example is the theoretical study by Wang et al., presenting O doping into β-Li3PS4, which showed that the oxygen insertion enabled lower activation energy barriers, improved electrochemical stability, and created a beneficial 3D connection pathway for Li diffusion. (41) Moreover, among non-crystalline materials, oxysulfide glasses such as combinations of Li2S–P2S5–P2O5 (43) or Li2S–SiS2–LiBO2 (44) have been studied as potential lithium solid electrolytes and showed promising properties.
In this study, we evaluate oxysulfides of aluminum as candidate lithium ion conductors due to the earth abundance, low cost and toxicity, high polarizability, and redox inactivity. The composition LiAlOS was previously identified as a new potential interesting solid electrolyte target in a computation-only study. (37) The present study of the Li–Al–O–S phase diagram was guided by computational evaluation of the stability of candidate compositions, which both highlights where new phases are likely to be found and allows assessment of the amount of experimental effort to be invested at each composition. Within this phase diagram, the new sulfide phase Li3AlS3 was identified and its structure and lithium ion conductivity were characterized.

2. Experimental Section

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2.1. Synthesis

2.1.1. Materials

Li2S (99.98%), LiNO3 (>99%), Li2CO3 (>99%), 7Li2CO3 (99% 7Li), and Al(OH)3 (reagent grade) were purchased from Sigma Aldrich, while Li2O (99.5%), urea (99.0%), Al2S3 (99%+), and Al(NO3)3·9H2O (98%) were obtained from Alfa Aesar.

2.1.2. Exploratory Synthesis of the Compounds in the Li–Al–O–S Phase Field

For all sulfide-containing materials, precursors and resulting powders were handled in a He-filled glovebox. Compositions belonging to the Li–Al–O–S phase diagram were synthesized from stoichiometric mixtures of Li2O, Al2S3, and, when needed, Li2S and pre-synthesized LiAlO2 (according to a procedure from Gao et al., (45)cf. the Supporting Information, SI). The precursors were weighed in the appropriate amount in order to obtain a total mass of 300 mg. The powders were then mixed and ground in an agate mortar for 15 min, transferred to an alumina crucible, and placed in a quartz tube before sealing under vacuum (10–4 mbar). The tube containing the sample was heated to 800 °C at a ramp rate of 5 °C·min–1, held at 800 °C for 48 h, and then quenched in water. The resulting powder was then manually ground in order to obtain a fine powder.

2.1.3. Final Synthesis of Li3AlS3

After identifying Li3AlS3 as a new phase through the described synthesis method above, its synthesis was slightly modified in order to improve purity. Li2S (1.4358 g, 31.2 mmol) and Al2S3 (1.5642 g, 10.4 mmol) were weighed according to the stoichiometric 3:1 ratio. The resulting powders were then mixed and ground in an agate mortar for 15 min, transferred in an alumina crucible, and placed in a quartz tube before sealing under vacuum (10–4 mbar). The tube containing the sample was heated at 700 °C for 12 h and then to 800 °C for 12 h with an intermediate grinding step in between both firings. The heating ramp rate of the furnace was 5 °C·min–1, and cooling was performed by quenching the tube in water. Neutron powder diffraction (NPD) experiments were conducted on 7Li-enriched samples of 7Li3AlS3, using 7Li2S as the precursor material, which was synthesized according to a method described by Leube et al. (46) starting from 7Li2CO3. For consistency of the structural analysis, the 7Li3AlS3 sample was also used for synchrotron diffraction experiments.
The importance of the quenching step was investigated by either letting the sample cool down by turning off the furnace or by setting the cooling ramp rate to 1 °C·min–1. The sample cooled down by turning the furnace off did not show any extra impurity peaks in the X-ray diffraction pattern; however, the sample cooled with the 1 °C·min–1 ramp resulted in the partial decomposition into Li5AlS4 and LiAlS2. This decomposition was also observed when a formerly prepared Li3AlS3 sample was heated slowly to 700 °C at 1 °C·min-1, maintained at this temperature for 30 min, and quenched to room temperature. We therefore maintained the 5 °C·min–1 fast heating ramp rate and the quenching step for the synthesis of the material.

2.2. Probe Structure Generation and Energy Calculations

All energies were computed using periodic DFT with the VASP program. (47) The PBE functional was used (48) with the projector augmented wave approach to treat core electrons. (49)
A probe structure approach was used to sample compositions in the Li+–Al3+–O2––S2– phase space. (36) Crystal structure prediction (CSP) was used to generate a probe structure at each composition. Each probe structure was assumed to have an energy close enough to the global minimum energy structure to assess the thermodynamic stability of a hypothetical compound at that composition against the formation of an assemblage of known phases.
The CSP was performed using the in-house code ChemDASH (Chemically Directed Atom Swap Hopping). Cells containing hexagonal close-packed (hcp) and cubic close-packed (ccp) anion lattices hosting O2– and S2– were constructed, and some octahedral and tetrahedral interstitial sites occupied by Li+ and Al3+ cations. The hcp cells contained eight anions, and the ccp cell contained nine anions, with a correct number of cations to satisfy charge neutrality at each composition. Structures were initialized with a random decoration of the anion and cation sublattices, and their structures were optimized. To generate new structures, the positions of some anions were swapped on the anion sublattice, or in the interstitial sites, the positions of some cations were either swapped or moved to previously vacant interstitial sites. The new structure was then optimized by relaxation of the atomic positions to the nearest local minimum. At each step, a Monte Carlo sampling algorithm was used to accept swaps, which lowered the energy of the system or increased it by an amount lower than the Monte Carlo energy threshold. The process was continued until 1000 structures had been generated and the lowest energy structure at each composition was taken forward for calculating the stability.
One of the features of ChemDASH is to perform structural optimizations in a number of stages, which can use different parameters. This was done when optimizing each of the structures generated during the CSP process, with each stage using an increasing level of accuracy. In the first stage of each geometry optimization, Γ point-only calculations were used with a plane wave cutoff of 400 eV. By the final stage of each geometry optimization, a 2 × 2 × 2 k-point grid was used with a plane wave cutoff of 600 eV. The cell vectors and atomic positions were optimized until forces fell below 0.02 eV·Å–1.
Once a probe structure had been obtained, its energy was recalculated at a more accurate level, which was also the level of accuracy used to calculate the energies of previously reported phases. These energies were used to generate the convex hulls of chemical stability. A plane wave cutoff of 700 eV was used with a k-point spacing of 0.15 Å–1. Cell vectors and atomic positions were optimized until forces fell below 0.001 eV·Å–1. The convex hull of chemically stable compositions was generated using pymatgen. (50)
DFT calculations were also performed on an ordered analogue of the experimentally refined crystal structure of Li3AlS3. The split Li sites were merged onto a single high-symmetry site, and all sites were given full occupancy. The structure was then optimized in VASP using the more accurate parameters detailed above. No imaginary frequency modes were found in phonon calculations, showing that the structure is stable against displacement of ions from their relaxed positions. The computed phonon frequencies are presented in Table S2 of the SI.

2.3. Elemental Analysis

Elemental analysis of Li3AlS3 was performed by Mikroanalytishes Labor Pascher at Remagen-Bandorf, Germany, after dissolution in a HF/HCl solution at elevated temperature and pressure.

2.4. Diffraction

2.4.1. X-ray Diffraction

Synchrotron X-ray diffraction (SXRD) was performed at Diamond Light Source UK, on high-resolution beamline I11, at λ = 0.82465 Å. The sample was introduced into a 0.7 mm diameter borosilicate glass capillary to record the pattern in transmission mode [0 ° < 2θ < 150°, and Δ(2θ) = 0.004°] using a high-resolution multianalyzer crystal (MAC) detector. The experiment was performed at room temperature. For the Rietveld refinement, the Thompson–Cox–Hastings function (54) with spherical harmonic expansion implemented in FullProf was used to model the peak shape anisotropy. (55) In particular, the (−311), (−402), (−602), and (331) reflections showed a pronounced anisotropic peak shape broadening, which could be due to the presence of structural defects such as antiphase domains and stacking faults. (56) The improvement of the fit thanks to the use of spherical harmonics is illustrated in Figure S3.

2.4.2. Neutron Diffraction

Time-of-flight neutron powder diffraction (NPD) data were collected on Li3AlS3 using a high-resolution powder diffractometer (HRPD) instrument at ISIS, UK. Experiments were carried out at ambient temperature on the 7Li-enriched sample sealed in thin-walled vanadium cans with a diameter of 8 mm, sealed with an indium gasket under 1 atm of helium gas. For the Rietveld refinement, all banks were fitted simultaneously with the TOF pseudo-Voigt back-to-back exponential function with spherical harmonic expansion as for the SXRD data refinement. The structure determination was performed using Jana2006 (68) in order to utilize the charge flipping method implemented in the software to yield an initial model. FullProf (70) then had our preference for complete refinement.

2.5. Nuclear Magnetic Resonance (NMR) Spectroscopy

The 6Li magic-angle Spinning (MAS) NMR spectra were recorded at 9.4 T on a Bruker DSX spectrometer using a 4 mm HXY MAS probe (in double resonance mode) and at 20 T on a Bruker NEO spectrometer using a 3.2 mm HXY MAS probe (in triple resonance mode). The 6Li MAS spectra were obtained at 9.4 T with a pulse length of 3 μs at a radiofrequency (f) field amplitude of ω1/2π = 83 kHz and a MAS rate of ωr/2π = 10 kHz and at 20 T with a pulse length of 4.5 μs at an rf field amplitude of ω1/2π = 56 kHz and a MAS rate of ωr/2π = 20 kHz. The 27Al MAS NMR data were recorded at 9.4 T on a Bruker Avance III HD under MAS at a rate of ωr/2π = 12 kHz using a 4 mm HXY MAS probe (in double resonance mode) and at 20 T on a Bruker NEO spectrometer using a 3.2 mm HXY MAS probe (in triple resonance mode). The 27Al spectra were obtained at 9.4 T with a short pulse angle of 30° of 0.33 μs duration at an rf amplitude of ω1/2π = 83 kHz and at 20 T with a short pulse angle of 30° of 0.55 μs duration at an rf amplitude of ω1/2π = 50 kHz. The 27Al triple quantum magic-angle spinning (MQMAS) (57) was obtained at 9.4 T with a z-filtered sequence (58) and using rf field amplitudes of ω1/2π = 83 kHz for the excitation and reconversion pulses and 4 kHz for the selective 90° pulse. All spectra were collected at room temperature and obtained under quantitative recycle delays of more than 5 times longer than the spin–lattice relaxation times T1, which were measured using the saturation recovery pulse sequence and fitted with a stretch exponential function of the form 1 – exp[−(τ/T1)β] (with β ranging from 0.3 to 1). The 6Li and 27Al shifts were referenced to 10 M LiCl in D2O and 0.1 M Al(NO3)3 in H2O at 0 ppm, respectively.

2.6. AC Impedance Spectroscopy

A pellet of the Li3AlS3 powder was made by uniaxially pressing ∼30 mg of powder in a 5 mm diameter cylindrical steel die at a pressure of 125 MPa, followed by sintering in an evacuated quartz tube at 800 °C for 12 h. A relative density of 80% was obtained by this method.
AC impedance measurements were performed using an impedance analyzer (Solartron 1296 dielectric interface coupled with a Solartron 1255B frequency response analyzer) in the frequency range from 1 MHz to 100 mHz (with an amplitude of 50 mV). Silver paint (RS silver conducting paint 186-3600), brushed on both sides of the pellet and dried under vacuum at room temperature, was used as ion blocking electrodes. Variable temperature conductivity measurements were carried out under argon (flow rate 50 mL·min–1), using a custom-built sample holder, in the temperature range 25–125 °C. The impedance spectra were fitted with an equivalent circuit using the ZView2 program. (59)

3. Results and Discussion

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3.1. Computational/Experimental Study of the Li–Al–O–S Phase Field

We explored the Li–Al–O–S phase field using probe structure-based material discovery. (35,36) This method involves identifying a set of unexplored compositions on the phase field of interest and computationally generating a probe structure for each one. By determining the energy of each of the probe structures compared to the convex hull, we can identify low-energy regions of the phase diagram and hence target synthetic efforts toward regions of the phase field where new compounds are more likely to be found. To ensure fully occupied anion sublattices, the compositions of unit cells used in calculations were constrained to contain eight or nine anions with a stoichiometric number of cations to satisfy charge neutrality. Under these constraints, a range of compositions were chosen to span the phase field, with more compositions at the Li rich end (Figure 1a). We sampled all of the possible compositions for the cells containing eight anions and then only considered the Li/Al ratios closest to 1:1 for the cells containing nine anions since these were the lowest energy regions following the initial screen. All possible S/O ratios were considered. The computed energy of the probe structure at each computed composition is presented in Figure 1a.

Figure 1

Figure 1. (a) Calculated energy of different compositions in the Li–Al–O–S phase field using cells containing hexagonal close-packed (hcp, black triangles) and cubic close-packed (ccp, black filled circles) anion lattices. Ehull is the energy above the convex hull. Reported oxide and sulfide phases in the Li–Al–O–S phase field (black rectangles). (b) First-stage experimentally tested compositions, which resulted in a mixture of already reported compounds (empty red squares with black letters), and a mixture of already reported compounds along with the presence of the new phase (filled red squares with white letters). Second-stage experimentally tested compositions (numbered black circles). Composition of points are as follows: A (Li3Al9O2S13), B (LiAlOS), C (LiAlO0.2S1.8), D (LiAlO1.8S0.2), E (Li7Al2O4S), F (Li5AlO3S), 1 (Li4Al2O2S3), 2 (Li6Al8O10S5), 3 (Li2Al4O4S3), 4 (Li2Al4O5S2), and 5 (Li3AlS3).

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A valley of lower energy is observed at a Li/(Li + Al) ratio of 0.5 (LiAlS2–LiAlO2 solid solution line), with a local energy minimum at 42 meV·atom–1 above the convex hull for the previously proposed composition of LiAlOS. (37) When using the full convex hull construction, LiAlOS is predicted to decompose into LiAl5O8, LiAlS2, and Li2S. In comparison, the probe structure in the previous study was also determined to be thermodynamically unstable, but with respect to LiAlS2 and LiAlO2, with a calculated formation reaction energy of 46 meV·atom–1 at 0 K. (37) Because these calculated energies are relatively low, LiAlOS could be a metastable structure that is possibly synthesizable and was therefore selected as a candidate composition for experiments.
Near the sulfur- and oxygen-rich regions of the LiAlS2–LiAlO2 solid solution line, the calculated energy is interestingly low compared to other regions close to the borders in the overall phase diagram. For instance, the energy of composition LiAlS1.8O0.2 is 34 meV·atom–1 above the convex hull. This value is close to the value of the known phase LiAl5S8 (38 meV·atom–1 above the convex hull), which has been synthesized in the literature. (60) The composition LiAlS1.8O0.2 was therefore selected for experimental synthesis. The symmetrical composition near the oxide end member, LiAlS0.2O1.8, shows a higher energy (51 meV·atom–1) but is close to that of LiAlOS and also synthesized as a matter of comparison.
Plateaus with energies below 60 meV·atom–1 above the convex hull are observed in the regions close to the terminal Al2S3 and Li2O. Within the former, the composition Li3Al9O2S13 was previously suggested by the Materials Project (61) as an interesting analogue candidate of Ga9Tl3O2S13. (62) The energy calculated for this compound in this work is 46 meV·atom–1 above the convex hull, which is also close to that calculated for LiAlOS. The plateau close to Li2O, as well as presenting relatively low energies, attracted our interest due to the high content of lithium, possibly favorable for attaining higher conductivities. Two compositions, Li5AlO3S and Li7Al2O4S, were selected for experimental synthesis in this region of the phase diagram.
Figure 1b and Table S1 summarize the six compositions (labeled A to F and represented by red squares) that were chosen, in a first stage, after analysis of the results from calculations. The experimental procedures for all samples were the same and were described in the Experimental Section. In particular, we used Li2O and LiAlO2 as oxide precursors whenever the composition enabled them, in order to improve the reactivity compared to the use of Al2O3. Moreover, a relatively high temperature of 800 °C and cooling by a quenching procedure were chosen in order to both facilitate the access to high-energy phases and to kinetically trap them and prevent the decomposition into binary or ternary phases during cooling.
Compositions highlighted with the empty red squares and black letters in Figure 1b consisted of a mixture of only already reported phases after annealing, which is detailed in Table S1. However, two points along the LiAlO2–LiAlS2 solid solution line (Figure 1b, points B and C) showed the presence of an unknown phase along with the already reported phases. Figure S1 shows the XRD patterns of samples A to F after reaction made in the first stage. For composition LiAlOS, the unknown phase seemed to be in a relatively high amount; thus, in a second stage, four new compositions were tested around this point (black circles in Figure 1b, composition given in the caption, and Table S1). For composition number 4 in particular (Li2Al4O5S2), this new phase was present along with Al2O3 as a single impurity. Figure S2 shows the XRD patterns of samples 1 to 4 after the reaction made in the second stage. Li2Al4O5S2 can then be written as Li2Al4O5S2 = a Al2O3 + Li2Al2/3(1+y)OyS2 (0 ≤ y < 5), highlighting the fact that the unknown phase must have a Li/S ratio of 1. By considering the two end members (y = 0 and y = 5), this result led us to investigate the solid solution line x Li2Al4O5S2 + (1 – x) Li2Al2/3S2, on which the composition Li2Al2/3(1+y)OyS2 is located. The synthesis of the pure sulfide end member (point number 5) gave the phase pure new compound sought, which was thus revealed to be a pure sulfide material, rewritten as Li3AlS3. The energy calculated for Li3AlS3 was found to be 16 meV·atom–1 above the convex hull. No other calculated energies in the phase diagram, which do not already correspond to known phases, drop below this threshold. We therefore concluded that no other oxysulfide phases are likely to form in the Li–Al–O–S field. The oxide analogue Li3AlO3 could not be stabilized by a similar quenching method (cf. Supporting Information) and leads to a calculated energy of 27 meV·atom–1 above the convex hull. The calculated energy of Li3AlS3 is slightly above the hull, which suggests that the phase is metastable.
In the Li–Al–S phase field, phases with compositions LiAlS2, (63) Li5AlS4, (64,65) and LiAl5S8 (60) have previously been reported. Moreover, an amorphous phase with composition Li3AlS3 was identified previously as the discharge product of an Al–S battery. (66) Although no experimental structural data was presented for this model, a local structure of this amorphous phase was modeled with DFT and displayed a network of isolated 4- and 5-coordinated aluminum. Both the LiAlS2 and Li5AlS4 structures possess nearly close-packed anion layers arranged in a hexagonal stacking sequence. LiAl5S8 is dimorphic and comprises a low-temperature modification with a normal spinel-type structure and a high-temperature modification related to the ZnIn2S4 structure. Both LiAl5S8 structures have a cubic close-packed arrangement of the anion lattice. The integrated computation–experiment approach described here enabled the identification of a new crystalline phase with the composition Li3AlS3. This phase was isolated by synthesis, and its structure and lithium transport properties were experimentally investigated.

3.2. Synthesis and Structure of Li3AlS3

3.2.1. Synthesis

Polycrystalline Li3AlS3 was synthesized via a solid-state reaction of Li2S and Al2S3 (described in the Experimental Section). The powder XRD profile of the product could be indexed to a phase whose structure does not match any of the compounds previously reported for Li–Al–S systems. A small quantity of Li5AlS4 (3.3(5) mol %) was also identified in the XRD pattern. Elemental analysis gave an overall composition of Li3.1(1)Al1.1(1)S3.0(1) (Table S3), but the ICP measurement is not sufficiently precise to distinguish between the nominal reaction stoichiometry (Li3AlS3), the measured composition, and the presence of the secondary Li5AlS4 phase, further complicating its interpretation; consequently, the compound is referred to as Li3AlS3 hereafter.

3.2.2. Structure Determination

The crystal structure of Li3AlS3 was solved by first indexing the SXRD pattern using the first 22 reflections using GSAS-II. (67) The unit cell was indexed in the space group C12/c1 with approximate lattice parameters of 14.3 × 12.0 × 6.6 Å with β ≈ 117°. The lattice parameters were then refined across the d spacing range 16–0.67 Å (2θ = [3–75°]) via a Le Bail fit in Jana2006. (68) The structure was solved initially by locating the S and Al atoms using superflip (69) implemented in Jana2006. From this solution, a Rietveld model was refined against the SXRD and NPD patterns. Once converged, the Li atoms were located using Fourier Difference mapping on the NPD patterns, searching for peaks in the difference map located at greater than 1 Å from existing atoms within the model. When no more new sites could be located, an initial Rietveld model was constructed and refined.
Final Rietveld refinement of the neutron and synchrotron diffraction data was carried out using the program FullProf. (70) First, the SXRD pattern was fitted on its own. Position, site occupancy factor (sof), and atomic displacement parameters (adp) of lithium atoms remained fixed in the refinement of the synchrotron data. The sof of aluminum refined to 0.974(1) on its site and significant drops in the conventional reliability factors were obtained: RBragg decreased from 2.79 to 2.68. Figure 2a shows the final fit of the SXRD pattern, and the following results were obtained for the cell parameters: a = 14.31901(5) Å, b = 11.98037(3) Å, c = 6.62700(2) Å, and β = 116.9231(3)°. The values of the refined cell parameters were then implemented and fixed in the refinement of neutron data. The final model of the structure was obtained through the combined refinement of the neutron data coming from the three neutron datasets. Figure 2b–d shows the final fits of the patterns. Refinement details and outcomes as well as the crystallographic data are summarized in Tables S4 and S5.

Figure 2

Figure 2. Final Rietveld refinement of (a) the synchrotron X-ray diffraction pattern of 7Li3AlS3 (Diamond Light Source, I11 beam line) with fixed Li positions and (b) 7Li3AlS3 against neutron powder diffraction data (ISIS neutron source, HRPD) from (b) bank 1 (2θ = 168.330°), (c) bank 2 (2θ = 89.580°), and (d) bank 3 (2θ = 30.000°), with Iobs (red dots), Icalc (black line), Iobs – Icalc (blue line), and Bragg reflections (red tick marks for Li3AlS3, black tick marks for Li5AlS4, and blue tick marks for the vanadium can).

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The unit cell shows three sulfur sites (S1, S2, and S3), three tetrahedral sites on general positions 8f (Table S5), two of them occupied by Li (Li1 and Li4) and one by Al and Li ions (Al and LiAl), and two occupied octahedral lithium sites (Li2 and Li3) located on two 4e Wyckoff positions on the 2-fold rotation axis (at the beginning of the refinement). The isotropic adp (Biso) were refined to large values: 3.3(5) Å2 for Li2 and 3.7(5) Å2 for Li3. In order to improve the model, the displacement was modeled as anisotropic, which led to the decrease of χ2 from 1.74, 6.46, and 1.54 to 1.73, 6.06, and 1.54 for banks 1, 2, and 3, respectively. The anisotropic ADPs for Li2 and Li3 remained high, and a marked anisotropic displacement along the a axis was found for Li3 in particular, as highlighted by the Fourier difference map in the ab plane in Figure S4a, thereby prompting us to consider site splitting. Li3 was moved from its fully occupied 4e position (0, y, 0.25) to a half occupied general 8f position (x, y, z), which then generates a second Li3 atom of coordinate (−x, y, z) from the other side of the rotation axis, within the same coordination polyhedra. For Li2, as the anisotropic displacement was not as straightforwardly along one single direction, moving the atom to one half occupied 8f position did not improve the fit. This site was split into two 8f positions (Li2 and Li2b), each allocated first with an occupancy of 0.25, generating 4 Li positions within the same coordination polyhedron, in order to model its large displacement. The occupancies of Li2 and Li2b were then refined by constraining their sum to be equal to 0.5. In that way, the total occupancy within each polyhedron is equal to one. The site splitting of Li2 and Li3 led to much smaller isotropic adp of 1.2(7) Å2 for Li2 (and Li2b) and 1.7(4) Å2 for Li3, along with a reduced residual density in the Fourier difference map around the sites (Figure S4b). Another indication for preferring the modeling of both sites with multiple atoms was the increase in the bond valence sum (BVS) from 0.76(1) to 0.83(16) for Li2 and 0.82(4) for Li2b, while keeping it to 0.80(3) for Li3.
Through occupancy refinement, a lithium antisite defect was identified and occupied 6.7% of the aluminum site. No other Li or Al antisite defects were found. Details of the refinement procedure are presented in the Supporting Information, page 7, and results of the final refinement of the occupancies are given in Table S4.
NMR spectroscopy at various fields was deployed to further confirm the overall pattern of site occupancy of the lithium atoms. The 6Li MAS NMR spectra at 9.4 and 20 T for Li3AlS3 are shown in Figure 3a and display three well-resolved resonances at 1.7, 1.3, and −0.2 ppm, which fit yield signals of equal integration. A small shoulder is also observed at 1 ppm (Figure S8) and corresponds to the Li5AlS4 impurity seen in the diffraction and 27Al NMR data (see below); (65) this signal was found to integrate 3.0(5) mol % Li3AlS3, in agreement with the 3.3(5) mol % value from diffraction. Based on the well-established semi-empirical correlations relating the lithium coordination environment and 6Li NMR shifts, (71) further aided by calculations of the NMR parameters using the GIPAW approach (52,53) as implemented in CASTEP (51) (cf. Supporting Information, Table S7), the signal at −0.2 ppm has been attributed to the octahedrally coordinated Li2/Li2b and Li3 sites while the resonances at 1.3 and 1.7 ppm correspond to Li4 and Li1, respectively. These assignments agree well with the structural refinement described above, which identified the sum of the contents of the three octahedrally coordinated sites Li2 (0.8(3)), Li2b (3.2(3)), and Li3 (4.0(4)) to 8.0(7) Li per unit cell and the contents of the two tetrahedrally coordinated Li4 and Li1 to 7.8(3) and 8.00 per unit cell, respectively.

Figure 3

Figure 3. (a) 6Li MAS spectrum of Li3AlS3 obtained at magnetic fields of 9.4 T (black) and 20 T (blue). The experimental spectrum (full lines), total fit (dashed lines) spectral deconvolution (dotted lines), Li5AlS4 impurity (red dotted lines), and GIPAW-simulated spectrum (green lines) are shown. (b) 27Al MQMAS NMR spectrum of Li3AlS3 recorded at a magnetic field of 9.4 T and 20 T. The dotted lines (black for a field of 9.4 T and blue for 20 T) and the red dotted lines represent the spectral deconvolution of Li3AlS3 and Li5AlS4, respectively. The dashed lines show the total fit for the sample, and the solid lines show the anisotropic one-dimensional 27Al spectrum, while the vertical spectrum shows the non-quantitative isotropic 27Al spectrum. The solid green line shows the GIPAW-simulated spectrum with an isotropic chemical shift of 117 ppm, a quadrupolar coupling constant of 5.1 MHz and an asymmetry parameter of 0.44 (Table S7).

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The 27Al one-dimensional MAS spectra for Li3AlS3 at 9.4 and 20 T are shown in Figure 3b and reveal a second order quadrupolar line shape that resonates at ∼100 ppm (at 9.4 T) and ∼120 ppm (at 20 T), typical of tetrahedrally coordinated Al sites, and a very sharp signal, which is field-independent, at ∼130 ppm, corresponding to the small amount of Li5AlS4 impurity (Figure S7). Note that no signal in the octahedral region (around 0 ppm) of the 27Al MAS NMR spectrum is present as expected. The z-filtered triple quantum MAS (53,54) NMR spectrum of Li3AlS3 is also shown in Figure 3b and demonstrates that the ∼100 ppm signal corresponds to one resonance only with an isotropic chemical shift of 117 ppm (cf. the Supporting Information) and a quadrupolar coupling constant (CQ) of 5.8 MHz in close agreement with the computed value of 5.1 MHz (cf. SI, Table S7).
The final model led to the overall refined composition Li3.13(2)Al0.958(4)S3, slightly different from the composition determined by ICP. The small differences can be explained by the presence of the Li5AlS4 impurity, which prevents the ICP measurement from producing an accuracy to the nearest two decimal places. The refined composition is different from the ideal, which will be discussed hereafter.

3.2.3. Structure Description

3.2.3.1. Polyhedral Arrangement
Li3AlS3 adopts a structure related to that of Na3InS3 reported by Eisenmann and Hofmann where In3+ and Na+ cations are replaced by Al3+ and Li+, respectively. (72) The only other isostructural phases reported are Na2Mn2S3, (73) Na2Mn2Se3, (74) and LixNa1–xMn2S3 (x ≈ 0.7) (75) in which half of the Mn2+ ions are replaced by aluminum atoms whereas the other half along with the sodium atoms are replaced by Li+ ions. The structure is constructed from an hcp arrangement of sulfur atoms with an AB A*B* stacking of anion layers where B is the equivalent of A through the c glide plane and 2-fold axis symmetry operations. A* and B* are the equivalent of A and B through the C centering translation (Figure 4a). In the tetrahedral layer, Li1 and Al atoms occupy 2/3 of the tetrahedral interstices between a pair of sulfur atom layers (B and A*, equivalent to the B*A pair). Between the second pair of sulfur layers (A and B, equivalent to the A*B* pair), Li2 and Li3 occupy octahedral interstices, whereas Li4 occupies a tetrahedral interstice, generating a mixed polyhedral (octahedral–tetrahedral) layer. The two different polyhedral layers are stacked alternately perpendicular to the bc plane (Figure 4a). Bond distances and angles of the different polyhedral and BVS calculations performed for all atoms are summarized in Table S6.

Figure 4

Figure 4. (a) Crystal structure of Li3AlS3 showing the alternating arrangement perpendicular to the bc plane of the tetrahedral layers containing AlS4 and LiS4 tetrahedra and the mixed polyhedral layers containing Li-only polyhedra. (b) T+ and T– interstices in the tetrahedral layer, showing the corner-sharing arrangement of the Li1, Al, and vacant (empty) tetrahedra in each network, as well as the interconnection (following the yellow arrow) of each T+ (thin lines) and T– (thick lines) network so that AlS4 dimers are formed. The highlighted yellow face of the Li1 tetrahedron corresponds to the only face that shares two edges with two vacant sites. (c) View of both the mixed polyhedral layer and the tetrahedral layer in the bc plane and of their interconnection (following the yellow arrow). Polyhedra colors: blue: Al tetrahedra; orange: Li tetrahedra; red: Li2 octahedra; light red: Li3 octahedra.

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In the tetrahedral layer, one tetrahedral site in every three is vacant in an ordered manner (Figure 4b). Each T+ and T– interstice forms a network of alternating Al, Li1, and vacancy corner-shared tetrahedra. The T+ and T– networks interlock in such a way that each AlS4 unit shares one edge (S3–S3) with another Al tetrahedron and a second edge with the Li1S4 unit within the layer. These 4-edge-shared tetrahedra (Li1S4(T+)–AlS4(T–)–AlS4(T+)–Li1S4(T+)) form a unit that is connected to other units of this type by corner-sharing (Figure 5a, circled part in Figure 4b). The Li1 tetrahedron has two S atoms that share corners with Li1 and Al, and there is no corner-sharing of Al tetrahedra.

Figure 5

Figure 5. Coordination polyhedra of (a) Li1 and Al in the tetrahedral layer, (b) Li4, (c) Li2 and Li2b, and (d) Li3 in the mixed polyhedral layer.

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In the mixed polyhedral layer, each of the Li2, Li2b, and Li3 atoms is surrounded by six sulfur atoms to form LiS6 octahedra (Figures 4c and 5b). Li2 and Li2b polyhedra form an infinite chain of edge-shared octahedra along the c axis, which are also connected to three Li3 octahedra also through three shared edges. Thus, both octahedra form infinite two octahedra-wide chains along the c axis. Each chain is separated along the b axis by a chain of edge-shared LiS4 T+ and T– tetrahedra occupied by the Li4 atom (Figure 4c). Li3 octahedra are linked to two consecutive T+ and T– Li4 tetrahedra, sharing one face with each of them (Figure 4c). These two Li4 tetrahedra form a unit (Figure 5b) and each T+ and T– of the unit shares one corner with one Li2/Li2b octahedron from the same chain as the face-shared Li3 octahedra, as well as one corner with one Li3 octahedron of the chain on the other side of the Li4 chain. Along the Li4 chain, octahedral interstices are vacant so that only 2/3 of the octahedral sites are occupied in the layer. As a result of crystallization, the ordered structure obtained experimentally in this study strongly differs with the structure modeled for the amorphous discharged product with the same composition described by Yu et al. (66)
Figure 4c shows the connection between the polyhedra of both layer types. Each of the Al and Li1 T+ (T–) tetrahedra is connected to the layer below (above) by sharing the face at the base of the tetrahedron with a vacant tetrahedral site of the mixed polyhedral layer. For the Al tetrahedra, this face shares one edge with the Li2 octahedra and another edge with the Li3 octahedra of the same chain, while the third edge is shared with the vacant octahedral site. For the Li1 tetrahedra, this face shares two edges with the Li2 octahedra and one edge with the Li3 octahedra of the same chain. The S3 atom, which is at the vertex of the Al T+ (T–) tetrahedra, is shared with one Li2, one Li3, and four Li4 of the above (below) mixed polyhedral layer, whereas the S1 atom, which is at the vertex of the Li1 T+ (T–) tetrahedra, is shared with one Li3 octahedron and four Li4 of the above (below) mixed polyhedral layer. The chain of vacant T+ (T–) sites along the c axis in the tetrahedral layer lies above (below) the chain of Li4 tetrahedra of the mixed polyhedral layer.
3.2.3.2. Polyhedral Distortions and Atom Displacements
Figure 6 shows the bonding environment of each of the cations. In the tetrahedral-only layer, Li1 atoms are strongly off-centered toward the S1–S2–S2 face so that it both does not share any edges with the AlS4 tetrahedra in the same layer and does not belong to the octahedral layer (Figure 6). This face is also the only one that shares two edges with two vacant sites of the tetrahedral layer as opposed to one for the other two faces that do not belong to the octahedral layer (highlighted yellow face in Figures 4b and 6). Moving away from the nearby Al cations as well as from the Li2 and Li3 atoms of the octahedral layer provides the electrostatic driving force for its displacement (Figure 6). The BVS of Li1 is 0.97(2), which is very close to the ideal value of +1, considering the oxidation state of lithium.

Figure 6

Figure 6. Crystal structure of Li3AlS3 showing the arrangement of octahedral (red) and tetrahedral (orange) lithium and tetrahedral aluminum (blue). The direction of the displacement of atoms is symbolized by arrows: blue for Al, orange for Li1 and Li4, and yellow for S.

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The tetrahedral Li4 site in the mixed layer shares a face with the vacant tetrahedral site of the tetrahedral layer. The Li4 position is strongly displaced toward the base of the tetrahedron and the adjacent sulfur layer, toward this vacant tetrahedral interstice (Figure 6). Li4 thus adopts a pseudo-trigonal bipyramid environment with one short axial Li4–S1 and one long axial Li4–S2 bond. BVS for Li4 is slightly lower than that of Li1 (0.93(2)), which is consistent with its pseudo-5-coordinated environment, making it more loosely bound to the S atoms compared to the 4-coordinated Li1.
This is reflected in the NMR resonance frequency of Li4 (1.3 ppm) for which the 5-coordinate environment provides this site with an intermediate chemical shift between the lithium atoms occupying a tetrahedral site (Li1 at 1.7 ppm) and octahedral sites (Li2/Li2b and Li3 at −0.2 ppm). The NMR shift calculation also suggests that the resonances of Li3 and Li2/Li2b should be resolved as the isotropic chemical shifts differ by 0.3 ppm; however, this is not observed experimentally, even at high field, perhaps due to the larger full width at half-maximum observed for this Li3/Li2/Li2b resonance (18 Hz compared to 10 and 11 Hz for Li4 and Li1, respectively). The presence of the occupied Li4 sites distinguishes both Li3 and Li2/Li2b sites: Li3 shares faces with Li4, whereas Li2 does not (Figure 4c). The shift of the Li4 toward the adjacent sulfur layer pushes the Li4 atom further away from the octahedral Li3 atoms and therefore reduces the structural difference between Li2 and Li3, further explaining the similar shifts observed experimentally for these octahedral sites (Table S7). On the contrary, the difference in the environment of Li1 and Li4 is more pronounced (tetrahedral vs trigonal bipyramid), which explains the resolution of their respective NMR peaks. The consistency between the experimental NMR data and the computed ones from the described structure further reinforces the accuracy of the selected structural model.
The geometry of the AlS4 dimer is represented in Figure 5a, and among the six edges of each AlS4 tetrahedron, four of them are directly connected to the S3–S3 edge-shared with the other tetrahedron of the dimer. Consequently, the aluminum position is shifted toward the S1–S2 edge that does not share a common sulfur atom with the other edge-shared Al tetrahedron of the dimer. This displacement is symbolized by blue arrows in Figure 6. This can be explained by the proximity to the other Al atom of the edge-shared dimers with which it tends to maximize its distance. The Al–Al distance is 3.015(6) Å, which is similar to distances obtained in other sulfide materials (Na6Al2S6, Na3FeS3) presenting these dimers. (76,77) This is also supported by the 27Al NMR data obtained experimentally and computed with GIPAW (cf. SITable S7) that yield a clear second-order quadrupolar line shape at both 9.4 and 20 T and from which large quadrupolar coupling constants (CQ = 5.8 and 5.1 MHz for experimental and computed values, respectively) and distorted asymmetry parameter values (ηQ = 0.56 vs 0.44 for experimental and computed values, respectively) are obtained. These data clearly demonstrate the non-symmetrical dimeric Al coordination environment in Li3AlS3 and is in sharp contrast to the symmetric AlS4 tetrahedra observed in Li5AlS4 (CQ ≈ 0 MHz, Figure S7) as evidenced by the field-independent NMR narrow line of this phase.
The dimerization leads to the strong repulsive force between both highly charged Al3+ cations. This in turn brings the S3 atoms inside the dimer toward each other and therefore toward the interior of the tetrahedral layer, in order to keep the BVS of Al and S close to their ideal values (symbolized by yellow arrows in Figure 6b,c). The S3–S3 distance (represented by a thick line in Figure 6b,c, dS3–S3 = 3.463(14) Å) is indeed the shortest in the structure. The compression of the S3–S3 edge of the Al2S6 dimer unit in the tetrahedral layer leads to the stretching of the S3–S3 edge of Li2(Li2b)S6 and Li3S6 octahedra in the mixed polyhedral layer (Figure 6b,c).
As shown in Figure 6a, the Li2b (and Li2) octahedron is highly distorted, and the S3–S3 edge is considerably longer than the other edges (dS3–S3 = 4.40(1) Å whereas the length of the other edges ranges from 3.66(1) to 3.951(7) Å). Also, the Li3 octahedron is elongated along an axis defined by two S3 atoms (dS3–S3 = 5.729(14) Å), whereas the equatorial plane defined by two S1 and two S2 atoms is close to a square (dS2–S2 = 3.893(13) Å, dS1–S1 = 3.713(14) Å, dS2–S1 = 3.682(8) Å). The explanation for the site splitting of Li2 can be linked to the distribution of the sulfur vacancies (Supporting Information, page 10). In contrast to the tetrahedral Li1 and Li4, the BVS values for octahedral Li2, Li2b, and Li3 are below the theoretical value (0.83(16), 0.82(4), and 0.80(3) for Li2, Li2b and Li3, respectively), which reflects the fact that they are weakly bonded to the sulfur atoms. This observation has also been made in similar structures. (65)
A sulfur deficiency was found on two S sites. This deficiency accounts for the charge compensation with the Al defect. The majority of sulfur vacancies are located on the S3 site, which bridges the two aluminum tetrahedra of the dimer. As explained above, the S3–S3 distance is the shortest in the structure; hence, vacancies here would reduce anion–anion repulsions. Again, the presence of the dimers leading to the short S3–S3 distance could be the trigger for the deficiency of the S site. Further, the occupancy of the Al site cation vacancies by Li creates a negatively charged antisite defect, which could also drive the localization of the positively charged sulfur vacancy on the S3 site.
The analysis of the Li3AlS3 structure highlights the importance that the Al2S6 dimers have on site geometries as well as on site occupancies of both lithium and sulfur atoms. Moreover, the comparison with the probe structure, which also shows the presence of these dimers (Supporting Information, page 11, and Figure S5), further suggests that the stability of the structure is connected to the presence of the Al2S6 dimers.

3.3. Comparison with Known Structures

Lithium sulfide materials showing different arrangements of cation polyhedra in hcp arrays are common, and some interesting compositions and structures have been described by Lim et al. (65) Among them, one can cite Li2FeS2, which consists of an octahedral-only layer whose interstices are 100% occupied by lithium atoms, alternating with a tetrahedral layer, where all the tetrahedral sites are occupied by Li and Fe atoms randomly distributed in a 50:50 ratio. (78) Li5AlS4 shows a similar structure where only half of the Fe atoms are replaced by Al3+ ions whereas the other half is occupied by Li+ ions. (65) The tetrahedral layer consists of ordered LiS4 and AlS4 units in a 3:1 arrangement. The authors note that these structures can be expressed as [LiFe]T[Li]OS2 and [Li1.5Al0.5]T[Li]OS2, respectively. We added the superscripts “T” and “O”, which refer to the tetrahedral and octahedral coordination of the cation in alternating layers. Following this representation, the material reported in this study, Li3AlS3, could be written as [Li2/3OLi2/3T][Li2/3Al2/3]TS2 where the cation in the same square bracket belong to the same layer. Recently, Leube et al. reported a family of compounds Li4.4M0.4M′0.6S4 (M = Al3+, Ga3+, M′ = Ge4+, Sn4+) whose structure is closely related to that of Li5AlS4. (46) The highly charged cations share the same site in the tetrahedral layer, the octahedral layer is made of ordered partially occupied lithium sites and fully vacant sites in a 3:1 arrangement, and the remaining lithium atoms share two crystallographically distinct tetrahedral sites in both the tetrahedral and octahedral layer in a 74:26 ratio. Following the same convention, this structure can be written as [Li0.66OLi0.38T][Li1.11M0.2M′0.3]TS2.
Other alkali metal sulfides with composition A3MS3, where A is an alkali monovalent cation and M is a trivalent cation, have been reported in the literature. As stated above, Na3InS3 in particular shows a closely related structure to Li3AlS3 and can be written as [Na2/3□1/3]O[Na]2/3T[Na2/3In2/3□2/3]T′S2 where In and Na occupy the same sites as Al and Li in Li3AlS3. Moreover, both compounds show identical distortions of the alkali octahedra and the same direction of displacements for the tetrahedral alkali cations. This particularity is most probably coming from the high degree of constraint imposed by the presence of the M3+S4 dimers, and the fact that this observation is made in both phases reinforces the validity of this explanation. Rothenberger et al. (79) reported a structure with the composition (M(AlS2)(GeS2)4 (M = Na, Ag, Cu) where 20% of the Al atoms are in similar dimeric tetrahedral units). However, these Al dimers were much less distorted with very similar Al–S interatomic distances within the tetrahedra (the average Al–S distance is 2.2117(5) Å and the standard deviation 1.3%). The absence of tetrahedral distortion in these dimers can be explained by the 3D polyanionic rigid structure imposed by the three other Al or Ge sites. This lessening of the distortion from tetrahedral symmetry is also reflected in the 27Al NMR where the resonance observed  shows,on the spectra, smaller values of CQ for (M(AlS2)(GeS2)4 (M = Na, Ag, Cu).
The splitting of the Li2 site in Li3AlS3 is not reported for Na3InS3, nor is the displacement from the Wyckoff position to a general position of the second octahedral alkali site. Lithium is smaller than sodium, and the volume occupied by each atom considering a hard sphere model is 12 and 18% of the total volume of each octahedron for Li and Na, respectively. The displacements and splitting modeled for lithium might therefore be key to generating an appropriate bonding environment as defined by the BVS.
Interestingly, Na3AlS3 along with Na3GaS3 shows a slightly different structure (Figure 7a,b). (76,80) In between two sulfide layers, Al2 occupies 1/3 of the tetrahedral sites and forms dimers between T+ and T– tetrahedra of the same slab. In this layer, Na4 occupies 1/3 of the distorted octahedral sites forming infinite chains along the c axis. In between the next two sulfide layers, Na1 occupies one distorted octahedral site, whereas Na2 and Na3 form 5-coordinated sulfide polyhedra in a trigonal bipyramid configuration and all three Na sites are in a 1:1:1 arrangement. The next slab consists of a similar AlS4 and NaS6 polyhedra arrangement to the first described slab, with a slight tilt of the polyhedra (Figure 7b). Na5 lies within each of the sulfide layers forming the Al2S4 slab and is 6-coordinated to four of the sulfur atoms of the same layer, one in the layer above and one in the layer below, therefore forming a 2D network of edge- and corner-shared octahedra. The structure difference between Na3InS3 or Li3AlS3 (for which Na or Li is 4-coordinated in the tetrahedral layer) and Na3AlS3 or Na3GaS3 (for which Na is 6-coordinated in the tetrahedral layer) could be attributed to the size of the M3+ cation with respect to that of the alkali cation. Indeed, the ionic radius of Al3+ (0.39 Å) and Ga3+ (0.47 Å) is considerably smaller than that of In3+ (0.62 Å), (81) so the size of tetrahedral interstices will decrease and might not be suitable to host Na+ cations, which would then prefer to occupy octahedral sites, in contrast with the smaller Li+ cation.

Figure 7

Figure 7. (a) Crystal structure of Na3AlS3 showing the alternating arrangement, along a, of the tetrahedral layers containing AlS4 and NaS4 tetrahedra and of the mixed polyhedral layers containing Na-only polyhedra. (b) View of the two consecutive tetrahedral layers of Na3AlS3 in the bc plane. (c) Crystal structure of Na3FeS3 showing one type of layer along b (d) View of the layer along b of Na3FeS3 showing the fully occupied octahedral sites by Na atoms and the 1/3 occupied tetrahedral interstices by Fe atoms in a dimer arrangement.

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Another known structure of similar composition showing different arrangements of metal and alkali cations within the hcp array is that of Na3FeS3, (77) which is also adopted by Na3FeSe3, (82) Na3AlSe3, (83) and Na3GaSe3 (84) (Figure 7c). In those phases, the M3+ cation assembles in tetrahedral dimers in between each of the sulfide layers, and the sodium atom occupies all of the octahedral sites in these layers (Figure 7c,d). Curiously, the absence of alkali-only layers and the stabilization of a single layer type containing both Fe or M (M = Al3+, Ga3+, and In3+) and Na or Li polyhedra seem to occur in all of the selenide compounds as well as both the iron sulfide and selenide phases. It seems that this could be linked to the less ionic character of the bonds in those structures. Indeed, the higher polarizability of Se2– compared to S2– anions generally leads to softer and more covalent bonds in selenides. (85) It has also been shown, through magnetic property measurements, that the 3d orbitals of Fe3+ in Na3FeS3 are more extended than that of ionic Fe3+, which can be attributed to Fe–S covalency. (86) Because Al3+, Ga3+, and In3+ do not show this effect, the ionic character of the M–S (M = Al3+, Ga3+ and In3+) bond might be more pronounced in Na3MS3 than in Na3FeS3. Different layer-type structures are often found in materials where ions have different chemical properties, in particular different polarizability, which results in different ionicity of the cation–anion bond in each layer. (87,88) A more covalent character of the bonds would then attenuate the difference in polarizability of the cations and favor the single layer-type structure.

3.4. Lithium Conductivity

The ionic conductivity of Li3AlS3 was assessed by electrochemical impedance spectroscopy on sintered pellets with an 80 ± 2% relative density. The Nyquist plot of the sample measured at room temperature under an argon atmosphere is shown in Figure 8a. The presence of the two semicircles is characteristic of two unique time constants and therefore of the dissociation between different scattering contributions. The plot has therefore been fitted by a two-component equivalent electrical circuit (inset in Figure 8a) that models these two contributions. Each component consists of a resistance associated in parallel with a constant phase element (CPE, a modified capacitor taking into account inhomogeneities in the sample, cf. Supporting Information). The values of the capacitance obtained for the semicircles at high and low frequencies were 8(1) × 10–12 and 2.6(4) × 10–9 F and are characteristic of the bulk and grain boundary response, respectively. (89) The high-frequency intercepts of both semicircles give direct values of the bulk and total resistance (Rbulk and Rt = Rbulk + RGB, respectively, where RGB is the resistance resulting from the grain boundary scattering). Bulk and grain boundary room-temperature conductivities of 1.3(1) × 10–8 and 2.2(2) × 10–9 S·cm–1, respectively, were obtained. The impedance of the pellet was measured over the temperature range (24–125 °C), and each Nyquist plot was fitted with the described equivalent circuit. Tables S8 and S9 present the results of the fits and the values of the different parameters obtained at each temperature. For each temperature, the conductivity of the bulk, σbulk, was therefore extracted and showed to follow the Arrhenius law (Figure 8b) with an activation energy of 0.48(1) eV.

Figure 8

Figure 8. (a) Nyquist plot at 30 °C of Li3AlS3 and (inset) electrical equivalent circuit showing the two contributions to the conductivity. (b) Arrhenius plot of the bulk conductivity of Li3AlS3 measured by AC impedance. Black squares correspond to the experimental data, and the red line corresponds to the fits.

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The room-temperature bulk conductivity is of the same order of magnitude as that of Li5AlS4 (σ = 9.7 × 10–9 S·cm–1). (65) In Li5AlS4, all Li sites are fully occupied, whereas in Li3AlS3, there are multiple ordered vacancy sites: one third of the octahedral interstices in the mixed polyhedral layer and two thirds of the tetrahedral interstices in the tetrahedral layer are vacant. Although the lowering of the activation energy (0.48 eV for Li3AlS3 and 0.61 eV for Li5AlS4) is indeed observed, the increase in Li mobility is not, which suggests that ordered vacancy sites are not sufficient to improve conductivity in this structure type.
In the recently reported related Li4.4M0.4M′0.6S4 compounds, which shows considerably higher conductivities σ = 10–5–10–6 S·cm–1, the presence of multiple disordered partially occupied lithium sites has been shown to play a major role in the improvement of the conductivity. In Li3AlS3, the only disordered vacancies can be found within the Li4 site, which was determined to be 98% occupied (Table S5), as all other Li sites are completely occupied. In order to highlight the different types of vacancies within the structure, Li3AlS3 can be written as
with □ and Δ being the disordered and ordered vacancies, respectively. The family of quaternary materials, using the same convention, can be written as
Overall, this structure shows fewer ordered vacant sites, but the content of disordered vacancies is considerably higher, which underlines the importance of this feature in order to improve conductivity.
It is interesting to note that, in the Na3FeS3 structure, only one type of layer in which all the sodium is located in octahedral sites is present. Because the mobile species are believed to be the octahedral lithium in these types of structures, (46) it would be of high interest to stabilize the Na3FeS3 structure in lithium-containing compounds while creating a large number of disordered vacancies.

3.5. Influence of the Al2S6 Dimers on the Structure and Li Ion Conductivity

The strong differences between Li5AlS4 or Li4.4M0.4M′0.6S4 (M = Al3+, Ga3+, M′ = Ge4+, Sn4+) structures and Li3AlS3 come from the ordering of the tetrahedral cations and the presence of edge-shared AlS4 tetrahedra pairs, which form Al2S6 dimers. The three structures have the same anion sublattice with tetrahedral Li and Al layers alternated with Li only layers (= mixed polyhedral layer). In the three structures, Al atoms must spread over the tetrahedral interstices of the tetrahedral layer, and when this is done in an ordered manner, the M/S ratio imposes the arrangement pattern. Indeed, in Li3AlS3, M/S = 1/3 means that there is one Al atom for three tetrahedral interstices (one tetrahedra contains four sulfur atoms, and each tetrahedra is connected to four other tetrahedra in a layer consisting of T+ and T– interstices, cf. Figure 4). Therefore, M/S = 1/3 imposes a 1:2 ordering in the Al tetrahedra by optimizing the distance between each AlS4 unit (Figure 9, entry 1). In the same way, M/S = 1/4 in Li5AlS4 and Li4.4M0.4M′0.6S4 leads to a 1:3 arrangement of the M (or M′) tetrahedra in the layer (Figure S6). The interconnection of both T+ and T– networks presenting this arrangement type inevitably leads to the presence of the Al2S6 dimers in Li3AlS3 on the contrary to the other two phases.

Figure 9

Figure 9. Representation of the influence of the M/S = 1/3 ratio on the structure and arrangement of Li polyhedra in Li3AlS3 having the “Li5AlS4-type” structure leading to the presence of ordered vacancies in the tetrahedral layer.

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These dimers have a crucial influence on the displacement of atoms within the structure. Because of the strong electronic repulsive forces between the two Al3+ cations in the dimer, the Al position is driven off the center of the tetrahedron and the S3–S3 distances are successively compressed and stretched among the layers (Figure 9, entry 2). In Li5AlS4 and Li4.4M0.4M′0.6S4, on the other hand, the S–S edges are not as compressed. This is reflected in the values of the standard deviations for the S–S distances: 0.13 (Li5AlS4), 0.20 (Li4.4Al0.4Ge0.6S4), and 0.24 (Li3AlS3) and in the maximum/minimum S–S distances (in Å): 4.1564/3.6805 (Li5AlS4), 4.3176/3.6016 (Li4.4Al0.4Ge.6S4), and 4.4206/3.4631 (Li3AlS3). This strongly impacts the geometry and the volume of the polyhedral sites in the adjacent layer, i.e., the Li-only layer (Figure 9, entry 3). In Li3AlS3, the volumes of the three different octahedral interstices are 26.7227, 27.1162, and 30.4551 Å3. The latter is considerably bigger than the other two and is not favorable to hosting small Li atoms. This explains why only 2/3 of the octahedral sites are occupied in the Li-only layer (Li2, Li2b, and Li3). In the same way, in Li4.4Al0.4Ge0.6S4, 3/4 of the octahedral sites are occupied, and the volume of the ordered vacant site is 31.5654 Å3. In Li5AlS4, all of the octahedral sites have the adequate geometry to host lithium, therefore leading to a full occupation of the octahedral sites within this layer. In Li3AlS3, it will be preferable for the remaining Li atoms to occupy a tetrahedral site. Li4 thus occupies the tetrahedral interstices, which are away from the already occupied octahedra as well as away from the above (or below) occupied Al tetrahedra (Figure 9, entry 3). The positions of the Li4 atoms are driven toward the above (or below) S–S slab to minimize repulsion with the other edge-shared Li4 tetrahedra, creating a pseudo-bipyramid trigonal environment. The displacement of the Li4 atoms is then detrimental to the occupation by another cation of the above or below tetrahedra in the tetrahedral layer. The latter would then more preferably be left vacant. This explains why among the two other tetrahedral sites not occupied by Al, only one is occupied by Li, and a 1:1:1 arrangement of Al, Li, and ordered vacancies is stabilized (Figure 9, entry 4). In Li4.4Al0.4Ge0.6S4, apart from the tetrahedral site that lies just below the MS4 tetrahedra of the above tetrahedral layer, all the other tetrahedral sites of the Li-only layer are equivalent and Li atoms therefore randomly occupy these positions. The motivation for the ordering of vacancies in the tetrahedral layer is therefore suppressed, and the remaining Li ions are delocalized among all tetrahedral sites in this layer. The ordered vacancy sites, unfavorable to host lithium atoms, are likely to act as a barrier for Li diffusion, and result in lower lithium ionic conductivity in Li3AlS3 than in Li4.4M0.4M′0.6S4. A complete study of the Li energy landscape to elucidate Li diffusion pathways will be undertaken to yield further insight into the role of these structural features.
In this structure type, the M/S ratio imposes the arrangement pattern of the Al tetrahedra in dimers or isolated tetrahedra and triggers the stabilization of ordered or disordered vacancies within both the tetrahedral and the Li-only layer. The lithium conductivity properties of each of the compounds can then directly be related to the structure through the amount of disordered Li vacancies, which itself can be explained by the composition through the M/S ratio. This work illustrates that, in this structure type, an M/S ratio that is too large causes structural arrangements that inhibit the diffusion of Li.

4. Conclusions

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We have investigated the Li–Al–O–S phase diagram through a probe structure approach, which combined experimental and computational studies to yield a new phase while ruling out others. Indeed, this study revealed that no oxysulfide phases could be successfully obtained, but led to the discovery of the new sulfide Li3AlS3. The structure and properties of this compound were determined by means of high-resolution X-ray and neutron diffraction, multinuclear NMR spectroscopy at various fields, and electrochemical impedance spectroscopy. The stability of the new phase is believed to rely on the presence of AlS4 dimers, a peculiar feature not observed before in other Li ion conducting phases. The structure was described by comparing the cation polyhedral arrangements with those of other related phases with similar compositions, such as Na3MCh3 (M = Al, Ga, In; Ch = S, Se), Li2FeS2, and Li5AlS4. The study of this new compound in comparison with other similar sodium and lithium chalcogenide phases widens the spectra of possibilities to explore new interesting structures in related phase fields.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.9b03230.

  • Experimental synthesis procedure for the preparation of LiAlO2 and the attempted Li3AlO3, X-ray diffraction patterns of the samples prepared in the Li–Al–O–S phase fields, comparison of the Le Bail fits of the SXRD data with and without the use of the spherical harmonics, details of the elemental analysis of Li3AlS3, structural information of Li3AlS3 determined by diffraction data refinement (refinement details, atomic positions, Fourier difference map of the Li2 and Li3 positions, bond distances and angles), NMR shift calculations, and additional NMR experimental results, analysis of the impedance data (PDF)

  • Crystallographic data (CIF)

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Author Information

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  • Corresponding Author
  • Authors
    • Jacinthe Gamon - Department of Chemistry, University of Liverpool, Crown Street, L69 7ZD Liverpool, U.K.;  Orcidhttp://orcid.org/0000-0002-0888-4248
    • Benjamin B. Duff - Department of Chemistry, University of Liverpool, Crown Street, L69 7ZD Liverpool, U.K.;  Stephenson Institute for Renewable Energy, University of Liverpool, Peach Street L69 7ZF Liverpool, U.K.;  Orcidhttp://orcid.org/0000-0002-7398-5002
    • Matthew S. Dyer - Department of Chemistry, University of Liverpool, Crown Street, L69 7ZD Liverpool, U.K.;  Orcidhttp://orcid.org/0000-0002-4923-3003
    • Christopher Collins - Department of Chemistry, University of Liverpool, Crown Street, L69 7ZD Liverpool, U.K.;  Orcidhttp://orcid.org/0000-0002-0101-4426
    • Luke M. Daniels - Department of Chemistry, University of Liverpool, Crown Street, L69 7ZD Liverpool, U.K.;  Orcidhttp://orcid.org/0000-0002-7077-6125
    • T. Wesley Surta - Department of Chemistry, University of Liverpool, Crown Street, L69 7ZD Liverpool, U.K.;  Orcidhttp://orcid.org/0000-0002-2882-6483
    • Paul M. Sharp - Department of Chemistry, University of Liverpool, Crown Street, L69 7ZD Liverpool, U.K.
    • Michael W. Gaultois - Department of Chemistry, University of Liverpool, Crown Street, L69 7ZD Liverpool, U.K.;  Orcidhttp://orcid.org/0000-0003-2172-2507
    • Frédéric Blanc - Department of Chemistry, University of Liverpool, Crown Street, L69 7ZD Liverpool, U.K.;  Stephenson Institute for Renewable Energy, University of Liverpool, Peach Street L69 7ZF Liverpool, U.K.;  Orcidhttp://orcid.org/0000-0001-9171-1454
    • John Bleddyn Claridge - Department of Chemistry, University of Liverpool, Crown Street, L69 7ZD Liverpool, U.K.;  Orcidhttp://orcid.org/0000-0003-4849-6714
  • Notes
    The authors declare no competing financial interest.

    Underlying data is available at doi.org/10.17638/datacat.liverpool.ac.uk/988.

Acknowledgments

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We thank EPSRC for funding under EP/N004884. M.W.G. thanks the Leverhulme Trust for funding via the Leverhulme Research Centre for Functional Materials Design. We acknowledge the ISCF Faraday Challenge project: “SOLBAT – The Solid-State (Li or Na) Metal-Anode Battery” including partial support of a studentship to B.D., also supported by the University of Liverpool. We thank Diamond Light Source for access to beamline I11 and Prof. Chiu Tang and Dr. Sarah Day for assistance on the beamline. We thank STFC for access to HRPD (Xpress proposals 1890295) and Dr. Dominic Fortes for running the measurements and for performing the absorption correction on the data. The UK 850 MHz solid-state NMR Facility used in this research was funded by EPSRC and BBSRC, as well as the University of Warwick including via part funding through Birmingham Science City Advanced Materials Projects 1 and 2 supported by Advantage West Midlands (AWM) and the European Regional Development Fund (ERDF). Collaborative assistance from the 850 MHz Facility Manager (Dr. Dinu Iuga, University of Warwick) is acknowledged. M.J.R. thanks the Royal Society for the award of a Research Professorship.

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    Compared with Li-ion batteries with liq. electrolytes, all-solid-state batteries offer an attractive option owing to their potential in improving the safety and achieving both high power and high energy densities. Despite extensive research efforts, the development of all-solid-state batteries still falls short of expectation largely because of the lack of suitable candidate materials for the electrolyte required for practical applications. Here the authors report Li superionic conductors with an exceptionally high cond. (25 mS cm-1 for Li9.54Si1.74P1.44S11.7Cl0.3), as well as high stability ( ∼0 V vs. Li metal for Li9.6P3S12). A fabricated all-solid-state cell based on this Li conductor has very small internal resistance, esp. at 100 oC. The cell possesses high specific power that is superior to that of conventional cells with liq. electrolytes. Stable cycling with a high c.d. of 18 C (charging/discharging in just 3 min; where C is the C-rate) is also demonstrated.
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    Yamane, H.; Shibata, M.; Shimane, Y.; Junke, T.; Seino, Y.; Adams, S.; Minami, K.; Hayashi, A.; Tatsumisago, M. Crystal Structure of a Superionic Conductor, Li7P3S11. Solid State Ionics 2007, 178, 1163– 1167,  DOI: 10.1016/j.ssi.2007.05.020
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    Crystal structure of a superionic conductor, Li7P3S11
    Yamane, Hisanori; Shibata, Masatoshi; Shimane, Yukio; Junke, Tadanori; Seino, Yoshikatsu; Adams, Stefan; Minami, Keiichi; Hayashi, Akitoshi; Tatsumisago, Masahiro
    Solid State Ionics (2007), 178 (15-18), 1163-1167CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
    A synchrotron x-ray powder diffraction pattern was measured for a Li superionic conductor, Li7P3S11, which has a high cond. of 3.2 × 10-3 S cm-1 at room temp. and a low activation energy of 12 kJ mol-1 [Mizuno et al. (2006)]. The crystal structure was solved by a direct space global optimization technique and refined by the Rietveld method. The compd. crystallizes in a triclinic cell, space group P-1, a = 12.5009(3), b = 6.03160(17), c = 12.5303(3) Å, α = 102.845(3)°, β = 113.2024(18)°, γ = 74.467(3)°, dc = 1.98 g/cm3, Rwp = 2.92%, Rp = 2.20%, RR = 7.69%, Re = 1.82%, RI = 1.95%, RF = 0.73%. PS4 tetrahedra and P2S7 ditetrahedra are contained in the structure and Li ions are situated between them.
  16. 16
    Seino, Y.; Ota, T.; Takada, K.; Hayashi, A.; Tatsumisago, M. A Sulphide Lithium Super Ion Conductor Is Superior to Liquid Ion Conductors for Use in Rechargeable Batteries. Energy Environ. Sci. 2014, 7, 627– 631,  DOI: 10.1039/C3EE41655K
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    A sulphide lithium super ion conductor is superior to liquid ion conductors for use in rechargeable batteries
    Seino, Yoshikatsu; Ota, Tsuyoshi; Takada, Kazunori; Hayashi, Akitoshi; Tatsumisago, Masahiro
    Energy & Environmental Science (2014), 7 (2), 627-631CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
    We report that a heat-treated Li2S-P2S5 glass-ceramic conductor has an extremely high ionic cond. of 1.7 × 10-2 S cm-1 and the lowest conduction activation energy of 17 kJ mol-1 at room temp. among lithium-ion conductors reported to date. The optimum conditions of the heat treatment reduce the grain boundary resistance, and the influence of voids, to increase the Li+ ionic cond. of the solid electrolyte so that it is greater than the conductivities of liq. electrolytes, when the transport no. of lithium ions in the inorg. electrolyte is unity.
  17. 17
    Boulineau, S.; Courty, M.; Tarascon, J.-M.; Viallet, V. Mechanochemical Synthesis of Li-Argyrodite Li6PS5X (X=Cl, Br, I) as Sulfur-Based Solid Electrolytes for All Solid State Batteries Application. Solid State Ionics 2012, 221, 1– 5,  DOI: 10.1016/j.ssi.2012.06.008
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    Mechanochemical synthesis of Li-argyrodite Li6PS5 X (X = Cl, Br, I) as sulfur-based solid electrolytes for all solid state batteries application
    Boulineau, Sylvain; Courty, Matthieu; Tarascon, Jean-Marie; Viallet, Virginie
    Solid State Ionics (2012), 221 (), 1-5CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
    Highly ion-conductive Li6PS5 X (X = Cl, Br, I) Li-argyrodites were prepd. through a high-energy ball milling. Elec. and electrochem. properties were investigated. Ball-milled compds. exhibit a high cond. between 2 and 7 × 10- 4 S/cm with an activation energy of 0.3-0.4 eV for conduction. These attractive properties were attributed to the spontaneous formation of crystd. Li-argyrodite during ball-milling. An optimization of milling time led to a cond. of 1.33 × 10- 3 S/cm for the Li6PS5Cl phase with an electrochem. stability up to 7 V vs. lithium. An all solid state LiCoO2/Elec./In lithium ion battery using ball-milled Li6PS5Cl as electrolyte was successfully assembled, and its room temp. performance is reported.
  18. 18
    Rao, R. P.; Adams, S. Studies of Lithium Argyrodite Solid Electrolytes for All-Solid-State Batteries. Phys. Status Solidi A 2011, 208, 1804– 1807,  DOI: 10.1002/pssa.201001117
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    Studies of lithium argyrodite solid electrolytes for all-solid-state batteries
    Rao, R. P.; Adams, S.
    Physica Status Solidi A: Applications and Materials Science (2011), 208 (8), 1804-1807CODEN: PSSABA; ISSN:1862-6300. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Rechargeable all-solid-state lithium Li-ion batteries (AS-LIBs) are attractive power sources for electrochem. applications; due to their potentiality in improving safety and stability over conventional batteries with liq. electrolytes. AS-LIBs require a Li-fast ion conductor (FIC) as the solid electrolyte. Finding a solid electrolyte with high ionic cond. and compatibility with other battery components is a key factor in building high performance AS-LIBs. There have been numerous studies, e.g., on lithium rich sulfide glasses as solid electrolytes. However, the limited c.d. remains a major obstacle in developing competitive batteries based on the known solid electrolytes. Here we prep. argyrodite-type Li6PS5X (X = Cl, Br, I) using mech. milling followed by annealing. XRD characterization reveals the formation and growth of Li6PS5X crystals in samples under varying annealing conditions. For Li6PS5Cl an ionic cond. of the order of 10-4 S/cm is reached at room temp., which is close to the Li mobility in conventional liq. electrolytes (LiPF6 in various carbonates) and well suitable for AS-LIBs.
  19. 19
    Bernges, T.; Culver, S. P.; Minafra, N.; Koerver, R.; Zeier, W. G. Competing Structural Influences in the Li Superionic Conducting Argyrodites Li6PS5–x SexBr (0 ≤ x ≤ 1) upon Se Substitution. Inorg. Chem. 2018, 57, 13920– 13928,  DOI: 10.1021/acs.inorgchem.8b02443
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    Competing Structural Influences in the Li Superionic Conducting Argyrodites Li6PS5-xSexBr (0 ≤ x ≤ 1) upon Se Substitution
    Bernges, Tim; Culver, Sean P.; Minafra, Nicolo; Koerver, Raimund; Zeier, Wolfgang G.
    Inorganic Chemistry (2018), 57 (21), 13920-13928CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)
    Li-ion conducting argyrodites have recently attracted significant interest as solid electrolytes for solid-state battery applications. To enhance the utility of materials in this class, a deeper understanding of the fundamental structure-property relations is still required. Using Rietveld refinements of x-ray diffraction data and pair distribution function anal. of neutron diffraction data, coupled with electrochem. impedance spectroscopy and speed of sound measurements, the structure and transport properties within Li6PS5-xSexBr (0 ≤ x ≤ 1) were monitored with increasing Se content. While it was previously suggested that the incorporation of larger, more polarizable anions within the argyrodite lattice should lead to enhancements in the ionic cond., the Li6PS5-xSexBr transport behavior is 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 cond. 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.
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    Wang, Y.; Richards, W. D.; Ong, S. P.; Miara, L. J.; Kim, J. C.; Mo, Y.; Ceder, G. Design Principles for Solid-State Lithium Superionic Conductors. Nat. Mater. 2015, 14, 1026– 1031,  DOI: 10.1038/nmat4369
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    Design principles for solid-state lithium superionic conductors
    Wang, Yan; Richards, William Davidson; Ong, Shyue Ping; Miara, Lincoln J.; Kim, Jae Chul; Mo, Yifei; Ceder, Gerbrand
    Nature Materials (2015), 14 (10), 1026-1031CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
    Lithium solid electrolytes can potentially address two key limitations of the org. electrolytes used in today's lithium-ion batteries, namely, their flammability and limited electrochem. stability. However, achieving a Li+ cond. in the solid state comparable to existing liq. electrolytes (>1 mS cm-1) is particularly challenging. In this work, we reveal a fundamental relationship between anion packing and ionic transport in fast Li-conducting materials and expose the desirable structural attributes of good Li-ion conductors. We find that an underlying body-centered cubic-like anion framework, which allows direct Li hops between adjacent tetrahedral sites, is most desirable for achieving high ionic cond., and that indeed this anion arrangement is present in several known fast Li-conducting materials and other fast ion conductors. These findings provide important insight towards the understanding of ionic transport in Li-ion conductors and serve as design principles for future discovery and design of improved electrolytes for Li-ion batteries.
  21. 21
    Kraft, M. A.; Culver, S. P.; Calderon, M.; Böcher, F.; Krauskopf, T.; Senyshyn, A.; Dietrich, C.; Zevalkink, A.; Janek, J.; Zeier, W. G. Influence of Lattice Polarizability on the Ionic Conductivity in the Lithium Superionic Argyrodites Li6PS5X (X = Cl, Br, I). J. Am. Chem. Soc. 2017, 139, 10909– 10918,  DOI: 10.1021/jacs.7b06327
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    Influence of Lattice Polarizability on the Ionic Conductivity in the Lithium Superionic Argyrodites Li6PS5X (X = Cl, Br, I)
    Kraft, Marvin A.; Culver, Sean P.; Calderon, Mario; Boecher, Felix; Krauskopf, Thorben; Senyshyn, Anatoliy; Dietrich, Christian; Zevalkink, Alexandra; Janek, Juergen; Zeier, Wolfgang G.
    Journal of the American Chemical Society (2017), 139 (31), 10909-10918CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    In the search for novel solid electrolytes for solid-state batteries, thiophosphate ionic conductors have been in recent focus owing to their high ionic conductivities, which are believed to stem from a softer, more polarizable anion framework. Inspired by the oft-cited connection between a soft anion lattice and ionic transport, this work aims to provide evidence on how changing the polarizability of the anion sublattice in one structure affects ionic transport. Here, we systematically alter the anion framework polarizability of the superionic argyrodites Li6PS5X by controlling the fractional occupancy of the halide anions (X = Cl, Br, I). Ultrasonic speed of sound measurements are used to quantify the variation in the lattice stiffness and Debye frequencies. In combination with electrochem. impedance spectroscopy and neutron diffraction, these results show that the lattice softness has a striking influence on the ionic transport: the softer bonds lower the activation barrier and simultaneously decrease the prefactor of the moving ion. Due to the contradicting influence of these parameters on ionic cond., we find that it is necessary to tailor the lattice stiffness of materials in order to obtain an optimum ionic cond.
  22. 22
    Zhu, Y.; He, X.; Mo, Y. Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations. ACS Appl. Mater. Interfaces 2015, 7, 23685– 23693,  DOI: 10.1021/acsami.5b07517
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    Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations
    Zhu, Yizhou; He, Xingfeng; Mo, Yifei
    ACS Applied Materials & Interfaces (2015), 7 (42), 23685-23693CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    First-principles calcns. were performed to investigate the electrochem. stability of lithium solid electrolyte materials in all-solid-state Li-ion batteries. The common solid electrolytes were found to have a limited electrochem. window. The results suggest that the outstanding stability of the solid electrolyte materials is not thermodynamically intrinsic but is originated from kinetic stabilizations. The sluggish kinetics of the decompn. reactions cause a high overpotential leading to a nominally wide electrochem. window obsd. in many expts. The decompn. products, similar to the solid-electrolyte-interphases, mitigate the extreme chem. potential from the electrodes and protect the solid electrolyte from further decompns. With the aid of the first-principles calcns., the passivation mechanism is revealed of these decompn. interphases and quantified the extensions of the electrochem. window from the interphases. It was also found that the artificial coating layers applied at the solid electrolyte and electrode interfaces have a similar effect of passivating the solid electrolyte. The newly gained understanding provided general principles for developing solid electrolyte materials with enhanced stability and for engineering interfaces in all-solid-state Li-ion batteries.
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    Zheng, F.; Kotobuki, M.; Song, S.; Lai, M. O.; Lu, L. Review on Solid Electrolytes for All-Solid-State Lithium-Ion Batteries. J. Power Sources 2018, 389, 198– 213,  DOI: 10.1016/j.jpowsour.2018.04.022
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    Review on solid electrolytes for all-solid-state lithium-ion batteries
    Zheng, Feng; Kotobuki, Masashi; Song, Shufeng; Lai, Man On; Lu, Li
    Journal of Power Sources (2018), 389 (), 198-213CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
    All-solid-state (ASS) lithium-ion battery has attracted great attention due to its high safety and increased energy d. One of key components in the ASS battery (ASSB) is solid electrolyte that dets. performance of the ASSB. Many types of solid electrolytes have been investigated in great detail in the past years, including NASICON-type, garnet-type, perovskite-type, LISICON-type, LiPON-type, Li3N-type, sulfide-type, argyrodite-type, anti-perovskite-type and many more. This paper aims to provide comprehensive reviews on some typical types of key solid electrolytes and some ASSBs, and on gaps that should be resolved.
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    Deng, Z.; Zhu, Z.; Chu, I.-H.; Ong, S. P. Data-Driven First-Principles Methods for the Study and Design of Alkali Superionic Conductors. Chem. Mater. 2017, 29, 281– 288,  DOI: 10.1021/acs.chemmater.6b02648
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    Data-Driven First-Principles Methods for the Study and Design of Alkali Superionic Conductors
    Deng, Zhi; Zhu, Zhuoying; Chu, Iek-Heng; Ong, Shyue Ping
    Chemistry of Materials (2017), 29 (1), 281-288CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    A detailed exposition of how first-principles methods can be used to guide alkali superionic conductor (ASIC) study and design is presented. Using the argyrodite Li6PS5Cl as a case study, it is demonstrated how modern information technol. (IT) infrastructure and software tools can facilitate the assessment of alkali superionic conductors in terms of various crit. properties of interest such as phase and electrochem. stability and ionic cond. The emphasis is on well-documented, reproducible anal. code that can be readily generalized to other material systems and design problems. For our chosen Li6PS5Cl case study material, it is shown that Li excess is crucial to enhancing its cond. by increasing the occupancy of interstitial sites that promote long-range Li+ diffusion between cage-like frameworks. The predicted room-temp. conductivities and activation barriers are in reasonably good agreement with exptl. values.
  25. 25
    Ceder, G. Opportunities and Challenges for First-Principles Materials Design and Applications to Li Battery Materials. MRS Bull. 2010, 35, 693– 701,  DOI: 10.1557/mrs2010.681
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    Opportunities and challenges for first-principles materials design and applications to Li battery materials
    Ceder, Gerbrand
    MRS Bulletin (2010), 35 (9), 693-701CODEN: MRSBEA; ISSN:0883-7694. (Materials Research Society)
    The idea of first-principles methods is to det. the properties of materials by solving the basic equations of quantum mechanics and statistical mechanics. With such an approach, one can, in principle, predict the behavior of novel materials without the need to synthesize them and create a virtual design lab. By showing several examples of new electrode materials that have been computationally designed, synthesized, and tested, the impact of first-principles methods in the field of Li battery electrode materials will be demonstrated. A significant advantage of computational property prediction is its scalability, which is currently being implemented into the Materials Genome Project at the Massachusetts Institute of Technol. Using a high-throughput computational environment, coupled to a database of all known inorg. materials, basic information on all known inorg. materials and a large no. of novel "designed" materials is being computed. Scalability of high-throughput computing can easily be extended to reach across the complete universe of inorg. compds., although challenges need to be overcome to further enable the impact of first-principles methods.
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    Sendek, A. D.; Yang, Q.; Cubuk, E. D.; Duerloo, K.-A. N.; Cui, Y.; Reed, E. J. Holistic Computational Structure Screening of More than 12000 Candidates for Solid Lithium-Ion Conductor Materials. Energy Environ. Sci. 2017, 10, 306– 320,  DOI: 10.1039/C6EE02697D
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    Holistic computational structure screening of more than 12 000 candidates for solid lithium-ion conductor materials
    Sendek, Austin D.; Yang, Qian; Cubuk, Ekin D.; Duerloo, Karel-Alexander N.; Cui, Yi; Reed, Evan J.
    Energy & Environmental Science (2017), 10 (1), 306-320CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
    We present a new type of large-scale computational screening approach for identifying promising candidate materials for solid state electrolytes for lithium ion batteries that is capable of screening all known lithium contg. solids. To be useful for batteries, high performance solid state electrolyte materials must satisfy many requirements at once, an optimization that is difficult to perform exptl. or with computationally expensive ab initio techniques. We first screen 12 831 lithium contg. cryst. solids for those with high structural and chem. stability, low electronic cond., and low cost. We then develop a data-driven ionic cond. classification model using logistic regression for identifying which candidate structures are likely to exhibit fast lithium conduction based on exptl. measurements reported in the literature. The screening reduces the list of candidate materials from 12 831 down to 21 structures that show promise as electrolytes, few of which have been examd. exptl. We discover that none of our simple atomistic descriptor functions alone provide predictive power for ionic cond., but a multi-descriptor model can exhibit a useful degree of predictive power. We also find that screening for structural stability, chem. stability and low electronic cond. eliminates 92.2% of all Li-contg. materials and screening for high ionic cond. eliminates a further 93.3% of the remainder. Our screening utilizes structures and electronic information contained in the Materials Project database.
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    Hautier, G.; Fischer, C. C.; Jain, A.; Mueller, T.; Ceder, G. Finding Nature’s Missing Ternary Oxide Compounds Using Machine Learning and Density Functional Theory. Chem. Mater. 2010, 22, 3762– 3767,  DOI: 10.1021/cm100795d
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    Finding Nature's Missing Ternary Oxide Compounds Using Machine Learning and Density Functional Theory
    Hautier, Geoffroy; Fischer, Christopher C.; Jain, Anubhav; Mueller, Tim; Ceder, Gerbrand
    Chemistry of Materials (2010), 22 (12), 3762-3767CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    Finding new compds. and their crystal structures is an essential step to new materials discoveries. We demonstrate how this search can be accelerated using a combination of machine learning techniques and high-throughput ab initio computations. Using a probabilistic model built on an exptl. crystal structure database, novel compns. that are most likely to form a compd., and their most-probable crystal structures, are identified and tested for stability by ab initio computations. We performed such a large-scale search for new ternary oxides, discovering 209 new compds. with a limited computational budget. A list of these predicted compds. is provided, and we discuss the chemistries in which high discovery rates can be expected.
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    Fujimura, K.; Seko, A.; Koyama, Y.; Kuwabara, A.; Kishida, I.; Shitara, K.; Fisher, C. A. J.; Moriwake, H.; Tanaka, I. Accelerated Materials Design of Lithium Superionic Conductors Based on First-Principles Calculations and Machine Learning Algorithms. Adv. Energy Mater. 2013, 3, 980– 985,  DOI: 10.1002/aenm.201300060
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    Accelerated materials design of lithium superionic conductors based on first-principles calculations and machine learning algorithms
    Fujimura, Koji; Seko, Atsuto; Koyama, Yukinori; Kuwabara, Akihide; Kishida, Ippei; Shitara, Kazuki; Fisher, Craig A. J.; Moriwake, Hiroki; Tanaka, Isao
    Advanced Energy Materials (2013), 3 (8), 980-985CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)
    In this article, results of systematic sets of first-principles calcns. based on the cluster expansion method, as well as first-principles mol. dynamics (FPMD) simulations carried out to calc. lithium-ion conductivities at high temp., for a diverse range of compns. is studied. A machine-learning technique is used to combine theor. and exptl. datasets to predict the cond. of each compn. at 373 K. The insights obtained show that an iterative combination of first-principles calcns. and focused expts. can greatly accelerate the materials design process by enabling a wide compositional and structural phase space to be examd. efficiently.
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    Adams, S. Bond Valence Analysis of Structure–Property Relationships in Solid Electrolytes. J. Power Sources 2006, 159, 200– 204,  DOI: 10.1016/j.jpowsour.2006.04.085
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    Bond valence analysis of structure-property relationships in solid electrolytes
    Adams, Stefan
    Journal of Power Sources (2006), 159 (1), 200-204CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
    The augmented bond valence approach may be used to establish structure-property relations in solid electrolytes, to identify the mobile species and to locate energetically favorable transport pathways for mobile ions, using the bond valence sum mismatch landscape created by the immobile substructure. Ion transport pathways of cryst. and glassy Li+ conductors are analyzed. The bond valence anal. provides the visualization of pathways and the relevant activation energies - thereby it helps to clarify transport mechanisms and to identify promising novel ion-conducting materials. The approach is particularly useful for the anal. of disordered systems such as ion-conducting glasses, where a structure-cond. correlation was identified.
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    Xiao, R.; Li, H.; Chen, L. High-Throughput Design and Optimization of Fast Lithium Ion Conductors by the Combination of Bond-Valence Method and Density Functional Theory. Sci. Rep. 2015, 5, 14227,  DOI: 10.1038/srep14227
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    High-throughput design and optimization of fast lithium ion conductors by the combination of bond-valence method and density functional theory
    Xiao, Ruijuan; Li, Hong; Chen, Liquan
    Scientific Reports (2015), 5 (), 14227CODEN: SRCEC3; ISSN:2045-2322. (Nature Publishing Group)
    Looking for solid state electrolytes with fast lithium ion conduction is an important prerequisite for developing all-solid-state lithium secondary batteries. By combining the simulation techniques in different levels of accuracy, e.g. the bond-valence (BV) method and the d. functional theory (DFT), a high-throughput design and optimization scheme is proposed for searching fast lithium ion conductors as candidate solid state electrolytes for lithium rechargeable batteries. The screening from more than 1000 compds. is performed through BV-based method, and the ability to predict reliable tendency of the Li+ migration energy barriers is confirmed by comparing with the results from DFT calcns. β-Li3PS4 is taken as a model system to demonstrate the application of this combination method in optimizing properties of solid electrolytes. By employing the high-throughput DFT simulations to more than 200 structures of the doping derivs. of β-Li3PS4, the effects of doping on the ionic conductivities in this material are predicted by the BV calcns. The O-doping scheme is proposed as a promising way to improve the kinetic properties of this materials, and the validity of the optimization is proved by the first-principles mol. dynamics (FPMD) simulations.
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    Adams, S.; Rao, R. P. Understanding Ionic Conduction and Energy Storage Materials with Bond-Valence-Based Methods. In Bond Valences; Brown, I. D.; Poeppelmeier, K. R. Eds. Structure and Bonding; Springer Berlin Heidelberg: Berlin, Heidelberg, 2014; pp 129– 159.
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    Kandagal, V. S.; Bharadwaj, M. D.; Waghmare, U. V. Theoretical Prediction of a Highly Conducting Solid Electrolyte for Sodium Batteries: Na10GeP2S12. J. Mater. Chem. A 2015, 3, 12992– 12999,  DOI: 10.1039/C5TA01616A
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    Theoretical prediction of a highly conducting solid electrolyte for sodium batteries: Na10GeP2S12
    Kandagal, Vinay S.; Bharadwaj, Mridula Dixit; Waghmare, Umesh V.
    Journal of Materials Chemistry A: Materials for Energy and Sustainability (2015), 3 (24), 12992-12999CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
    Using 1st-principles simulations, the authors predict a high-performance solid electrolyte Na10GeP2S12 for use in Na-S (Na-S) batteries. The thermodn. stability of its structure is established through detn. of decompn. reaction energies and phonons, while Na-ionic cond. is obtained using ab initio mol. dynamics at elevated temps. The est. of the room-temp. (RT) cond. is 4.7 × 10-3 S cm-1, which is slightly higher than those of other superionic solid electrolytes such as β''-alumina and Na3Zr2Si2PO12, currently used in practical high-temp. Na-S batteries. Activation energy obtained from the Arrhenius plot (in the range 800-1400 K) is 0.2 eV, which is slightly lower than the typical values exhibited by other ceramic conductors (0.25-1 V) (Hueso et al., Energy Environ. Sci., 2013, 6, 734). Soft Na-S phonon modes are responsible for its thermodn. stability and the lower activation barrier for diffusion of Na-ions. Finally, the calcd. electronic bandgap of 2.7 eV (a wide electrochem. window) augurs well for its safe use in Na batteries. Opening up a possibility for realizing RT operation of Na-S batteries, the prediction of a new phase in the Na-Ge-P-S system will stimulate exptl. studies of the material.
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    Zhang, Y.; Miller, G. J.; Fokwa, B. P. T. Computational Design of Rare-Earth-Free Magnets with the Ti3Co5B2-Type Structure. Chem. Mater. 2017, 29, 2535– 2541,  DOI: 10.1021/acs.chemmater.6b04114
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    Computational Design of Rare-Earth-Free Magnets with the Ti3Co5B2-Type Structure
    Zhang, Yuemei; Miller, Gordon J.; Fokwa, Boniface P. T.
    Chemistry of Materials (2017), 29 (6), 2535-2541CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    The prolific Ti3Co5B2 structure type produced exciting materials with tunable magnetic properties, ranging from soft magnetic Ti2FeRh5B2, to semihard magnetic Ti2FeRu4RhB2 and hard magnetic Sc2FeRu3Ir2B2. D. functional theory (DFT) was employed to study their spin-orbit coupling effect, spin exchange, and magnetic dipole-dipole interactions to understand their magnetic anisotropy and relate it to their various coercivities, with the objective of being able to predict new materials with large magnetic anisotropy. The authors' calcns. show that the contribution of magnetic dipole-dipole interactions to the magnetocryst. anisotropy energy (MAE) in Ti3Co5B2-type compds. is much weaker than the spin-orbit coupling effect, and Sc2FeRu3Ir2B2 has, by far, the largest MAE and strong intrachain and interchain Fe-Fe spin exchange coupling, thus confirming its hard magnetic properties. The authors then targeted materials contg. the more earth-abundant and less expensive Co, instead of Rh, Ru or Ir, so that the authors' study started with Ti3Co5B2, which the authors found to be nonmagnetic. In the next step, substitutions on the Ti sites in Ti3Co5B2 led to new potential quaternary phases T2T'Co5B2 (T = Ti, Hf; T' = Mn, Fe). For Hf2MnCo5B2, the authors found a large MAE (+0.96 meV/f.u.) but relatively weak interchain Mn-Mn spin exchange interactions, whereas for Hf2FeCo5B2, there is a relatively smaller MAE (+0.17 meV/f.u.) but strong Fe-Fe interchain and intrachain spin exchange interactions. Therefore, these two Co-rich phases are predicted to be new rare-earth-free, semihard to hard magnetic materials.
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    Wang, Y.; Richards, W. D.; Bo, S.-H.; Miara, L. J.; Ceder, G. Computational Prediction and Evaluation of Solid-State Sodium Superionic Conductors Na7P3X11 (X = O, S, Se). Chem. Mater. 2017, 29, 7475– 7482,  DOI: 10.1021/acs.chemmater.7b02476
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    34
    Computational Prediction and Evaluation of Solid-State Sodium Superionic Conductors Na7P3X11 (X = O, S, Se)
    Wang, Yan; Richards, William D.; Bo, Shou-Hang; Miara, Lincoln J.; Ceder, Gerbrand
    Chemistry of Materials (2017), 29 (17), 7475-7482CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    Inorg. solid-state ionic conductors with high ionic cond. are of great interest for their application in safe and high-energy-d. solid-state batteries. Our previous study reveals that the crystal structure of the ionic conductor Li7P3S11 contains a body-centered-cubic (bcc) arrangement of sulfur anions and that such a bcc anion framework facilitates high ionic cond. Here, we apply a set of first-principles calcns. techniques to investigate A7P3X11-type (A = Li, Na; X = O, S, Se) lithium and sodium superionic conductors derived from Li7P3S11, focusing on their structural, dynamic and thermodn. properties. We find that the ionic cond. of Na7P3S11 and Na7P3Se11 is over 10 mS cm-1 at room temp., significantly higher than that of any known solid Na-ion sulfide or selenide conductor. However, thermodn. calcns. suggest that the isostructural sodium compds. may not be trivial to synthesize, which clarifies the puzzle concerning the exptl. problems in trying to synthesize these compds.
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    Collins, C.; Dyer, M. S.; Pitcher, M. J.; Whitehead, G. F. S.; Zanella, M.; Mandal, P.; Claridge, J. B.; Darling, G. R.; Rosseinsky, M. J. Accelerated Discovery of Two Crystal Structure Types in a Complex Inorganic Phase Field. Nature 2017, 546, 280,  DOI: 10.1038/nature22374
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    Accelerated discovery of two crystal structure types in a complex inorganic phase field
    Collins, C.; Dyer, M. S.; Pitcher, M. J.; Whitehead, G. F. S.; Zanella, M.; Mandal, P.; Claridge, J. B.; Darling, G. R.; Rosseinsky, M. J.
    Nature (London, United Kingdom) (2017), 546 (7657), 280-284CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
    The discovery of new materials is hampered by the lack of efficient approaches to the exploration of both the large no. of possible elemental compns. for such materials, and of the candidate structures at each compn. For example, the discovery of inorg. extended solid structures has relied on knowledge of crystal chem. coupled with time-consuming materials synthesis with systematically varied elemental ratios. Computational methods have been developed to guide synthesis by predicting structures at specific compns. and predicting compns. for known crystal structures, with notable successes. However, the challenge of finding qual. new, exptl. realizable compds., with crystal structures where the unit cell and the atom positions within it differ from known structures, remains for compositionally complex systems. Many valuable properties arise from substitution into known crystal structures, but materials discovery using this approach alone risks both missing best-in-class performance and attempting design with incomplete knowledge. Here we report the exptl. discovery of two structure types by computational identification of the region of a complex inorg. phase field that contains them. This is achieved by computing probe structures that capture the chem. and structural diversity of the system and whose energies can be ranked against combinations of currently known materials. Subsequent exptl. exploration of the lowest-energy regions of the computed phase diagram affords two materials with previously unreported crystal structures featuring unusual structural motifs. This approach will accelerate the systematic discovery of new materials in complex compositional spaces by efficiently guiding synthesis and enhancing the predictive power of the computational tools through expansion of the knowledge base underpinning them.
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    Dyer, M. S.; Collins, C.; Hodgeman, D.; Chater, P. A.; Demont, A.; Romani, S.; Sayers, R.; Thomas, M. F.; Claridge, J. B.; Darling, G. R. Computationally Assisted Identification of Functional Inorganic Materials. Science 2013, 340, 847– 852,  DOI: 10.1126/science.1226558
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    Computationally Assisted Identification of Functional Inorganic Materials
    Dyer, Matthew S.; Collins, Christopher; Hodgeman, Darren; Chater, Philip A.; Demont, Antoine; Romani, Simon; Sayers, Ruth; Thomas, Michael F.; Claridge, John B.; Darling, George R.; Rosseinsky, Matthew J.
    Science (Washington, DC, United States) (2013), 340 (6134), 847-852CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
    The design of complex inorg. materials is a challenge because of the diversity of their potential structures. We present a method for the computational identification of materials contg. multiple atom types in multiple geometries by ranking candidate structures assembled from extended modules contg. chem. realistic at. environments. Many existing functional materials can be described in this way, and their properties are often detd. by the chem. and electronic structure of their constituent modules. To demonstrate the approach, we isolated the oxide Y2.24Ba2.28Ca3.48Fe7.44Cu0.56O21, with a largest unit cell dimension of over 60 angstroms and 148 atoms in the unit cell, by using a combination of this method and exptl. work and show that it has the properties necessary to function as a solid oxide fuel-cell cathode.
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    Wang, X.; Xiao, R.; Li, H.; Chen, L. Oxysulfide LiAlSO: A Lithium Superionic Conductor from First Principles. Phys. Rev. Lett. 2017, 118, 195901,  DOI: 10.1103/PhysRevLett.118.195901
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    Oxysulfide LiAlSO: a lithium superionic conductor from first principles
    Wang, Xuelong; Xiao, Ruijuan; Li, Hong; Chen, Liquan
    Physical Review Letters (2017), 118 (19), 195901/1-195901/6CODEN: PRLTAO; ISSN:1079-7114. (American Physical Society)
    Through first-principles calcns. and crystal structure prediction techniques, we identify a new layered oxysulfide LiAlSO in orthorhombic structure as a novel lithium superionic conductor. Two kinds of stacking sequences of layers of AlS2O2 are found in different temp. ranges. Phonon and mol. dynamics simulations verify their dynamic stabilities, and wide band gaps up to 5.6 eV are found by electronic structure calcns. The lithium migration energy barrier simulations reveal the collective interstitial-host ion "kick-off" hopping mode with barriers lower than 50 meV as the dominating conduction mechanism for LiAlSO, indicating it to be a promising solid-state electrolyte in lithium secondary batteries with fast ionic cond. and a wide electrochem. window. This is a first attempt in which the lithium superionic conductors are designed by the crystal structure prediction method and may help explore other mixed-anion battery materials.
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    Huang, B. Energy Harvesting and Conversion Mechanisms for Intrinsic Upconverted Mechano-Persistent Luminescence in CaZnOS. Phys. Chem. Chem. Phys. 2016, 18, 25946– 25974,  DOI: 10.1039/C6CP04706H
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    Energy harvesting and conversion mechanisms for intrinsic upconverted mechano-persistent luminescence in CaZnOS
    Huang, Bolong
    Physical Chemistry Chemical Physics (2016), 18 (37), 25946-25974CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
    The authors interpreted the mechanisms of energy harvesting and conversion for intrinsic upconverted mechano-persistent luminescence in CaZnOS through a native point defects study. Vacancy defects such as Zn and O vacancies, as well as Schottky pair defects, act as energy harvesting centers; they are very readily formed and very active. They are extra deep electron or hole trap levels near the valence or conduction band edges, resp. This leads to a coupling and exchange effect to continuously collect and transport host charges along a path via localized states to deep recombination levels. The initiating energy barrier is small and can be overcome by ambient thermal stimulation or quantum tunneling. Native activators such as V2+O, V2+ZnO, and V2+CaZnOS function as energy conversion centers to transfer energy into photon emissions. This gives a solid theor. ref. for developing upconverted mechano-persistent luminescence.
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    Rangasamy, E.; Sahu, G.; Keum, J. K.; Rondinone, A. J.; Dudney, N. J.; Liang, C. A High Conductivity Oxide–Sulfide Composite Lithium Superionic Conductor. J. Mater. Chem. A 2014, 2, 4111– 4116,  DOI: 10.1039/C3TA15223E
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    A high conductivity oxide-sulfide composite lithium superionic conductor
    Rangasamy, Ezhiylmurugan; Sahu, Gayatri; Keum, Jong Kahk; Rondinone, Adam J.; Dudney, Nancy J.; Liang, Chengdu
    Journal of Materials Chemistry A: Materials for Energy and Sustainability (2014), 2 (12), 4111-4116CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
    A composite electrolyte of LLZO (Li7La3Zr2O12) and LPS (β-Li3PS4) successfully combines low grain boundary resistance, room temp. processability, and low interfacial resistance of LPS with the excellent electrochem. stability and ionic cond. of LLZO. The composite electrolyte improves the ionic cond. of parent electrolytes and augments exceptional compatibility with metallic lithium, thereby making the electrolyte attractive for practical solid-state batteries.
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    Suzuki, K.; Sakuma, M.; Hori, S.; Nakazawa, T.; Nagao, M.; Yonemura, M.; Hirayama, M.; Kanno, R. Synthesis, Structure, and Electrochemical Properties of Crystalline Li-P-S-O Solid Electrolytes: Novel Lithium-Conducting Oxysulfides of Li10GeP2S12 Family. Solid State Ionics 2016, 288, 229– 234,  DOI: 10.1016/j.ssi.2016.02.002
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    Synthesis, structure, and electrochemical properties of crystalline Li-P-S-O solid electrolytes: Novel lithium-conducting oxysulfides of Li10GeP2S12 family
    Suzuki, Kota; Sakuma, Masamitsu; Hori, Satoshi; Nakazawa, Tetsuya; Nagao, Miki; Yonemura, Masao; Hirayama, Masaaki; Kanno, Ryoji
    Solid State Ionics (2016), 288 (), 229-234CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
    Novel lithium-ion (Li+)-conducting oxysulfides of the Li10GeP2S12 family were found in the ternary Li2S-P2S5-P2O5 system; Li10GeP2S12-type solid solns. with compns. Li3 + 5xP1 - xS4 - zOz (x = 0.03-0.08, z = 0.4-0.8) were confirmed. The solid solns. showed ionic conductivities from 4.14 × 10- 5 to 2.64 × 10- 4 S cm- 1 at 298 K and a wide electrochem. window of 0-5.0 V (vs. Li/Li+). Among the solid solns. synthesized, the purest phase had the compn. Li3.35P0.93S3.5O0.5 (x = 0.07, z = 0.5). Structural anal. revealed that the novel oxysulfides are isostructural to the original Li10GeP2S12 structure and the (P/.box.)(S/O)4 tetrahedra, which indicates the presence of cation defects with oxygen substitution in the crystal structure. Electrochem. stability of the oxysulfides was confirmed in the voltage range of 0-5.0 V. The solid-electrolyte interphase (SEI) resistivity and its cycle-dependence evaluation for new materials demonstrated that the oxysulfides had lower resistivities and furnished well-contacted SEI layers during the charge-discharge process.
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    Wang, X.; Xiao, R.; Li, H.; Chen, L. Oxygen-Driven Transition from Two-Dimensional to Three-Dimensional Transport Behaviour in β-Li3PS4 Electrolyte. Phys. Chem. Chem. Phys. 2016, 18, 21269– 21277,  DOI: 10.1039/C6CP03179J
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    Oxygen-driven transition from two-dimensional to three-dimensional transport behaviour in β-Li3PS4 electrolyte
    Wang, Xuelong; Xiao, Ruijuan; Li, Hong; Chen, Liquan
    Physical Chemistry Chemical Physics (2016), 18 (31), 21269-21277CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
    Solid state electrolytes with high Li ion conduction are vital to the development of all-solid-state lithium batteries. Lithium thiophosphate Li3PS4 is the parent material of a series of Li superionic conductors Li10MX2S12 (M = Ge, Sn,...; X = P, Si,...), and β-Li3PS4 shows relatively high ionic cond. itself, though it is not room-temp. stable. The pos. effects of introducing O dopants into β-Li3PS4 to stabilize the crystal phase and improve the ionic conducting behavior are revealed in this study. With the aid of first-principles d. functional theory (DFT) computations and quasi-empirical bond-valence calcns., the effects of O doping at different concns. on the properties of β-Li3PS4 is thoroughly investigated from the aspects of lattice structures, electronic structures, ionic transport properties, the interface stability against Li and the thermodn. stability. An oxygen-driven transition from two-dimensional to three-dimensional transport behavior is found and the oxygen dopants play the role as a connector of 2D paths. Based on all these simulation results, hopefully our research can provide a new strategy for the modification of lithium thiophosphate solid electrolytes.
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    Kim, K.-H.; Martin, S. W. Structures and Properties of Oxygen-Substituted Li10SiP2S12–xOx Solid-State Electrolytes. Chem. Mater. 2019, 31, 3984– 3991,  DOI: 10.1021/acs.chemmater.9b00505
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    Structures and Properties of Oxygen-Substituted Li10SiP2S12-xOx Solid-State Electrolytes
    Kim, Kwang-Hyun; Martin, Steve W.
    Chemistry of Materials (2019), 31 (11), 3984-3991CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    Li10SiP2S12 (LSiPS), which has an Li10GeP2S12 (LGPS)-type cryst. structure, was synthesized by solid-state reaction and then doped with O to produce oxy-sulfide compns. Li10SiP2S12-xOx (LSiPSO), where 0 ≤ x ≤ 1.75. The phase distribution and local structural units present in the LSiPSO materials were detd. via a combination of powder x-ray diffraction and Raman, FTIR, and solid-state NMR spectroscopies. At smaller amts. of O substitution for S, x < 1, in LSiPS, the structure of the LSiPSO phases became more uniform in the LGPS structure from smaller amts. of the impurity β-Li3PS4 and more of the O-substituted LGPS-like structure. Consistent with this, the Li ion cond. increases in proportion to the decrease in the amt. of the β-Li3PS4 phase and the growth of the LGPS-like phase. The highest Li ionic cond. was found for x = 0.7 at 3.1 (±0.4) × 10-3 S/cm at 25°. However, for x ≥ 0.9, ionic cond. decreased as a result of the degrdn. of the cryst. LGPS-like phase and generation of the O-rich Li3PO4 phase. 31P and 29Si NMR were used to det. the type and concn. of the various P and Si short-range order (SRO) structural units present as a function of x. Both pure sulfide, pure oxide, and mixed oxy-sulfide P and S SRO polyhedra were obsd. with the general trend being that as x increased, the fraction of mixed oxy-sulfide and pure oxide SRO polyhedra increased. Significantly, only pure oxide orthophosphate polyhedra PO4-3 were obsd., and no pure orthosilicate SiO44- SRO units were obsd., even at the highest x values examd.
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    Tao, Y.; Chen, S.; Liu, D.; Peng, G.; Yao, X.; Xu, X. Lithium Superionic Conducting Oxysulfide Solid Electrolyte with Excellent Stability against Lithium Metal for All-Solid-State Cells. J. Electrochem. Soc. 2016, 163, A96– A101,  DOI: 10.1149/2.0311602jes
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    Lithium Superionic Conducting Oxysulfide Solid Electrolyte with Excellent Stability against Lithium Metal for All-Solid-State Cells
    Tao, Yicheng; Chen, Shaojie; Liu, Deng; Peng, Gang; Yao, Xiayin; Xu, Xiaoxiong
    Journal of the Electrochemical Society (2016), 163 (2), A96-A101CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
    For the high-energy battery using Li metal as a neg. electrode, the electrolyte is one of the most crit. factors that significantly affects the cell performance. Herein, new 75Li2S·(25-x)P2S5·xP2O5 (mol%) solid state electrolytes are prepd. by optimized mech. milling technique and subsequent heat-treatment process. The electrolyte substituted with 1 mol% P2O5 presents the highest cond. of 8 × 10-4 S cm-1 at room temp., which increases up to 56% compared to that of the pristine sample. The enhanced cond. could be attributed to the decrease of the activation energy for Li+-ion diffusion. The as-prepd. 75Li2S·24P2S5·1P2O5 electrolyte exhibits good electrochem. stability and compatibility with the metallic lithium electrode. The all-solid-state cell with a structure of LiCoO2/75Li2S·24P2S5·1P2O5/Li shows a discharge capacity of 109 mAh g-1 at 0.1 C and high capacity retention 85.2% after 30 cycles at 25°C, which are better than these of the cell use the 75Li2S·25P2S5 as electrolyte.
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    Changming, F.; Haichun, G.; Yan, H.; Zengliang, C.; Yi, Z. Oxysulfide Glasses - a New Kind of Lithium Ion Conductors. Solid State Ionics 1991, 48, 289– 293,  DOI: 10.1016/0167-2738(91)90045-D
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    Gao, J.; Shi, S.; Xiao, R.; Li, H. Synthesis and Ionic Transport Mechanisms of α-LiAlO2. Solid State Ionics 2016, 286, 122– 134,  DOI: 10.1016/j.ssi.2015.12.028
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    Synthesis and ionic transport mechanisms of α-LiAlO2
    Gao, Jian; Shi, Siqi; Xiao, Ruijuan; Li, Hong
    Solid State Ionics (2016), 286 (), 122-134CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
    The pure phase α-LiAlO2 is synthesized by a solid-state reaction. The obtained product has nanocryst. structure with the Li deficient regions near the surfaces. Combining X-ray diffraction (XRD) and thermogravimetry-differential scanning calorimetry (TG-DSC), the synthesis mechanism is revealed. The measured room-temp. ionic cond. of the α-LiAlO2 ceramic pellet is as low as 10- 21 S·cm- 1. This could be caused by the absence of conduction pathways, as calcd. from the bond-valence (BV) method. In addn., a first-principles calcn. is performed. The calcd. result suggests that although the α-LiAlO2 bulk has the extremely low ionic cond., its ionic cond. could be increased significantly when applied the bias voltage, which is due to the introduction of external lithium sources (lithium reservoirs of interstitials/vacancies) and external charge sources (electrons/holes). This may explain why α-LiAlO2 as the coating layer on cathode for Li-ion batteries does not block the transport of lithium ions.
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    Leube, B. T.; Inglis, K. K.; Carrington, E. J.; Sharp, P. M.; Shin, J. F.; Neale, A. R.; Manning, T. D.; Pitcher, M. J.; Hardwick, L. J.; Dyer, M. S. Lithium Transport in Li4.4M0.4M′0.6S4 (M = Al3+, Ga3+, and M′ = Ge4+, Sn4+): Combined Crystallographic, Conductivity, Solid State NMR, and Computational Studies. Chem. Mater. 2018, 30, 7183– 7200,  DOI: 10.1021/acs.chemmater.8b03175
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    Lithium Transport in Li4.4M0.4M'0.6S4 (M =Al3+, Ga3+, and M' =Ge4+, Sn4+): Combined Crystallographic, Conductivity, Solid State NMR, and Computational Studies
    Leube, Bernhard T.; Inglis, Kenneth K.; Carrington, Elliot J.; Sharp, Paul M.; Shin, J. Felix; Neale, Alex R.; Manning, Troy D.; Pitcher, Michael J.; Hardwick, Laurence J.; Dyer, Matthew S.; Blanc, Frederic; Claridge, John B.; Rosseinsky, Matthew J.
    Chemistry of Materials (2018), 30 (20), 7183-7200CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    To understand the structural and compositional factors controlling Li transport in sulfides, we explored the Li5AlS4-Li4GeS4 phase field for new materials. Both parent compds. are defined structurally by a hcp. sulfide lattice, where distinct arrangements of tetrahedral metal sites give Li5AlS4 a layered structure and Li4GeS4 a 3-dimensional structure related to γ-Li3PO4. The combination of the 2 distinct structural motifs is expected to lead to new structural chem. We identified the new cryst. phase Li4.4Al0.4Ge0.6S4, and investigated the structure and Li+ ion dynamics of the family of structurally related materials Li4.4M0.4M'0.6S4 (M =Al3+, Ga3+ and M' =Ge4+, Sn4+). We used neutron diffraction to solve the full structures of the Al-homologues, which adopt a layered close-packed structure with a new arrangement of tetrahedral (M/M') sites and a novel combination of ordered and disordered lithium vacancies. AC impedance spectroscopy revealed lithium conductivities in the range of 3(2) × 10-6 to 4.3(3) × 10-5 S/cm at room temp. with activation energies between 0.43(1) and 0.38(1) eV. Electrochem. performance was tested in a plating and stripping expt. against Li metal electrodes and showed good stability of the Li4.4Al0.4Ge0.6S4 phase over 200 h. A combination of variable temp. 7Li solid state NMR spectroscopy and ab initio mol. dynamics calcns. on selected phases showed that 2-dimensional diffusion with a low energy barrier of 0.17 eV is responsible for long-range Li transport, with diffusion pathways mediated by the disordered vacancies while the ordered vacancies do not contribute to the cond. This new structural family of sulfide Li+ ion conductors offers insight into the role of disordered vacancies on Li+ ion cond. mechanisms in hexagonally close packed sulfides that can inform future materials design.
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    Kresse, G.; Furthmüller, J. Efficient Iterative Schemes for Ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set. Phys. Rev. B 1996, 54, 11169– 11186,  DOI: 10.1103/PhysRevB.54.11169
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    Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
    Kresse, G.; Furthmueller, J.
    Physical Review B: Condensed Matter (1996), 54 (16), 11169-11186CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
    The authors present an efficient scheme for calcg. the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set. In the first part the application of Pulay's DIIS method (direct inversion in the iterative subspace) to the iterative diagonalization of large matrixes will be discussed. This approach is stable, reliable, and minimizes the no. of order Natoms3 operations. In the second part, we will discuss an efficient mixing scheme also based on Pulay's scheme. A special "metric" and a special "preconditioning" optimized for a plane-wave basis set will be introduced. Scaling of the method will be discussed in detail for non-self-consistent and self-consistent calcns. It will be shown that the no. of iterations required to obtain a specific precision is almost independent of the system size. Altogether an order Natoms2 scaling is found for systems contg. up to 1000 electrons. If we take into account that the no. of k points can be decreased linearly with the system size, the overall scaling can approach Natoms. They have implemented these algorithms within a powerful package called VASP (Vienna ab initio simulation package). The program and the techniques have been used successfully for a large no. of different systems (liq. and amorphous semiconductors, liq. simple and transition metals, metallic and semiconducting surfaces, phonons in simple metals, transition metals, and semiconductors) and turned out to be very reliable.
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    Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 1996, 77, 3865– 3868,  DOI: 10.1103/PhysRevLett.77.3865
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    Physical Review Letters (1996), 77 (18), 3865-3868CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
    Generalized gradient approxns. (GGA's) for the exchange-correlation energy improve upon the local spin d. (LSD) description of atoms, mols., and solids. We present a simple derivation of a simple GGA, in which all parameters (other than those in LSD) are fundamental consts. Only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked. Improvements over PW91 include an accurate description of the linear response of the uniform electron gas, correct behavior under uniform scaling, and a smoother potential.
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    Kresse, G.; Joubert, D. From Ultrasoft Pseudopotentials to the Projector Augmented-Wave Method. Phys. Rev. B 1999, 59, 1758– 1775,  DOI: 10.1103/PhysRevB.59.1758
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    From ultrasoft pseudopotentials to the projector augmented-wave method
    Kresse, G.; Joubert, D.
    Physical Review B: Condensed Matter and Materials Physics (1999), 59 (3), 1758-1775CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
    The formal relationship between ultrasoft (US) Vanderbilt-type pseudopotentials and Blochl's projector augmented wave (PAW) method is derived. The total energy functional for US pseudopotentials can be obtained by linearization of two terms in a slightly modified PAW total energy functional. The Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional. A simple way to implement the PAW method in existing plane-wave codes supporting US pseudopotentials is pointed out. In addn., crit. tests are presented to compare the accuracy and efficiency of the PAW and the US pseudopotential method with relaxed-core all-electron methods. These tests include small mols. (H2, H2O, Li2, N2, F2, BF3, SiF4) and several bulk systems (diamond, Si, V, Li, Ca, CaF2, Fe, Co, Ni). Particular attention is paid to the bulk properties and magnetic energies of Fe, Co, and Ni.
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    Ong, S. P.; Richards, W. D.; Jain, A.; Hautier, G.; Kocher, M.; Cholia, S.; Gunter, D.; Chevrier, V. L.; Persson, K. A.; Ceder, G. Python Materials Genomics (Pymatgen): A Robust, Open-Source Python Library for Materials Analysis. Comput. Mater. Sci. 2013, 68, 314– 319,  DOI: 10.1016/j.commatsci.2012.10.028
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    Computational Materials Science (2013), 68 (), 314-319CODEN: CMMSEM; ISSN:0927-0256. (Elsevier B.V.)
    We present the Python Materials Genomics (pymatgen) library, a robust, open-source Python library for materials anal. A key enabler in high-throughput computational materials science efforts is a robust set of software tools to perform initial setup for the calcns. (e.g., generation of structures and necessary input files) and post-calcn. anal. to derive useful material properties from raw calcd. data. The pymatgen library aims to meet these needs by (1) defining core Python objects for materials data representation, (2) providing a well-tested set of structure and thermodn. analyses relevant to many applications, and (3) establishing an open platform for researchers to collaboratively develop sophisticated analyses of materials data obtained both from first principles calcns. and expts. The pymatgen library also provides convenient tools to obtain useful materials data via the Materials Project's REpresentational State Transfer (REST) Application Programming Interface (API). As an example, using pymatgen's interface to the Materials Project's RESTful API and phase diagram package, we demonstrate how the phase and electrochem. stability of a recently synthesized material, Li4SnS4, can be analyzed using a min. of computing resources. We find that Li4SnS4 is a stable phase in the Li-Sn-S phase diagram (consistent with the fact that it can be synthesized), but the narrow range of lithium chem. potentials for which it is predicted to be stable would suggest that it is not intrinsically stable against typical electrodes used in lithium-ion batteries.
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    Clark, S. J.; Segall, M. D.; Pickard, C. J.; Hasnip, P. J.; Probert, M. I. J.; Refson, K.; Payne, M. C. First Principles Methods Using CASTEP. Z. Kristallogr. - Cryst. Mater. 2005, 220, 567– 570,  DOI: 10.1524/zkri.220.5.567.65075
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    The CASTEP code for first principles electronic structure calcns. is described. A brief, non-tech. overview is given and some of the features and capabilities highlighted. Some features which are unique to CASTEP are described and near-future development plans outlined.
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    Physical Review B: Condensed Matter and Materials Physics (2001), 63 (24), 245101/1-245101/13CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
    A theory for the ab initio calcn. of all-electron NMR chem. shifts in insulators using pseudopotentials is presented. It is formulated for both finite and infinitely periodic systems and is based on an extension to the projector augmented-wave approach of Blochl [P. E. Blochl, Phys. Rev. B 50, 17953 (1994)] and the method of Mauri et al. [F. Mauri, B. G. Pfrommer, and S. G. Louie, Phys. Rev. Lett. 77, 5300 (1996)]. The theory is successfully validated for mols. by comparison with a selection of quantum chem. results, and in periodic systems by comparison with plane-wave all-electron results for diamond.
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    Yates, J. R.; Pickard, C. J.; Mauri, F. Calculation of NMR Chemical Shifts for Extended Systems Using Ultrasoft Pseudopotentials. Phys. Rev. B 2007, 76, 024401  DOI: 10.1103/PhysRevB.76.024401
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    Calculation of NMR chemical shifts for extended systems using ultrasoft pseudopotentials
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    The authors present a scheme for the calcn. of magnetic response parameters in insulators using ultrasoft pseudopotentials. It uses the gauge-including projector augmented wave method [C. J. Pickard and F. Mauri, Phys. Rev. B 63, 245101(2001)] to obtain all-electron accuracy for both finite and infinitely periodic systems. In detail the calcn. of NMR chem. shieldings are considered. The approach is successfully validated 1st for mol. systems by comparing calcd. chem. shieldings for a range of mols. with quantum chem. results and then in the solid state by comparing 17O NMR parameters calcd. for silicates with expt.
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    Anal. of a crystal structure using the Rietveld profile technique requires a suitable description of the shape of the peaks. In general, modern refinement codes include accurate formulations for most effects; however, the functions used for peak asymmetry are semi-empirical and take very little account of diffraction optics. The deficiencies in these methods are most obvious for high-resoln. instruments. This study describes the implementation of powder diffraction peak profile for mutations devised by van Laar and Yelon [J. Appl. Cryst. (1984) 17, 47-54]. This formalism, which describes the asymmetry due to axial divergence in terms of finite sample and detector sizes,does not require any free parameters and contains intrinsic corrections for the angular dependence of the peak shape. The method results in an accurate description of the obsd. profiles for a variety of geometries, including conventional x-ray diffractometers, synchrotron instruments with or without crystal analyzers and neutron diffractometers.
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    Multiple-Quantum Magic-Angle Spinning NMR: A New Method for the Study of Quadrupolar Nuclei in Solids
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    Journal of the American Chemical Society (1995), 117 (51), 12779-87CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Whereas solid state isotropic spectra can be obtained from spin-1/2 by fast magic-angle spinning (MAS), this methodol. fails when applied on half-integer quadrupoles due to the presence of non-negligible second-order anisotropic effects. Very recently, however, we have shown that the combined use of MAS and bidimensional multiple-quantum (MQ) spectroscopy can refocus these anisotropies; the present paper discusses theor. and exptl. aspects of this novel MQMAS methodol. and illustrates its application on a series of sodium salts. It is shown that even under fixed magnetic field operation, a simple model-free inspection of the peaks in a bidimensional MQMAS NMR spectrum can sep. the contributions of isotropic chem. and isotropic quadrupolar shifts for different chem. sites. Moreover the anisotropic line shapes that can be resolved from these spectra are almost unaffected by excitation distortions and can thus be used to discern the values of a site's quadrupolar coupling const. and asymmetry parameter. The conditions that maximize the MQMAS signal-to-noise ratio for a spin-3/2 are then explored with the aid of a simple anal. model, which can also be used to explain the absence of distortions in the anisotropic line shapes. The MQMAS method thus optimized was applied to the high-resoln. 23Na NMR anal. of the multi-site ionic compds. Na2TeO3, Na2SO3, Na3P5O10, and Na2HPO4; extensions of the MQMAS NMR methodol. to the quant. anal. of inequivalent sites are also discussed and demonstrated.
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    A Z-filtering method is applied to MQMAS NMR which greatly improves the efficiency of the method. This approach was used to analyze the 27Al 3QMAS NMR spectrum of AlPO-14.
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    APL Materials (2013), 1 (1), 011002/1-011002/11CODEN: AMPADS; ISSN:2166-532X. (American Institute of Physics)
    Accelerating the discovery of advanced materials is essential for human welfare and sustainable, clean energy. In this paper, we introduce the Materials Project (www.materialsproject.org), a core program of the Materials Genome Initiative that uses high-throughput computing to uncover the properties of all known inorg. materials. This open dataset can be accessed through multiple channels for both interactive exploration and data mining. The Materials Project also seeks to create open-source platforms for developing robust, sophisticated materials analyses. Future efforts will enable users to perform rapid-prototyping'' of new materials in silico, and provide researchers with new avenues for cost-effective, data-driven materials design. (c) 2013 American Institute of Physics.
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    Jaulmes, S.; Julien-Pouzol, M.; Dugué, J.; Laruelle, P.; Guittard, M. Structure d’un oxysulfure de gallium et de thallium. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 1986, 42, 1111– 1113,  DOI: 10.1107/S0108270186093228
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    Hellstrom, E. E.; Huggins, R. A. A Study of the Systems M2S·Al2S3, M = Li, Na, K; Preparation, Phase Study and Electric Conductivity. Mater. Res. Bull. 1979, 14, 881– 889,  DOI: 10.1016/0025-5408(79)90153-3
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    A study of the systems metal sulfide-aluminum sulfide, M = lithium, sodium, potassium; preparation, phase study and electrical conductivity
    Hellstrom, E. E.; Huggins, R. A.
    Materials Research Bulletin (1979), 14 (7), 881-9CODEN: MRBUAC; ISSN:0025-5408.
    A study of the systems M2S-Al2S3 (M = Li, Na, K) was undertaken to det. the phases present in these systems. New phases identified were LiAlS2, NaAlS2, Na2S.(10±1)Al2S3, KAlS2, and K2S.(10±1)Al2S3, none of which were analogous to the beta-alumina structure. Elec. cond. measurements were made on the K phases, and KAlS2 is an electronic conductor, while K2S.(10±1)Al2S3 is an ionic conductor (2 × 10-5 (S/m) at 573 K).
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    Murayama, M. Synthesis of New Lithium Ionic Conductor Thio-LISICON—Lithium Silicon Sulfides System. J. Solid State Chem. 2002, 168, 140– 148,  DOI: 10.1006/jssc.2002.9701
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    Synthesis of New Lithium Ionic Conductor Thio-LISICON - Lithium Silicon Sulfides System
    Murayama, Masahiro; Kanno, Ryoji; Irie, Michihiko; Ito, Shinya; Hata, Takayuki; Sonoyama, Noriyuki; Kawamoto, Yoji
    Journal of Solid State Chemistry (2002), 168 (1), 140-148CODEN: JSSCBI; ISSN:0022-4596. (Elsevier Science)
    New Li-ion conductors, thio-LISICON (lithium superionic conductor), can be based on the ternary systems Li2S-SiS2-Al2S3 and Li2S-SiS2-P2S5. The structures of the new materials, Li4+xSi1-xAlxS4 and Li4-xSi1-xPxS4 were detd. by x-ray Rietveld anal. Their elec. and electrochem. properties were studied by electronic cond., a.c. cond., and cyclic voltammetry. The structure of the host material, Li4SiS4, is related to the γ-Li3PO4-type structure, and when Li+ interstitials or Li+ vacancies are created by partial substitution of Al3+ or P5+ for Si4+, the cond. increases significantly. The solid soln. member Li3.4Si0.4P0.6S4 had an ionic cond. of 6.4 × 10-4 S/cm at 27° and negligible electronic cond. The solid solns., Li4-xSi1-xPxS4, also had high electrochem. stability up to ∼5 V vs. Li at room temp. All-solid-state Li batteries were studied using the Li3.4Si0.4P0.6S4 electrolyte, a LiCoO2 cathode and an In anode.
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    Lim, H.; Kim, S.-C.; Kim, J.; Kim, Y.-I.; Kim, S.-J. Structure of Li5AlS4 and Comparison with Other Lithium-Containing Metal Sulfides. J. Solid State Chem. 2018, 257, 19– 25,  DOI: 10.1016/j.jssc.2017.09.018
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    Structure of Li5AlS4 and comparison with other lithium-containing metal sulfides
    Lim, Hanjin; Kim, Sung-Chul; Kim, Jaegyeom; Kim, Young-Il; Kim, Seung-Joo
    Journal of Solid State Chemistry (2018), 257 (), 19-25CODEN: JSSCBI; ISSN:0022-4596. (Elsevier B.V.)
    Lithium aluminum sulfide (Li5AlS4) was synthesized by solid state reaction, and its crystal structure was characterized by ab initio structure detn. on the basis of powder neutron diffraction (ND) data. Li5AlS4 was found to have monoclinic unit cell (space group, P21/m) with the lattice parameters: a = 6.8583(4) Å, b = 7.8369(4) Å, c = 6.2488(4) Å, and β = 90.333(4)°. This structure is built from a hcp. (hcp) arrangement of sulfur atoms with a stacking sequence of ...ABAB. The hcp sulfide lattice consists of two different double-sulfide layers alternately stacked along the c-axis. Between the first pair of sulfur layers all the tetrahedral interstices (T+ and T- sites) are filled with lithium and aluminum atoms. All octahedral interstices between the second pair of sulfur layers are occupied by the remaining lithium atoms. The structure of Li5AlS4 is compared with those of various lithium-contg. metal sulfides like Li2FeS2, NaLiMS2 (M = Zn, Cd), Li4GeS4, LiM'S2 (M' = Al, Ga, In) and γ-Li3PS4. Each sulfide represents a specific distribution of lithium atoms in the lattice depending on how the octahedral and tetrahedral interstitial sites are filled. The low ionic cond. of Li5AlS4 (9.7 × 10-9 S cm-1 at 323 K) relative to other sulfides may be due to the highly-ordered distribution of the lithium atoms in the layered structure and the lack of adjacent void spaces that can be used for lithium ion hopping.
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    Yu, X.; Boyer, M. J.; Hwang, G. S.; Manthiram, A. Room-Temperature Aluminum-Sulfur Batteries with a Lithium-Ion-Mediated Ionic Liquid Electrolyte. Chem 2018, 4, 586– 598,  DOI: 10.1016/j.chempr.2017.12.029
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    Room-Temperature Aluminum-Sulfur Batteries with a Lithium-Ion-Mediated Ionic Liquid Electrolyte
    Yu, Xingwen; Boyer, Mathew J.; Hwang, Gyeong S.; Manthiram, Arumugam
    Chem (2018), 4 (3), 586-598CODEN: CHEMVE; ISSN:2451-9294. (Cell Press)
    Aluminum-sulfur (Al-S) chem. is attractive for the development of future-generation electrochem. energy storage technologies. However, to date, only limited reversible Al-S chem. has been demonstrated. This paper demonstrates a highly reversible room-temp. Al-S battery with a lithium-ion (Li+-ion)-mediated ionic liq. electrolyte. Mechanistic studies with electrochem. and spectroscopic methodologies revealed that the enhancement in reversibility by Li+-ion mediation is attributed to the chem. reactivation of aluminum polysulfides and/or sulfide by Li+ during electrochem. cycling. The results obtained with XPS and d. functional theory calcns. suggest the presence of a Li3AlS3-like product with a mixt. of Li2S- and Al2S3-like phases in the discharged sulfur cathode. With Li+-ion mediation, the cycle life of room-temp. Al-S batteries is greatly improved. The cell delivers an initial capacity of ∼1,000 mA hr g-1 and maintains a capacity of up to 600 mA hr g-1 after 50 cycles.
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    Toby, B. H.; Von Dreele, R. B. GSAS-II: The Genesis of a Modern Open-Source All Purpose Crystallography Software Package. J. Appl. Crystallogr. 2013, 46, 544– 549,  DOI: 10.1107/S0021889813003531
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    Toby, Brian H.; Von Dreele, Robert B.
    Journal of Applied Crystallography (2013), 46 (2), 544-549CODEN: JACGAR; ISSN:0021-8898. (International Union of Crystallography)
    The newly developed GSAS-II software is a general purpose package for data redn., structure soln. and structure refinement that can be used with both single-crystal and powder diffraction data from both neutron and x-ray sources, including lab. and synchrotron sources, collected on both two- and 1-dimensional detectors. It is intended that GSAS-II will eventually replace both the GSAS and the EXPGUI packages, as well as many other utilities. GSAS-II is open source and is written largely in object-oriented Python but offers speeds comparable to compiled code because of its reliance on the Python NumPy and SciPy packages for computation. It runs on all common computer platforms and offers highly integrated graphics, both for a user interface and for interpretation of parameters. The package can be applied to all stages of crystallog. anal. for const.-wavelength x-ray and neutron data. Plans for considerable addnl. development are discussed.
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    Petříček, V.; Dušek, M.; Palatinus, L. Crystallographic Computing System JANA2006: General Features. Z. Kristallogr. - Cryst. Mater. 2014, 229, 345– 352,  DOI: 10.1515/zkri-2014-1737
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    Crystallographic Computing System JANA2006: General features
    Petricek, Vaclav; Dusek, Michal; Palatinus, Lukas
    Zeitschrift fuer Kristallographie - Crystalline Materials (2014), 229 (5), 345-352CODEN: ZKCMAJ; ISSN:2194-4946. (Oldenbourg Wissenschaftsverlag GmbH)
    JANA2006 is a freely available program for structure detn. of std., modulated and magnetic samples based on X-ray or neutron single crystal/ powder diffraction or on electron diffraction. The system has been developed for 30 years from specialized tool for refinement of modulated structures to a universal program covering std. as well as advanced crystallog. The aim of this article is to describe the basic features of JANA2006 and explain its scope and philosophy. It will also serve as a basis for future publications detailing tools and methods of JANA.
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    Palatinus, L.; Chapuis, G. SUPERFLIP – a Computer Program for the Solution of Crystal Structures by Charge Flipping in Arbitrary Dimensions. J. Appl. Crystallogr. 2007, 40, 786– 790,  DOI: 10.1107/S0021889807029238
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    SUPERFLIP is a computer program that can solve crystal structures from diffraction data using the recently developed charge-flipping algorithm. It can solve periodic structures, incommensurately modulated structures and quasicrystals from x-ray and neutron diffraction data. Structure soln. from powder diffraction data is supported by combining the charge-flipping algorithm with a histogram-matching procedure. SUPERFLIP is written in Fortran90 and is distributed as a source code and as precompiled binaries. It was successfully compiled and tested on a variety of operating systems.
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    Xu, Z.; Stebbins, J. F. 6Li Nuclear Magnetic Resonance Chemical Shifts, Coordination Number and Relaxation in Crystalline and Glassy Silicates. Solid State Nucl. Magn. Reson. 1995, 5, 103– 112,  DOI: 10.1016/0926-2040(95)00026-M
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    Xu, Z.; Stebbins, Jonathan F.
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    Unlike 7Li magic-angle spinning NMR (MAS NMR) spectra, 6Li MAS NMR spectra of silicates are dominated by chem. shift effects, often have a very high resoln., and hence can provide significant structural information. In this study, the authors demonstrate a good correlation between 6Li isotropic chem. shifts and oxygen coordination no., and use this result to describe the range of coordination environments for Li in silicate glasses. They also show that the second-order quadrupolar shift for 7Li can often be derived from 7Li and 6Li MAS spectra acquired at a single magnetic field. For a series of natural lepidolite samples with significant but varying contents of Mn and Fe, spin-lattice relaxation data show a power-law behavior and a three-dimensional distribution of paramagnetic centers, but homonuclear dipolar couplings can be important. The 6Li spectrum for lithium orthosilicate (which has three-, four-, five-, and six-coordinated Li) is consistent with that predicted by the X-ray structure.
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    Eisenmann, B.; Hofmann, A. Crystal Structure of Hexasodium Di-μ-Thio-Bis(Dithioindate), Na6In2S6. Z. Kristallogr. - Cryst. Mater. 1991, 197, 151– 152,  DOI: 10.1524/zkri.1991.197.1-2.151
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    Crystal structure of hexasodium di-μ-thio-bis(dithioindate), Na6In2S6
    Eisenmann, B.; Hofmann, A.
    Zeitschrift fuer Kristallographie (1991), 197 (1-2), 151-2CODEN: ZEKRDZ; ISSN:0044-2968.
    The title compd. is monoclinic, space group C2/c, with a 15.945(6), b 13.456(6), c 7.358(4) Å, and β 117.41(6)°; Z = 4; R = 0.044. At. coordinates are given. The anionic partial structure is characterized by dimers In2S66- of 2 edge-sharing InS4 tetrahedra.
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    Klepp, K.; Böttcher, P.; Bronger, W. Preparation and Crystal Structure of Na2Mn2S3. J. Solid State Chem. 1983, 47, 301– 306,  DOI: 10.1016/0022-4596(83)90022-1
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    Preparation and crystal structure of sodium thiomanganate (Na2Mn2S3)
    Klepp, K.; Boettcher, P.; Bronger, W.
    Journal of Solid State Chemistry (1983), 47 (3), 301-6CODEN: JSSCBI; ISSN:0022-4596.
    Na2Mn2S3 was prepd. by reacting Mn powder with an excess of anhyd. Na2CO3 and elemental S at 870 K. Extn. of the solidified melt with water and alc. yielded well-developed, bright red crystals. Na2Mn2S3 crystallizes with a new monoclinic structure type, space group C2/c, Z = 8, with a 14.942(2), b = 13.276(2), c 6.851(2) Å, and β 116.50(1)°. The crystal structure was detd. from single crystal diffractometer data and refined to a conventional R value of 0.026 for 1613 obsd. reflections. The at. arrangement shows S-Mn-S slabs which are sepd. from each other by corrugated layers of Na atoms. A prominent feature of the crystal structure is the formation of short, 4-membered zigzag chains built up by MnS4 tetrahedra sharing edges. These chains are further connected by the remaining apexes to form an infinite sheet. Short Mn-Mn distances (3.02 and 3.05 Å, resp.) are found within the 4-membered chains. Susceptibility measurements show antiferromagnetic interactions between the Mn atoms.
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    Kim, J.; Hughbanks, T. Synthesis and Structures of New Layered Ternary Manganese Selenides: AMnSe2 (A=Li, Na, K, Rb, Cs) and Na2Mn2Se3. J. Solid State Chem. 1999, 146, 217– 225,  DOI: 10.1006/jssc.1999.8339
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    Synthesis and Structures of New Layered Ternary Manganese Selenides: AMnSe2 (A = Li, Na, K, Rb, Cs) and Na2Mn2Se3
    Kim, Joonyeong; Hughbanks, Timothy
    Journal of Solid State Chemistry (1999), 146 (1), 217-225CODEN: JSSCBI; ISSN:0022-4596. (Academic Press)
    The synthesis and crystal structures of new ternary Mn selenides, AMnSe2 (A = Li, Na, K, Rb, Cs) and Na2Mn2Se3, are reported. These compds. were synthesized by solid state reaction and cation exchange techniques. Crystal data are: LiMnSe2: a 4.1905(3), c 6.619(2) Å, and space group P3m1, (No. 156, Z = 1); NaMnSe2: a 4.2330(7), c 6.942(3) Å, and space group P3m1, (No. 156, Z = 1); RbMnSe2: a 4.2660(4), c 14.033(2) Å, and I4m2 (No. 119, Z = 2); Na2Mn2Se3: a 15.689(2), b 13.888(2), c 7.220(1) Å, β 115.65(2)°, and C2/c (No. 15, Z = 8). The fundamental building blocks of the title compds. are MnSe4 tetrahedra. AMnSe2 (A = Li, Na) are layered compds. in which MnSe4 tetrahedra share three corners in the formation of polar 2∞[MnSe3/3Se]- layers. AMnSe2 (A = K, Rb, Cs) exhibit 2∞[MnSe4/2]- layers which are built up by four-corner-shared MnSe4 tetrahedra. Na2Mn2Se3 shows four-membered zigzag chains formed by edge-shared MnSe4 tetrahedra. These chains are fused by the remaining apexes to form a two-dimensional layer, 2∞[MnSe2/3Se1/3Se1/2]-. Magnetic susceptibility data for these compds. were fit with a modified Curie-Weiss expression. (c) 1999 Academic Press.
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    Luthy, J. A.; Goodman, P. L.; Martin, B. R. Synthesis of Li(x)Na(2–x)Mn2S3 and LiNaMnS2 through Redox-Induced Ion Exchange Reactions. J. Solid State Chem. 2009, 182, 580– 585,  DOI: 10.1016/j.jssc.2008.11.025
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    Synthesis of Li(x)Na(2-x)Mn2S3 and LiNaMnS2 through redox-induced ion exchange reactions
    Luthy, Joshua A.; Goodman, Phillip L.; Martin, Benjamin R.
    Journal of Solid State Chemistry (2009), 182 (3), 580-585CODEN: JSSCBI; ISSN:0022-4596. (Elsevier B.V.)
    Na2Mn2S3 was oxidatively deintercalated using I in MeCN to yield Na1.3Mn2S3, with lattice consts. nearly identical to that of the reactant. Li was then reductively intercalated into the oxidized product to yield Li0.7Na1.3Mn2S3. When heated, this metastable compd. decompd. to form a new cryst. compd., LiNaMnS2, along with MnS and residual Na2Mn2S3. Single crystal x-ray diffraction structural anal. of LiNaMnS2 revealed that this compd. crystallizes in P‾3m1 with a 4.0479(6), c 6.7759(14) Å, V = 96.15(3) Å3 (Z = 1, wR2 = 0.0367) in the NaLiCdS2 structure-type.
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    Eisenmann, B.; Hofmann, A. Crystal Structure of Hexasodium Di-μ-Thio-Bis(Dithioaluminate) – HT, Na6Al2S6. Z. Kristallogr. - Cryst. Mater. 1991, 197, 161– 162,  DOI: 10.1524/zkri.1991.197.1-2.161
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    Crystal structure of hexasodium di-μ-thio-bis(dithioaluminate) - HT, Na6Al2S6
    Eisenmann, B.; Hofmann, A.
    Zeitschrift fuer Kristallographie (1991), 197 (1-2), 161-2CODEN: ZEKRDZ; ISSN:0044-2968.
    The title compd. is monoclinic, space group P21/c, with a 13.706(5), b 12.071(5), c 7.608(3) Å, and β 98.60(6)°; Z = 4; R = 0.078. At. coordinates are given. This high temp. (H.T.) modification, stable above 775 K, is characterized by dimeric anions Al2S66- of 2 edge-sharing AlS4 tetrahedra.
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    Müller, P.; Bronger, W. Na3FeS3, Ein Thioferrat Mit Isolierten [Fe2S6]− Anionen /Na3FeS3, a Thioferrate with Isolated [Fe2S6]− Anions. Z. Naturforsch., B: J. Chem. Sci. 2014, 34, 1264– 1266,  DOI: 10.1515/znb-1979-0920
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  • Abstract

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    Figure 1

    Figure 1. (a) Calculated energy of different compositions in the Li–Al–O–S phase field using cells containing hexagonal close-packed (hcp, black triangles) and cubic close-packed (ccp, black filled circles) anion lattices. Ehull is the energy above the convex hull. Reported oxide and sulfide phases in the Li–Al–O–S phase field (black rectangles). (b) First-stage experimentally tested compositions, which resulted in a mixture of already reported compounds (empty red squares with black letters), and a mixture of already reported compounds along with the presence of the new phase (filled red squares with white letters). Second-stage experimentally tested compositions (numbered black circles). Composition of points are as follows: A (Li3Al9O2S13), B (LiAlOS), C (LiAlO0.2S1.8), D (LiAlO1.8S0.2), E (Li7Al2O4S), F (Li5AlO3S), 1 (Li4Al2O2S3), 2 (Li6Al8O10S5), 3 (Li2Al4O4S3), 4 (Li2Al4O5S2), and 5 (Li3AlS3).

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    Figure 2

    Figure 2. Final Rietveld refinement of (a) the synchrotron X-ray diffraction pattern of 7Li3AlS3 (Diamond Light Source, I11 beam line) with fixed Li positions and (b) 7Li3AlS3 against neutron powder diffraction data (ISIS neutron source, HRPD) from (b) bank 1 (2θ = 168.330°), (c) bank 2 (2θ = 89.580°), and (d) bank 3 (2θ = 30.000°), with Iobs (red dots), Icalc (black line), Iobs – Icalc (blue line), and Bragg reflections (red tick marks for Li3AlS3, black tick marks for Li5AlS4, and blue tick marks for the vanadium can).

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    Figure 3

    Figure 3. (a) 6Li MAS spectrum of Li3AlS3 obtained at magnetic fields of 9.4 T (black) and 20 T (blue). The experimental spectrum (full lines), total fit (dashed lines) spectral deconvolution (dotted lines), Li5AlS4 impurity (red dotted lines), and GIPAW-simulated spectrum (green lines) are shown. (b) 27Al MQMAS NMR spectrum of Li3AlS3 recorded at a magnetic field of 9.4 T and 20 T. The dotted lines (black for a field of 9.4 T and blue for 20 T) and the red dotted lines represent the spectral deconvolution of Li3AlS3 and Li5AlS4, respectively. The dashed lines show the total fit for the sample, and the solid lines show the anisotropic one-dimensional 27Al spectrum, while the vertical spectrum shows the non-quantitative isotropic 27Al spectrum. The solid green line shows the GIPAW-simulated spectrum with an isotropic chemical shift of 117 ppm, a quadrupolar coupling constant of 5.1 MHz and an asymmetry parameter of 0.44 (Table S7).

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    Figure 4

    Figure 4. (a) Crystal structure of Li3AlS3 showing the alternating arrangement perpendicular to the bc plane of the tetrahedral layers containing AlS4 and LiS4 tetrahedra and the mixed polyhedral layers containing Li-only polyhedra. (b) T+ and T– interstices in the tetrahedral layer, showing the corner-sharing arrangement of the Li1, Al, and vacant (empty) tetrahedra in each network, as well as the interconnection (following the yellow arrow) of each T+ (thin lines) and T– (thick lines) network so that AlS4 dimers are formed. The highlighted yellow face of the Li1 tetrahedron corresponds to the only face that shares two edges with two vacant sites. (c) View of both the mixed polyhedral layer and the tetrahedral layer in the bc plane and of their interconnection (following the yellow arrow). Polyhedra colors: blue: Al tetrahedra; orange: Li tetrahedra; red: Li2 octahedra; light red: Li3 octahedra.

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    Figure 5

    Figure 5. Coordination polyhedra of (a) Li1 and Al in the tetrahedral layer, (b) Li4, (c) Li2 and Li2b, and (d) Li3 in the mixed polyhedral layer.

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    Figure 6

    Figure 6. Crystal structure of Li3AlS3 showing the arrangement of octahedral (red) and tetrahedral (orange) lithium and tetrahedral aluminum (blue). The direction of the displacement of atoms is symbolized by arrows: blue for Al, orange for Li1 and Li4, and yellow for S.

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    Figure 7

    Figure 7. (a) Crystal structure of Na3AlS3 showing the alternating arrangement, along a, of the tetrahedral layers containing AlS4 and NaS4 tetrahedra and of the mixed polyhedral layers containing Na-only polyhedra. (b) View of the two consecutive tetrahedral layers of Na3AlS3 in the bc plane. (c) Crystal structure of Na3FeS3 showing one type of layer along b (d) View of the layer along b of Na3FeS3 showing the fully occupied octahedral sites by Na atoms and the 1/3 occupied tetrahedral interstices by Fe atoms in a dimer arrangement.

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    Figure 8

    Figure 8. (a) Nyquist plot at 30 °C of Li3AlS3 and (inset) electrical equivalent circuit showing the two contributions to the conductivity. (b) Arrhenius plot of the bulk conductivity of Li3AlS3 measured by AC impedance. Black squares correspond to the experimental data, and the red line corresponds to the fits.

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    Figure 9

    Figure 9. Representation of the influence of the M/S = 1/3 ratio on the structure and arrangement of Li polyhedra in Li3AlS3 having the “Li5AlS4-type” structure leading to the presence of ordered vacancies in the tetrahedral layer.

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      Knauth, Philippe
      Solid State Ionics (2009), 180 (14-16), 911-916CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
      This short review presents the state-of-the-art knowledge on cryst., composite and amorphous inorg. solid lithium ion conductors, which are of interest as potential solid electrolytes in lithium batteries and might replace the currently used polymeric lithium ion conductors. The discussion of cryst. Li ion conductors includes perovskite-type Lithium Lanthanum Titanates, NASICON-type, LiSICON- and Thio-LiSICON-type Li ion conductors, as well as garnet-type Li ion conducting oxides. The part on composite Li ion conductors discusses materials contg. oxides and mesoporous oxides. In the amorphous Li ion conductor part, mech. attrition of Li compds., oxide and sulfide-based glasses as well as LIPON and related systems are presented.
    4. 4
      Goodenough, J. B. Rechargeable Batteries: Challenges Old and New. J. Solid State Electrochem. 2012, 16, 2019– 2029,  DOI: 10.1007/s10008-012-1751-2
      4
      Rechargeable batteries: challenges old and new
      Goodenough, John B.
      Journal of Solid State Electrochemistry (2012), 16 (6), 2019-2029CODEN: JSSEFS; ISSN:1432-8488. (Springer)
      The challenges for rechargeable batteries are cost, safety, energy, d., life, and rate. Traditional rechargeable batteries based on aq. electrolytes have good rate capabilities but limited energy d. because the voltage for a long shelf-life is restricted to 1.5 V. The discovery of fast Na ion cond. in β-alumina in 1967 introduced the novel concept of a solid oxide electrolyte and molten electrodes: the sodium-sulfur battery operates at 350 °C. Interest in rechargeable batteries with aprotic electrolytes was further stimulated by the first energy crisis in the early 1970s. Since protons are not mobile in aprotic electrolytes, the Li+ ion was the logical choice for the working ion, and on-going work on reversible Li intercalation into layered sulfides suggested the TiS2//Li cell, which was shown in 1976 to have a voltage of V ≃ 2.2 V and good rate capability. However, the org. liq. carbonates used as electrolytes are flammable, and dendrites growing across the electrolyte from the lithium anode on repeated charge/discharge cycles short-circuited the cells with disastrous consequences. Safety concerns caused this effort to be dropped. However, substitution of the layered oxides LiMO2 for the layered sulfides MS2 and reversible intercalation of Li into graphitic carbon without dendrite formation at slow charging rates gave a safe rechargeable lithium ion battery (LIB) of large-enough energy d. to enable the wireless revolution. Although carbon-buffered alloys now provide anodes that allow a fast charge and have a higher capacity, nevertheless a passivation layer permeable to Li+ forms on the anode surface, and the Li+ in the passivation layer is taken irreversibly from the cathode on the initial charge. Since the specific capacity of a cell with an insertion-compd. cathode is limited by the latter, strategies to increase the specific capacity for a LIB powering an elec. vehicle or storing electricity from wind or solar farms include a return to consideration of a solid electrolyte.
    5. 5
      Zhang, Z.; Shao, Y.; Lotsch, B.; Hu, Y.-S.; Li, H.; Janek, J.; Nazar, L. F.; Nan, C.-W.; Maier, J.; Armand, M. New Horizons for Inorganic Solid State Ion Conductors. Energy Environ. Sci. 2018, 11, 1945– 1976,  DOI: 10.1039/C8EE01053F
      5
      New horizons for inorganic solid state ion conductors
      Zhang, Zhizhen; Shao, Yuanjun; Lotsch, Bettina; Hu, Yong-Sheng; Li, Hong; Janek, Jurgen; Nazar, Linda F.; Nan, Ce-Wen; Maier, Joachim; Armand, Michel; Chen, Liquan
      Energy & Environmental Science (2018), 11 (8), 1945-1976CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
      A review. Among the contenders in the new generation energy storage arena, all-solid-state batteries (ASSBs) have emerged as particularly promising, owing to their potential to exhibit high safety, high energy d. and long cycle life. The relatively low cond. of most solid electrolytes and the often sluggish charge transfer kinetics at the interface between solid electrolyte and electrode layers are considered to be amongst the major challenges facing ASSBs. This review presents an overview of the state of the art in solid lithium and sodium ion conductors, with an emphasis on inorg. materials. The correlations between the compn., structure and cond. of these solid electrolytes are illustrated and strategies to boost ion cond. are proposed. In particular, the high grain boundary resistance of solid oxide electrolytes is identified as a challenge. Crit. issues of solid electrolytes beyond ion cond. are also discussed with respect to their potential problems for practical applications. The chem. and electrochem. stabilities of solid electrolytes are discussed, as are chemo-mech. effects which have been overlooked to some extent. Furthermore, strategies to improve the practical performance of ASSBs, including optimizing the interface between solid electrolytes and electrode materials to improve stability and lower charge transfer resistance are also suggested.
    6. 6
      Manthiram, A.; Yu, X.; Wang, S. Lithium Battery Chemistries Enabled by Solid-State Electrolytes. Nat. Rev. Mater. 2017, 2, 16103,  DOI: 10.1038/natrevmats.2016.103
      6
      Lithium battery chemistries enabled by solid-state electrolytes
      Manthiram, Arumugam; Yu, Xingwen; Wang, Shaofei
      Nature Reviews Materials (2017), 2 (3), 16103CODEN: NRMADL; ISSN:2058-8437. (Nature Publishing Group)
      Solid-state electrolytes are attracting increasing interest for electrochem. energy storage technologies. In this Review, we provide a background overview and discuss the state of the art, ion-transport mechanisms and fundamental properties of solid-state electrolyte materials of interest for energy storage applications. We focus on recent advances in various classes of battery chemistries and systems that are enabled by solid electrolytes, including all-solid-state lithium-ion batteries and emerging solid-electrolyte lithium batteries that feature cathodes with liq. or gaseous active materials (for example, lithium-air, lithium-sulfur and lithium-bromine systems). A low-cost, safe, aq. electrochem. energy storage concept with a 'mediator-ion' solid electrolyte is also discussed. Advanced battery systems based on solid electrolytes would revitalize the rechargeable battery field because of their safety, excellent stability, long cycle lives and low cost. However, great effort will be needed to implement solid-electrolyte batteries as viable energy storage systems. In this context, we discuss the main issues that must be addressed, such as achieving acceptable ionic cond., electrochem. stability and mech. properties of the solid electrolytes, as well as a compatible electrolyte/electrode interface.
    7. 7
      Lotsch, B. V.; Maier, J. Relevance of Solid Electrolytes for Lithium-Based Batteries: A Realistic View. J. Electroceram. 2017, 38, 128– 141,  DOI: 10.1007/s10832-017-0091-0
      There is no corresponding record for this reference.
    8. 8
      Ma, J.; Chen, B.; Wang, L.; Cui, G. Progress and Prospect on Failure Mechanisms of Solid-State Lithium Batteries. J. Power Sources 2018, 392, 94– 115,  DOI: 10.1016/j.jpowsour.2018.04.055
      8
      Progress and prospect on failure mechanisms of solid-state lithium batteries
      Ma, Jun; Chen, Bingbing; Wang, Longlong; Cui, Guanglei
      Journal of Power Sources (2018), 392 (), 94-115CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      By replacing traditional liq. org. electrolyte with solid-state electrolyte, the solid-state lithium batteries powerfully come back to the energy storage field due to their eminent safety and energy d. In recent years, a variety of solid-state lithium batteries based on excellent solid-state electrolytes are developed. However, the performance degrdn. of solid-state lithium batteries during cycling and storing is still a serious challenge for practical application. Therefore, this review summarizes the research progress of solid-state lithium batteries from the perspectives of failure phenomena and failure mechanisms. Addnl., the development of methodologies on studying the failure mechanisms of solid-state lithium batteries is also reviewed. Moreover, some perspectives on the remaining questions for understanding the failure behaviors and achieving long cycle life, high safety and high energy d. solid-state lithium batteries are presented. This review will help researchers to recognize the status of solid-state lithium batteries objectively and attract much more research interest in conquering the failure issues of solid-state lithium batteries.
    9. 9
      Janek, J.; Zeier, W. G. A Solid Future for Battery Development. Nat. Energy 2016, 1, 16141,  DOI: 10.1038/nenergy.2016.141
      There is no corresponding record for this reference.
    10. 10
      Kanno, R.; Murayama, M. Lithium Ionic Conductor Thio-LISICON: The Li2S - GeS2 - P2S5 System. J. Electrochem. Soc. 2001, 148, A742– A746,  DOI: 10.1149/1.1379028
      10
      Lithium ionic conductor thio-LISICON: the Li2S-GeS2-P2S5 system
      Kanno, Ryoji; Murayama, Masahiro
      Journal of the Electrochemical Society (2001), 148 (7), A742-A746CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
      The new cryst. material family, lithium superionic conductor (thio-LISICON), was obsd. in the Li2S-GeS2-P2S5 system. The solid soln. member x = 0.75 in Li4-xGe1-xPxS4 shows the highest cond. of 2.2 × 10-3 S cm-1 at 25°C of any sintered ceramic, together with negligible electronic cond., high electrochem. stability, no reaction with lithium metal, and no phase transition up to 500°C. Its material design concepts of changing constituent ions with various ionic radii, valence, and polarizability are described.
    11. 11
      Kamaya, N.; Homma, K.; Yamakawa, Y.; Hirayama, M.; Kanno, R.; Yonemura, M.; Kamiyama, T.; Kato, Y.; Hama, S.; Kawamoto, K. A Lithium Superionic Conductor. Nat. Mater. 2011, 10, 682– 686,  DOI: 10.1038/nmat3066
      11
      A lithium superionic conductor
      Kamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro; Hirayama, Masaaki; Kanno, Ryoji; Yonemura, Masao; Kamiyama, Takashi; Kato, Yuki; Hama, Shigenori; Kawamoto, Koji; Mitsui, Akio
      Nature Materials (2011), 10 (9), 682-686CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
      Batteries are a key technol. in modern society. They are used to power elec. and hybrid elec. vehicles and to store wind and solar energy in smart grids. Electrochem. devices with high energy and power densities can currently be powered only by batteries with org. liq. electrolytes. However, such batteries require relatively stringent safety precautions, making large-scale systems complicated and expensive. The application of solid electrolytes is currently limited because they attain practically useful conductivities (10-2 S/cm) only at 50-80°, which is one order of magnitude lower than those of org. liq. electrolytes. Here, the authors report a Li superionic conductor, Li10GeP2S12 that has a new 3-dimensional framework structure. It exhibits an extremely high Li ionic cond. of 12 mS/cm at room temp. This represents the highest cond. achieved in a solid electrolyte, exceeding even those of liq. org. electrolytes. This new solid-state battery electrolyte has many advantages in terms of device fabrication (facile shaping, patterning and integration), stability (non-volatile), safety (non-explosive) and excellent electrochem. properties (high cond. and wide potential window).
    12. 12
      Kuhn, A.; Duppel, V.; Lotsch, B. V. Tetragonal Li10GeP2S12 and Li7GePS8 – Exploring the Li Ion Dynamics in LGPS Li Electrolytes. Energy Environ. Sci. 2013, 6, 3548– 3552,  DOI: 10.1039/c3ee41728j
      12
      Tetragonal Li10GeP2S12 and Li7GePS8 - exploring the Li ion dynamics in LGPS Li electrolytes
      Kuhn, Alexander; Duppel, Viola; Lotsch, Bettina V.
      Energy & Environmental Science (2013), 6 (12), 3548-3552CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
      Tetragonal Li10GeP2S12 (LGPS) is the best solid Li electrolyte reported in the literature. In this study we present the first in-depth study on the structure and Li ion dynamics of this structure type. We prepd. two different tetragonal LGPS samples, Li10GeP2S12 and the new compd. Li7GePS8. The Li ion dynamics and the structure of these materials were characterized using a multitude of complementary techniques, including impedance spectroscopy, 7Li PFG NMR, 7Li NMR relaxometry, X-ray diffraction, electron diffraction, and 31P MAS NMR. The exceptionally high ionic cond. of tetragonal LGPS of ∼10-2 S cm-1 is traced back to nearly isotropic Li hopping processes in the bulk lattice of LGPS with EA ≈ 0.22 eV.
    13. 13
      Bron, P.; Johansson, S.; Zick, K.; Schmedt auf der Günne, J.; Dehnen, S.; Roling, B. Li10SnP2S12: An Affordable Lithium Superionic Conductor. J. Am. Chem. Soc. 2013, 135, 15694– 15697,  DOI: 10.1021/ja407393y
      13
      Li10SnP2S12: An Affordable Lithium Superionic Conductor
      Bron, Philipp; Johansson, Sebastian; Zick, Klaus; Schmedtauf der Guenne, Joern; Dehnen, Stefanie; Roling, Bernhard
      Journal of the American Chemical Society (2013), 135 (42), 15694-15697CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      The reaction of Li2S and P2S5 with Li4[SnS4], a recently discovered, good Li+ ion conductor, yields Li10SnP2S12, the thiostannate analog of the record holder Li10GeP2S12 and the 2nd compd. of this class of superionic conductors with very high values of 7 mS/cm for the grain cond. and 4 mS/cm for the total cond. at 27°. The replacement of Ge by Sn should reduce the raw material cost by a factor of ∼3.
    14. 14
      Kato, Y.; Hori, S.; Saito, T.; Suzuki, K.; Hirayama, M.; Mitsui, A.; Yonemura, M.; Iba, H.; Kanno, R. High-Power All-Solid-State Batteries Using Sulfide Superionic Conductors. Nat. Energy 2016, 1, 16030,  DOI: 10.1038/nenergy.2016.30
      14
      High-power all-solid-state batteries using sulfide superionic conductors
      Kato, Yuki; Hori, Satoshi; Saito, Toshiya; Suzuki, Kota; Hirayama, Masaaki; Mitsui, Akio; Yonemura, Masao; Iba, Hideki; Kanno, Ryoji
      Nature Energy (2016), 1 (4), 16030CODEN: NEANFD; ISSN:2058-7546. (Nature Publishing Group)
      Compared with Li-ion batteries with liq. electrolytes, all-solid-state batteries offer an attractive option owing to their potential in improving the safety and achieving both high power and high energy densities. Despite extensive research efforts, the development of all-solid-state batteries still falls short of expectation largely because of the lack of suitable candidate materials for the electrolyte required for practical applications. Here the authors report Li superionic conductors with an exceptionally high cond. (25 mS cm-1 for Li9.54Si1.74P1.44S11.7Cl0.3), as well as high stability ( ∼0 V vs. Li metal for Li9.6P3S12). A fabricated all-solid-state cell based on this Li conductor has very small internal resistance, esp. at 100 oC. The cell possesses high specific power that is superior to that of conventional cells with liq. electrolytes. Stable cycling with a high c.d. of 18 C (charging/discharging in just 3 min; where C is the C-rate) is also demonstrated.
    15. 15
      Yamane, H.; Shibata, M.; Shimane, Y.; Junke, T.; Seino, Y.; Adams, S.; Minami, K.; Hayashi, A.; Tatsumisago, M. Crystal Structure of a Superionic Conductor, Li7P3S11. Solid State Ionics 2007, 178, 1163– 1167,  DOI: 10.1016/j.ssi.2007.05.020
      15
      Crystal structure of a superionic conductor, Li7P3S11
      Yamane, Hisanori; Shibata, Masatoshi; Shimane, Yukio; Junke, Tadanori; Seino, Yoshikatsu; Adams, Stefan; Minami, Keiichi; Hayashi, Akitoshi; Tatsumisago, Masahiro
      Solid State Ionics (2007), 178 (15-18), 1163-1167CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
      A synchrotron x-ray powder diffraction pattern was measured for a Li superionic conductor, Li7P3S11, which has a high cond. of 3.2 × 10-3 S cm-1 at room temp. and a low activation energy of 12 kJ mol-1 [Mizuno et al. (2006)]. The crystal structure was solved by a direct space global optimization technique and refined by the Rietveld method. The compd. crystallizes in a triclinic cell, space group P-1, a = 12.5009(3), b = 6.03160(17), c = 12.5303(3) Å, α = 102.845(3)°, β = 113.2024(18)°, γ = 74.467(3)°, dc = 1.98 g/cm3, Rwp = 2.92%, Rp = 2.20%, RR = 7.69%, Re = 1.82%, RI = 1.95%, RF = 0.73%. PS4 tetrahedra and P2S7 ditetrahedra are contained in the structure and Li ions are situated between them.
    16. 16
      Seino, Y.; Ota, T.; Takada, K.; Hayashi, A.; Tatsumisago, M. A Sulphide Lithium Super Ion Conductor Is Superior to Liquid Ion Conductors for Use in Rechargeable Batteries. Energy Environ. Sci. 2014, 7, 627– 631,  DOI: 10.1039/C3EE41655K
      16
      A sulphide lithium super ion conductor is superior to liquid ion conductors for use in rechargeable batteries
      Seino, Yoshikatsu; Ota, Tsuyoshi; Takada, Kazunori; Hayashi, Akitoshi; Tatsumisago, Masahiro
      Energy & Environmental Science (2014), 7 (2), 627-631CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
      We report that a heat-treated Li2S-P2S5 glass-ceramic conductor has an extremely high ionic cond. of 1.7 × 10-2 S cm-1 and the lowest conduction activation energy of 17 kJ mol-1 at room temp. among lithium-ion conductors reported to date. The optimum conditions of the heat treatment reduce the grain boundary resistance, and the influence of voids, to increase the Li+ ionic cond. of the solid electrolyte so that it is greater than the conductivities of liq. electrolytes, when the transport no. of lithium ions in the inorg. electrolyte is unity.
    17. 17
      Boulineau, S.; Courty, M.; Tarascon, J.-M.; Viallet, V. Mechanochemical Synthesis of Li-Argyrodite Li6PS5X (X=Cl, Br, I) as Sulfur-Based Solid Electrolytes for All Solid State Batteries Application. Solid State Ionics 2012, 221, 1– 5,  DOI: 10.1016/j.ssi.2012.06.008
      17
      Mechanochemical synthesis of Li-argyrodite Li6PS5 X (X = Cl, Br, I) as sulfur-based solid electrolytes for all solid state batteries application
      Boulineau, Sylvain; Courty, Matthieu; Tarascon, Jean-Marie; Viallet, Virginie
      Solid State Ionics (2012), 221 (), 1-5CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
      Highly ion-conductive Li6PS5 X (X = Cl, Br, I) Li-argyrodites were prepd. through a high-energy ball milling. Elec. and electrochem. properties were investigated. Ball-milled compds. exhibit a high cond. between 2 and 7 × 10- 4 S/cm with an activation energy of 0.3-0.4 eV for conduction. These attractive properties were attributed to the spontaneous formation of crystd. Li-argyrodite during ball-milling. An optimization of milling time led to a cond. of 1.33 × 10- 3 S/cm for the Li6PS5Cl phase with an electrochem. stability up to 7 V vs. lithium. An all solid state LiCoO2/Elec./In lithium ion battery using ball-milled Li6PS5Cl as electrolyte was successfully assembled, and its room temp. performance is reported.
    18. 18
      Rao, R. P.; Adams, S. Studies of Lithium Argyrodite Solid Electrolytes for All-Solid-State Batteries. Phys. Status Solidi A 2011, 208, 1804– 1807,  DOI: 10.1002/pssa.201001117
      18
      Studies of lithium argyrodite solid electrolytes for all-solid-state batteries
      Rao, R. P.; Adams, S.
      Physica Status Solidi A: Applications and Materials Science (2011), 208 (8), 1804-1807CODEN: PSSABA; ISSN:1862-6300. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Rechargeable all-solid-state lithium Li-ion batteries (AS-LIBs) are attractive power sources for electrochem. applications; due to their potentiality in improving safety and stability over conventional batteries with liq. electrolytes. AS-LIBs require a Li-fast ion conductor (FIC) as the solid electrolyte. Finding a solid electrolyte with high ionic cond. and compatibility with other battery components is a key factor in building high performance AS-LIBs. There have been numerous studies, e.g., on lithium rich sulfide glasses as solid electrolytes. However, the limited c.d. remains a major obstacle in developing competitive batteries based on the known solid electrolytes. Here we prep. argyrodite-type Li6PS5X (X = Cl, Br, I) using mech. milling followed by annealing. XRD characterization reveals the formation and growth of Li6PS5X crystals in samples under varying annealing conditions. For Li6PS5Cl an ionic cond. of the order of 10-4 S/cm is reached at room temp., which is close to the Li mobility in conventional liq. electrolytes (LiPF6 in various carbonates) and well suitable for AS-LIBs.
    19. 19
      Bernges, T.; Culver, S. P.; Minafra, N.; Koerver, R.; Zeier, W. G. Competing Structural Influences in the Li Superionic Conducting Argyrodites Li6PS5–x SexBr (0 ≤ x ≤ 1) upon Se Substitution. Inorg. Chem. 2018, 57, 13920– 13928,  DOI: 10.1021/acs.inorgchem.8b02443
      19
      Competing Structural Influences in the Li Superionic Conducting Argyrodites Li6PS5-xSexBr (0 ≤ x ≤ 1) upon Se Substitution
      Bernges, Tim; Culver, Sean P.; Minafra, Nicolo; Koerver, Raimund; Zeier, Wolfgang G.
      Inorganic Chemistry (2018), 57 (21), 13920-13928CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)
      Li-ion conducting argyrodites have recently attracted significant interest as solid electrolytes for solid-state battery applications. To enhance the utility of materials in this class, a deeper understanding of the fundamental structure-property relations is still required. Using Rietveld refinements of x-ray diffraction data and pair distribution function anal. of neutron diffraction data, coupled with electrochem. impedance spectroscopy and speed of sound measurements, the structure and transport properties within Li6PS5-xSexBr (0 ≤ x ≤ 1) were monitored with increasing Se content. While it was previously suggested that the incorporation of larger, more polarizable anions within the argyrodite lattice should lead to enhancements in the ionic cond., the Li6PS5-xSexBr transport behavior is 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 cond. 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.
    20. 20
      Wang, Y.; Richards, W. D.; Ong, S. P.; Miara, L. J.; Kim, J. C.; Mo, Y.; Ceder, G. Design Principles for Solid-State Lithium Superionic Conductors. Nat. Mater. 2015, 14, 1026– 1031,  DOI: 10.1038/nmat4369
      20
      Design principles for solid-state lithium superionic conductors
      Wang, Yan; Richards, William Davidson; Ong, Shyue Ping; Miara, Lincoln J.; Kim, Jae Chul; Mo, Yifei; Ceder, Gerbrand
      Nature Materials (2015), 14 (10), 1026-1031CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
      Lithium solid electrolytes can potentially address two key limitations of the org. electrolytes used in today's lithium-ion batteries, namely, their flammability and limited electrochem. stability. However, achieving a Li+ cond. in the solid state comparable to existing liq. electrolytes (>1 mS cm-1) is particularly challenging. In this work, we reveal a fundamental relationship between anion packing and ionic transport in fast Li-conducting materials and expose the desirable structural attributes of good Li-ion conductors. We find that an underlying body-centered cubic-like anion framework, which allows direct Li hops between adjacent tetrahedral sites, is most desirable for achieving high ionic cond., and that indeed this anion arrangement is present in several known fast Li-conducting materials and other fast ion conductors. These findings provide important insight towards the understanding of ionic transport in Li-ion conductors and serve as design principles for future discovery and design of improved electrolytes for Li-ion batteries.
    21. 21
      Kraft, M. A.; Culver, S. P.; Calderon, M.; Böcher, F.; Krauskopf, T.; Senyshyn, A.; Dietrich, C.; Zevalkink, A.; Janek, J.; Zeier, W. G. Influence of Lattice Polarizability on the Ionic Conductivity in the Lithium Superionic Argyrodites Li6PS5X (X = Cl, Br, I). J. Am. Chem. Soc. 2017, 139, 10909– 10918,  DOI: 10.1021/jacs.7b06327
      21
      Influence of Lattice Polarizability on the Ionic Conductivity in the Lithium Superionic Argyrodites Li6PS5X (X = Cl, Br, I)
      Kraft, Marvin A.; Culver, Sean P.; Calderon, Mario; Boecher, Felix; Krauskopf, Thorben; Senyshyn, Anatoliy; Dietrich, Christian; Zevalkink, Alexandra; Janek, Juergen; Zeier, Wolfgang G.
      Journal of the American Chemical Society (2017), 139 (31), 10909-10918CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      In the search for novel solid electrolytes for solid-state batteries, thiophosphate ionic conductors have been in recent focus owing to their high ionic conductivities, which are believed to stem from a softer, more polarizable anion framework. Inspired by the oft-cited connection between a soft anion lattice and ionic transport, this work aims to provide evidence on how changing the polarizability of the anion sublattice in one structure affects ionic transport. Here, we systematically alter the anion framework polarizability of the superionic argyrodites Li6PS5X by controlling the fractional occupancy of the halide anions (X = Cl, Br, I). Ultrasonic speed of sound measurements are used to quantify the variation in the lattice stiffness and Debye frequencies. In combination with electrochem. impedance spectroscopy and neutron diffraction, these results show that the lattice softness has a striking influence on the ionic transport: the softer bonds lower the activation barrier and simultaneously decrease the prefactor of the moving ion. Due to the contradicting influence of these parameters on ionic cond., we find that it is necessary to tailor the lattice stiffness of materials in order to obtain an optimum ionic cond.
    22. 22
      Zhu, Y.; He, X.; Mo, Y. Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations. ACS Appl. Mater. Interfaces 2015, 7, 23685– 23693,  DOI: 10.1021/acsami.5b07517
      22
      Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations
      Zhu, Yizhou; He, Xingfeng; Mo, Yifei
      ACS Applied Materials & Interfaces (2015), 7 (42), 23685-23693CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      First-principles calcns. were performed to investigate the electrochem. stability of lithium solid electrolyte materials in all-solid-state Li-ion batteries. The common solid electrolytes were found to have a limited electrochem. window. The results suggest that the outstanding stability of the solid electrolyte materials is not thermodynamically intrinsic but is originated from kinetic stabilizations. The sluggish kinetics of the decompn. reactions cause a high overpotential leading to a nominally wide electrochem. window obsd. in many expts. The decompn. products, similar to the solid-electrolyte-interphases, mitigate the extreme chem. potential from the electrodes and protect the solid electrolyte from further decompns. With the aid of the first-principles calcns., the passivation mechanism is revealed of these decompn. interphases and quantified the extensions of the electrochem. window from the interphases. It was also found that the artificial coating layers applied at the solid electrolyte and electrode interfaces have a similar effect of passivating the solid electrolyte. The newly gained understanding provided general principles for developing solid electrolyte materials with enhanced stability and for engineering interfaces in all-solid-state Li-ion batteries.
    23. 23
      Zheng, F.; Kotobuki, M.; Song, S.; Lai, M. O.; Lu, L. Review on Solid Electrolytes for All-Solid-State Lithium-Ion Batteries. J. Power Sources 2018, 389, 198– 213,  DOI: 10.1016/j.jpowsour.2018.04.022
      23
      Review on solid electrolytes for all-solid-state lithium-ion batteries
      Zheng, Feng; Kotobuki, Masashi; Song, Shufeng; Lai, Man On; Lu, Li
      Journal of Power Sources (2018), 389 (), 198-213CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      All-solid-state (ASS) lithium-ion battery has attracted great attention due to its high safety and increased energy d. One of key components in the ASS battery (ASSB) is solid electrolyte that dets. performance of the ASSB. Many types of solid electrolytes have been investigated in great detail in the past years, including NASICON-type, garnet-type, perovskite-type, LISICON-type, LiPON-type, Li3N-type, sulfide-type, argyrodite-type, anti-perovskite-type and many more. This paper aims to provide comprehensive reviews on some typical types of key solid electrolytes and some ASSBs, and on gaps that should be resolved.
    24. 24
      Deng, Z.; Zhu, Z.; Chu, I.-H.; Ong, S. P. Data-Driven First-Principles Methods for the Study and Design of Alkali Superionic Conductors. Chem. Mater. 2017, 29, 281– 288,  DOI: 10.1021/acs.chemmater.6b02648
      24
      Data-Driven First-Principles Methods for the Study and Design of Alkali Superionic Conductors
      Deng, Zhi; Zhu, Zhuoying; Chu, Iek-Heng; Ong, Shyue Ping
      Chemistry of Materials (2017), 29 (1), 281-288CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      A detailed exposition of how first-principles methods can be used to guide alkali superionic conductor (ASIC) study and design is presented. Using the argyrodite Li6PS5Cl as a case study, it is demonstrated how modern information technol. (IT) infrastructure and software tools can facilitate the assessment of alkali superionic conductors in terms of various crit. properties of interest such as phase and electrochem. stability and ionic cond. The emphasis is on well-documented, reproducible anal. code that can be readily generalized to other material systems and design problems. For our chosen Li6PS5Cl case study material, it is shown that Li excess is crucial to enhancing its cond. by increasing the occupancy of interstitial sites that promote long-range Li+ diffusion between cage-like frameworks. The predicted room-temp. conductivities and activation barriers are in reasonably good agreement with exptl. values.
    25. 25
      Ceder, G. Opportunities and Challenges for First-Principles Materials Design and Applications to Li Battery Materials. MRS Bull. 2010, 35, 693– 701,  DOI: 10.1557/mrs2010.681
      25
      Opportunities and challenges for first-principles materials design and applications to Li battery materials
      Ceder, Gerbrand
      MRS Bulletin (2010), 35 (9), 693-701CODEN: MRSBEA; ISSN:0883-7694. (Materials Research Society)
      The idea of first-principles methods is to det. the properties of materials by solving the basic equations of quantum mechanics and statistical mechanics. With such an approach, one can, in principle, predict the behavior of novel materials without the need to synthesize them and create a virtual design lab. By showing several examples of new electrode materials that have been computationally designed, synthesized, and tested, the impact of first-principles methods in the field of Li battery electrode materials will be demonstrated. A significant advantage of computational property prediction is its scalability, which is currently being implemented into the Materials Genome Project at the Massachusetts Institute of Technol. Using a high-throughput computational environment, coupled to a database of all known inorg. materials, basic information on all known inorg. materials and a large no. of novel "designed" materials is being computed. Scalability of high-throughput computing can easily be extended to reach across the complete universe of inorg. compds., although challenges need to be overcome to further enable the impact of first-principles methods.
    26. 26
      Sendek, A. D.; Yang, Q.; Cubuk, E. D.; Duerloo, K.-A. N.; Cui, Y.; Reed, E. J. Holistic Computational Structure Screening of More than 12000 Candidates for Solid Lithium-Ion Conductor Materials. Energy Environ. Sci. 2017, 10, 306– 320,  DOI: 10.1039/C6EE02697D
      26
      Holistic computational structure screening of more than 12 000 candidates for solid lithium-ion conductor materials
      Sendek, Austin D.; Yang, Qian; Cubuk, Ekin D.; Duerloo, Karel-Alexander N.; Cui, Yi; Reed, Evan J.
      Energy & Environmental Science (2017), 10 (1), 306-320CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
      We present a new type of large-scale computational screening approach for identifying promising candidate materials for solid state electrolytes for lithium ion batteries that is capable of screening all known lithium contg. solids. To be useful for batteries, high performance solid state electrolyte materials must satisfy many requirements at once, an optimization that is difficult to perform exptl. or with computationally expensive ab initio techniques. We first screen 12 831 lithium contg. cryst. solids for those with high structural and chem. stability, low electronic cond., and low cost. We then develop a data-driven ionic cond. classification model using logistic regression for identifying which candidate structures are likely to exhibit fast lithium conduction based on exptl. measurements reported in the literature. The screening reduces the list of candidate materials from 12 831 down to 21 structures that show promise as electrolytes, few of which have been examd. exptl. We discover that none of our simple atomistic descriptor functions alone provide predictive power for ionic cond., but a multi-descriptor model can exhibit a useful degree of predictive power. We also find that screening for structural stability, chem. stability and low electronic cond. eliminates 92.2% of all Li-contg. materials and screening for high ionic cond. eliminates a further 93.3% of the remainder. Our screening utilizes structures and electronic information contained in the Materials Project database.
    27. 27
      Hautier, G.; Fischer, C. C.; Jain, A.; Mueller, T.; Ceder, G. Finding Nature’s Missing Ternary Oxide Compounds Using Machine Learning and Density Functional Theory. Chem. Mater. 2010, 22, 3762– 3767,  DOI: 10.1021/cm100795d
      27
      Finding Nature's Missing Ternary Oxide Compounds Using Machine Learning and Density Functional Theory
      Hautier, Geoffroy; Fischer, Christopher C.; Jain, Anubhav; Mueller, Tim; Ceder, Gerbrand
      Chemistry of Materials (2010), 22 (12), 3762-3767CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      Finding new compds. and their crystal structures is an essential step to new materials discoveries. We demonstrate how this search can be accelerated using a combination of machine learning techniques and high-throughput ab initio computations. Using a probabilistic model built on an exptl. crystal structure database, novel compns. that are most likely to form a compd., and their most-probable crystal structures, are identified and tested for stability by ab initio computations. We performed such a large-scale search for new ternary oxides, discovering 209 new compds. with a limited computational budget. A list of these predicted compds. is provided, and we discuss the chemistries in which high discovery rates can be expected.
    28. 28
      Fujimura, K.; Seko, A.; Koyama, Y.; Kuwabara, A.; Kishida, I.; Shitara, K.; Fisher, C. A. J.; Moriwake, H.; Tanaka, I. Accelerated Materials Design of Lithium Superionic Conductors Based on First-Principles Calculations and Machine Learning Algorithms. Adv. Energy Mater. 2013, 3, 980– 985,  DOI: 10.1002/aenm.201300060
      28
      Accelerated materials design of lithium superionic conductors based on first-principles calculations and machine learning algorithms
      Fujimura, Koji; Seko, Atsuto; Koyama, Yukinori; Kuwabara, Akihide; Kishida, Ippei; Shitara, Kazuki; Fisher, Craig A. J.; Moriwake, Hiroki; Tanaka, Isao
      Advanced Energy Materials (2013), 3 (8), 980-985CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)
      In this article, results of systematic sets of first-principles calcns. based on the cluster expansion method, as well as first-principles mol. dynamics (FPMD) simulations carried out to calc. lithium-ion conductivities at high temp., for a diverse range of compns. is studied. A machine-learning technique is used to combine theor. and exptl. datasets to predict the cond. of each compn. at 373 K. The insights obtained show that an iterative combination of first-principles calcns. and focused expts. can greatly accelerate the materials design process by enabling a wide compositional and structural phase space to be examd. efficiently.
    29. 29
      Adams, S. Bond Valence Analysis of Structure–Property Relationships in Solid Electrolytes. J. Power Sources 2006, 159, 200– 204,  DOI: 10.1016/j.jpowsour.2006.04.085
      29
      Bond valence analysis of structure-property relationships in solid electrolytes
      Adams, Stefan
      Journal of Power Sources (2006), 159 (1), 200-204CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      The augmented bond valence approach may be used to establish structure-property relations in solid electrolytes, to identify the mobile species and to locate energetically favorable transport pathways for mobile ions, using the bond valence sum mismatch landscape created by the immobile substructure. Ion transport pathways of cryst. and glassy Li+ conductors are analyzed. The bond valence anal. provides the visualization of pathways and the relevant activation energies - thereby it helps to clarify transport mechanisms and to identify promising novel ion-conducting materials. The approach is particularly useful for the anal. of disordered systems such as ion-conducting glasses, where a structure-cond. correlation was identified.
    30. 30
      Xiao, R.; Li, H.; Chen, L. High-Throughput Design and Optimization of Fast Lithium Ion Conductors by the Combination of Bond-Valence Method and Density Functional Theory. Sci. Rep. 2015, 5, 14227,  DOI: 10.1038/srep14227
      30
      High-throughput design and optimization of fast lithium ion conductors by the combination of bond-valence method and density functional theory
      Xiao, Ruijuan; Li, Hong; Chen, Liquan
      Scientific Reports (2015), 5 (), 14227CODEN: SRCEC3; ISSN:2045-2322. (Nature Publishing Group)
      Looking for solid state electrolytes with fast lithium ion conduction is an important prerequisite for developing all-solid-state lithium secondary batteries. By combining the simulation techniques in different levels of accuracy, e.g. the bond-valence (BV) method and the d. functional theory (DFT), a high-throughput design and optimization scheme is proposed for searching fast lithium ion conductors as candidate solid state electrolytes for lithium rechargeable batteries. The screening from more than 1000 compds. is performed through BV-based method, and the ability to predict reliable tendency of the Li+ migration energy barriers is confirmed by comparing with the results from DFT calcns. β-Li3PS4 is taken as a model system to demonstrate the application of this combination method in optimizing properties of solid electrolytes. By employing the high-throughput DFT simulations to more than 200 structures of the doping derivs. of β-Li3PS4, the effects of doping on the ionic conductivities in this material are predicted by the BV calcns. The O-doping scheme is proposed as a promising way to improve the kinetic properties of this materials, and the validity of the optimization is proved by the first-principles mol. dynamics (FPMD) simulations.
    31. 31
      Adams, S.; Rao, R. P. Understanding Ionic Conduction and Energy Storage Materials with Bond-Valence-Based Methods. In Bond Valences; Brown, I. D.; Poeppelmeier, K. R. Eds. Structure and Bonding; Springer Berlin Heidelberg: Berlin, Heidelberg, 2014; pp 129– 159.
      There is no corresponding record for this reference.
    32. 32
      Kandagal, V. S.; Bharadwaj, M. D.; Waghmare, U. V. Theoretical Prediction of a Highly Conducting Solid Electrolyte for Sodium Batteries: Na10GeP2S12. J. Mater. Chem. A 2015, 3, 12992– 12999,  DOI: 10.1039/C5TA01616A
      32
      Theoretical prediction of a highly conducting solid electrolyte for sodium batteries: Na10GeP2S12
      Kandagal, Vinay S.; Bharadwaj, Mridula Dixit; Waghmare, Umesh V.
      Journal of Materials Chemistry A: Materials for Energy and Sustainability (2015), 3 (24), 12992-12999CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
      Using 1st-principles simulations, the authors predict a high-performance solid electrolyte Na10GeP2S12 for use in Na-S (Na-S) batteries. The thermodn. stability of its structure is established through detn. of decompn. reaction energies and phonons, while Na-ionic cond. is obtained using ab initio mol. dynamics at elevated temps. The est. of the room-temp. (RT) cond. is 4.7 × 10-3 S cm-1, which is slightly higher than those of other superionic solid electrolytes such as β''-alumina and Na3Zr2Si2PO12, currently used in practical high-temp. Na-S batteries. Activation energy obtained from the Arrhenius plot (in the range 800-1400 K) is 0.2 eV, which is slightly lower than the typical values exhibited by other ceramic conductors (0.25-1 V) (Hueso et al., Energy Environ. Sci., 2013, 6, 734). Soft Na-S phonon modes are responsible for its thermodn. stability and the lower activation barrier for diffusion of Na-ions. Finally, the calcd. electronic bandgap of 2.7 eV (a wide electrochem. window) augurs well for its safe use in Na batteries. Opening up a possibility for realizing RT operation of Na-S batteries, the prediction of a new phase in the Na-Ge-P-S system will stimulate exptl. studies of the material.
    33. 33
      Zhang, Y.; Miller, G. J.; Fokwa, B. P. T. Computational Design of Rare-Earth-Free Magnets with the Ti3Co5B2-Type Structure. Chem. Mater. 2017, 29, 2535– 2541,  DOI: 10.1021/acs.chemmater.6b04114
      33
      Computational Design of Rare-Earth-Free Magnets with the Ti3Co5B2-Type Structure
      Zhang, Yuemei; Miller, Gordon J.; Fokwa, Boniface P. T.
      Chemistry of Materials (2017), 29 (6), 2535-2541CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      The prolific Ti3Co5B2 structure type produced exciting materials with tunable magnetic properties, ranging from soft magnetic Ti2FeRh5B2, to semihard magnetic Ti2FeRu4RhB2 and hard magnetic Sc2FeRu3Ir2B2. D. functional theory (DFT) was employed to study their spin-orbit coupling effect, spin exchange, and magnetic dipole-dipole interactions to understand their magnetic anisotropy and relate it to their various coercivities, with the objective of being able to predict new materials with large magnetic anisotropy. The authors' calcns. show that the contribution of magnetic dipole-dipole interactions to the magnetocryst. anisotropy energy (MAE) in Ti3Co5B2-type compds. is much weaker than the spin-orbit coupling effect, and Sc2FeRu3Ir2B2 has, by far, the largest MAE and strong intrachain and interchain Fe-Fe spin exchange coupling, thus confirming its hard magnetic properties. The authors then targeted materials contg. the more earth-abundant and less expensive Co, instead of Rh, Ru or Ir, so that the authors' study started with Ti3Co5B2, which the authors found to be nonmagnetic. In the next step, substitutions on the Ti sites in Ti3Co5B2 led to new potential quaternary phases T2T'Co5B2 (T = Ti, Hf; T' = Mn, Fe). For Hf2MnCo5B2, the authors found a large MAE (+0.96 meV/f.u.) but relatively weak interchain Mn-Mn spin exchange interactions, whereas for Hf2FeCo5B2, there is a relatively smaller MAE (+0.17 meV/f.u.) but strong Fe-Fe interchain and intrachain spin exchange interactions. Therefore, these two Co-rich phases are predicted to be new rare-earth-free, semihard to hard magnetic materials.
    34. 34
      Wang, Y.; Richards, W. D.; Bo, S.-H.; Miara, L. J.; Ceder, G. Computational Prediction and Evaluation of Solid-State Sodium Superionic Conductors Na7P3X11 (X = O, S, Se). Chem. Mater. 2017, 29, 7475– 7482,  DOI: 10.1021/acs.chemmater.7b02476
      34
      Computational Prediction and Evaluation of Solid-State Sodium Superionic Conductors Na7P3X11 (X = O, S, Se)
      Wang, Yan; Richards, William D.; Bo, Shou-Hang; Miara, Lincoln J.; Ceder, Gerbrand
      Chemistry of Materials (2017), 29 (17), 7475-7482CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      Inorg. solid-state ionic conductors with high ionic cond. are of great interest for their application in safe and high-energy-d. solid-state batteries. Our previous study reveals that the crystal structure of the ionic conductor Li7P3S11 contains a body-centered-cubic (bcc) arrangement of sulfur anions and that such a bcc anion framework facilitates high ionic cond. Here, we apply a set of first-principles calcns. techniques to investigate A7P3X11-type (A = Li, Na; X = O, S, Se) lithium and sodium superionic conductors derived from Li7P3S11, focusing on their structural, dynamic and thermodn. properties. We find that the ionic cond. of Na7P3S11 and Na7P3Se11 is over 10 mS cm-1 at room temp., significantly higher than that of any known solid Na-ion sulfide or selenide conductor. However, thermodn. calcns. suggest that the isostructural sodium compds. may not be trivial to synthesize, which clarifies the puzzle concerning the exptl. problems in trying to synthesize these compds.
    35. 35
      Collins, C.; Dyer, M. S.; Pitcher, M. J.; Whitehead, G. F. S.; Zanella, M.; Mandal, P.; Claridge, J. B.; Darling, G. R.; Rosseinsky, M. J. Accelerated Discovery of Two Crystal Structure Types in a Complex Inorganic Phase Field. Nature 2017, 546, 280,  DOI: 10.1038/nature22374
      35
      Accelerated discovery of two crystal structure types in a complex inorganic phase field
      Collins, C.; Dyer, M. S.; Pitcher, M. J.; Whitehead, G. F. S.; Zanella, M.; Mandal, P.; Claridge, J. B.; Darling, G. R.; Rosseinsky, M. J.
      Nature (London, United Kingdom) (2017), 546 (7657), 280-284CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
      The discovery of new materials is hampered by the lack of efficient approaches to the exploration of both the large no. of possible elemental compns. for such materials, and of the candidate structures at each compn. For example, the discovery of inorg. extended solid structures has relied on knowledge of crystal chem. coupled with time-consuming materials synthesis with systematically varied elemental ratios. Computational methods have been developed to guide synthesis by predicting structures at specific compns. and predicting compns. for known crystal structures, with notable successes. However, the challenge of finding qual. new, exptl. realizable compds., with crystal structures where the unit cell and the atom positions within it differ from known structures, remains for compositionally complex systems. Many valuable properties arise from substitution into known crystal structures, but materials discovery using this approach alone risks both missing best-in-class performance and attempting design with incomplete knowledge. Here we report the exptl. discovery of two structure types by computational identification of the region of a complex inorg. phase field that contains them. This is achieved by computing probe structures that capture the chem. and structural diversity of the system and whose energies can be ranked against combinations of currently known materials. Subsequent exptl. exploration of the lowest-energy regions of the computed phase diagram affords two materials with previously unreported crystal structures featuring unusual structural motifs. This approach will accelerate the systematic discovery of new materials in complex compositional spaces by efficiently guiding synthesis and enhancing the predictive power of the computational tools through expansion of the knowledge base underpinning them.
    36. 36
      Dyer, M. S.; Collins, C.; Hodgeman, D.; Chater, P. A.; Demont, A.; Romani, S.; Sayers, R.; Thomas, M. F.; Claridge, J. B.; Darling, G. R. Computationally Assisted Identification of Functional Inorganic Materials. Science 2013, 340, 847– 852,  DOI: 10.1126/science.1226558
      36
      Computationally Assisted Identification of Functional Inorganic Materials
      Dyer, Matthew S.; Collins, Christopher; Hodgeman, Darren; Chater, Philip A.; Demont, Antoine; Romani, Simon; Sayers, Ruth; Thomas, Michael F.; Claridge, John B.; Darling, George R.; Rosseinsky, Matthew J.
      Science (Washington, DC, United States) (2013), 340 (6134), 847-852CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
      The design of complex inorg. materials is a challenge because of the diversity of their potential structures. We present a method for the computational identification of materials contg. multiple atom types in multiple geometries by ranking candidate structures assembled from extended modules contg. chem. realistic at. environments. Many existing functional materials can be described in this way, and their properties are often detd. by the chem. and electronic structure of their constituent modules. To demonstrate the approach, we isolated the oxide Y2.24Ba2.28Ca3.48Fe7.44Cu0.56O21, with a largest unit cell dimension of over 60 angstroms and 148 atoms in the unit cell, by using a combination of this method and exptl. work and show that it has the properties necessary to function as a solid oxide fuel-cell cathode.
    37. 37
      Wang, X.; Xiao, R.; Li, H.; Chen, L. Oxysulfide LiAlSO: A Lithium Superionic Conductor from First Principles. Phys. Rev. Lett. 2017, 118, 195901,  DOI: 10.1103/PhysRevLett.118.195901
      37
      Oxysulfide LiAlSO: a lithium superionic conductor from first principles
      Wang, Xuelong; Xiao, Ruijuan; Li, Hong; Chen, Liquan
      Physical Review Letters (2017), 118 (19), 195901/1-195901/6CODEN: PRLTAO; ISSN:1079-7114. (American Physical Society)
      Through first-principles calcns. and crystal structure prediction techniques, we identify a new layered oxysulfide LiAlSO in orthorhombic structure as a novel lithium superionic conductor. Two kinds of stacking sequences of layers of AlS2O2 are found in different temp. ranges. Phonon and mol. dynamics simulations verify their dynamic stabilities, and wide band gaps up to 5.6 eV are found by electronic structure calcns. The lithium migration energy barrier simulations reveal the collective interstitial-host ion "kick-off" hopping mode with barriers lower than 50 meV as the dominating conduction mechanism for LiAlSO, indicating it to be a promising solid-state electrolyte in lithium secondary batteries with fast ionic cond. and a wide electrochem. window. This is a first attempt in which the lithium superionic conductors are designed by the crystal structure prediction method and may help explore other mixed-anion battery materials.
    38. 38
      Huang, B. Energy Harvesting and Conversion Mechanisms for Intrinsic Upconverted Mechano-Persistent Luminescence in CaZnOS. Phys. Chem. Chem. Phys. 2016, 18, 25946– 25974,  DOI: 10.1039/C6CP04706H
      38
      Energy harvesting and conversion mechanisms for intrinsic upconverted mechano-persistent luminescence in CaZnOS
      Huang, Bolong
      Physical Chemistry Chemical Physics (2016), 18 (37), 25946-25974CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
      The authors interpreted the mechanisms of energy harvesting and conversion for intrinsic upconverted mechano-persistent luminescence in CaZnOS through a native point defects study. Vacancy defects such as Zn and O vacancies, as well as Schottky pair defects, act as energy harvesting centers; they are very readily formed and very active. They are extra deep electron or hole trap levels near the valence or conduction band edges, resp. This leads to a coupling and exchange effect to continuously collect and transport host charges along a path via localized states to deep recombination levels. The initiating energy barrier is small and can be overcome by ambient thermal stimulation or quantum tunneling. Native activators such as V2+O, V2+ZnO, and V2+CaZnOS function as energy conversion centers to transfer energy into photon emissions. This gives a solid theor. ref. for developing upconverted mechano-persistent luminescence.
    39. 39
      Rangasamy, E.; Sahu, G.; Keum, J. K.; Rondinone, A. J.; Dudney, N. J.; Liang, C. A High Conductivity Oxide–Sulfide Composite Lithium Superionic Conductor. J. Mater. Chem. A 2014, 2, 4111– 4116,  DOI: 10.1039/C3TA15223E
      39
      A high conductivity oxide-sulfide composite lithium superionic conductor
      Rangasamy, Ezhiylmurugan; Sahu, Gayatri; Keum, Jong Kahk; Rondinone, Adam J.; Dudney, Nancy J.; Liang, Chengdu
      Journal of Materials Chemistry A: Materials for Energy and Sustainability (2014), 2 (12), 4111-4116CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
      A composite electrolyte of LLZO (Li7La3Zr2O12) and LPS (β-Li3PS4) successfully combines low grain boundary resistance, room temp. processability, and low interfacial resistance of LPS with the excellent electrochem. stability and ionic cond. of LLZO. The composite electrolyte improves the ionic cond. of parent electrolytes and augments exceptional compatibility with metallic lithium, thereby making the electrolyte attractive for practical solid-state batteries.
    40. 40
      Suzuki, K.; Sakuma, M.; Hori, S.; Nakazawa, T.; Nagao, M.; Yonemura, M.; Hirayama, M.; Kanno, R. Synthesis, Structure, and Electrochemical Properties of Crystalline Li-P-S-O Solid Electrolytes: Novel Lithium-Conducting Oxysulfides of Li10GeP2S12 Family. Solid State Ionics 2016, 288, 229– 234,  DOI: 10.1016/j.ssi.2016.02.002
      40
      Synthesis, structure, and electrochemical properties of crystalline Li-P-S-O solid electrolytes: Novel lithium-conducting oxysulfides of Li10GeP2S12 family
      Suzuki, Kota; Sakuma, Masamitsu; Hori, Satoshi; Nakazawa, Tetsuya; Nagao, Miki; Yonemura, Masao; Hirayama, Masaaki; Kanno, Ryoji
      Solid State Ionics (2016), 288 (), 229-234CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
      Novel lithium-ion (Li+)-conducting oxysulfides of the Li10GeP2S12 family were found in the ternary Li2S-P2S5-P2O5 system; Li10GeP2S12-type solid solns. with compns. Li3 + 5xP1 - xS4 - zOz (x = 0.03-0.08, z = 0.4-0.8) were confirmed. The solid solns. showed ionic conductivities from 4.14 × 10- 5 to 2.64 × 10- 4 S cm- 1 at 298 K and a wide electrochem. window of 0-5.0 V (vs. Li/Li+). Among the solid solns. synthesized, the purest phase had the compn. Li3.35P0.93S3.5O0.5 (x = 0.07, z = 0.5). Structural anal. revealed that the novel oxysulfides are isostructural to the original Li10GeP2S12 structure and the (P/.box.)(S/O)4 tetrahedra, which indicates the presence of cation defects with oxygen substitution in the crystal structure. Electrochem. stability of the oxysulfides was confirmed in the voltage range of 0-5.0 V. The solid-electrolyte interphase (SEI) resistivity and its cycle-dependence evaluation for new materials demonstrated that the oxysulfides had lower resistivities and furnished well-contacted SEI layers during the charge-discharge process.
    41. 41
      Wang, X.; Xiao, R.; Li, H.; Chen, L. Oxygen-Driven Transition from Two-Dimensional to Three-Dimensional Transport Behaviour in β-Li3PS4 Electrolyte. Phys. Chem. Chem. Phys. 2016, 18, 21269– 21277,  DOI: 10.1039/C6CP03179J
      41
      Oxygen-driven transition from two-dimensional to three-dimensional transport behaviour in β-Li3PS4 electrolyte
      Wang, Xuelong; Xiao, Ruijuan; Li, Hong; Chen, Liquan
      Physical Chemistry Chemical Physics (2016), 18 (31), 21269-21277CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
      Solid state electrolytes with high Li ion conduction are vital to the development of all-solid-state lithium batteries. Lithium thiophosphate Li3PS4 is the parent material of a series of Li superionic conductors Li10MX2S12 (M = Ge, Sn,...; X = P, Si,...), and β-Li3PS4 shows relatively high ionic cond. itself, though it is not room-temp. stable. The pos. effects of introducing O dopants into β-Li3PS4 to stabilize the crystal phase and improve the ionic conducting behavior are revealed in this study. With the aid of first-principles d. functional theory (DFT) computations and quasi-empirical bond-valence calcns., the effects of O doping at different concns. on the properties of β-Li3PS4 is thoroughly investigated from the aspects of lattice structures, electronic structures, ionic transport properties, the interface stability against Li and the thermodn. stability. An oxygen-driven transition from two-dimensional to three-dimensional transport behavior is found and the oxygen dopants play the role as a connector of 2D paths. Based on all these simulation results, hopefully our research can provide a new strategy for the modification of lithium thiophosphate solid electrolytes.
    42. 42
      Kim, K.-H.; Martin, S. W. Structures and Properties of Oxygen-Substituted Li10SiP2S12–xOx Solid-State Electrolytes. Chem. Mater. 2019, 31, 3984– 3991,  DOI: 10.1021/acs.chemmater.9b00505
      42
      Structures and Properties of Oxygen-Substituted Li10SiP2S12-xOx Solid-State Electrolytes
      Kim, Kwang-Hyun; Martin, Steve W.
      Chemistry of Materials (2019), 31 (11), 3984-3991CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      Li10SiP2S12 (LSiPS), which has an Li10GeP2S12 (LGPS)-type cryst. structure, was synthesized by solid-state reaction and then doped with O to produce oxy-sulfide compns. Li10SiP2S12-xOx (LSiPSO), where 0 ≤ x ≤ 1.75. The phase distribution and local structural units present in the LSiPSO materials were detd. via a combination of powder x-ray diffraction and Raman, FTIR, and solid-state NMR spectroscopies. At smaller amts. of O substitution for S, x < 1, in LSiPS, the structure of the LSiPSO phases became more uniform in the LGPS structure from smaller amts. of the impurity β-Li3PS4 and more of the O-substituted LGPS-like structure. Consistent with this, the Li ion cond. increases in proportion to the decrease in the amt. of the β-Li3PS4 phase and the growth of the LGPS-like phase. The highest Li ionic cond. was found for x = 0.7 at 3.1 (±0.4) × 10-3 S/cm at 25°. However, for x ≥ 0.9, ionic cond. decreased as a result of the degrdn. of the cryst. LGPS-like phase and generation of the O-rich Li3PO4 phase. 31P and 29Si NMR were used to det. the type and concn. of the various P and Si short-range order (SRO) structural units present as a function of x. Both pure sulfide, pure oxide, and mixed oxy-sulfide P and S SRO polyhedra were obsd. with the general trend being that as x increased, the fraction of mixed oxy-sulfide and pure oxide SRO polyhedra increased. Significantly, only pure oxide orthophosphate polyhedra PO4-3 were obsd., and no pure orthosilicate SiO44- SRO units were obsd., even at the highest x values examd.
    43. 43
      Tao, Y.; Chen, S.; Liu, D.; Peng, G.; Yao, X.; Xu, X. Lithium Superionic Conducting Oxysulfide Solid Electrolyte with Excellent Stability against Lithium Metal for All-Solid-State Cells. J. Electrochem. Soc. 2016, 163, A96– A101,  DOI: 10.1149/2.0311602jes
      43
      Lithium Superionic Conducting Oxysulfide Solid Electrolyte with Excellent Stability against Lithium Metal for All-Solid-State Cells
      Tao, Yicheng; Chen, Shaojie; Liu, Deng; Peng, Gang; Yao, Xiayin; Xu, Xiaoxiong
      Journal of the Electrochemical Society (2016), 163 (2), A96-A101CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
      For the high-energy battery using Li metal as a neg. electrode, the electrolyte is one of the most crit. factors that significantly affects the cell performance. Herein, new 75Li2S·(25-x)P2S5·xP2O5 (mol%) solid state electrolytes are prepd. by optimized mech. milling technique and subsequent heat-treatment process. The electrolyte substituted with 1 mol% P2O5 presents the highest cond. of 8 × 10-4 S cm-1 at room temp., which increases up to 56% compared to that of the pristine sample. The enhanced cond. could be attributed to the decrease of the activation energy for Li+-ion diffusion. The as-prepd. 75Li2S·24P2S5·1P2O5 electrolyte exhibits good electrochem. stability and compatibility with the metallic lithium electrode. The all-solid-state cell with a structure of LiCoO2/75Li2S·24P2S5·1P2O5/Li shows a discharge capacity of 109 mAh g-1 at 0.1 C and high capacity retention 85.2% after 30 cycles at 25°C, which are better than these of the cell use the 75Li2S·25P2S5 as electrolyte.
    44. 44
      Changming, F.; Haichun, G.; Yan, H.; Zengliang, C.; Yi, Z. Oxysulfide Glasses - a New Kind of Lithium Ion Conductors. Solid State Ionics 1991, 48, 289– 293,  DOI: 10.1016/0167-2738(91)90045-D
      There is no corresponding record for this reference.
    45. 45
      Gao, J.; Shi, S.; Xiao, R.; Li, H. Synthesis and Ionic Transport Mechanisms of α-LiAlO2. Solid State Ionics 2016, 286, 122– 134,  DOI: 10.1016/j.ssi.2015.12.028
      45
      Synthesis and ionic transport mechanisms of α-LiAlO2
      Gao, Jian; Shi, Siqi; Xiao, Ruijuan; Li, Hong
      Solid State Ionics (2016), 286 (), 122-134CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
      The pure phase α-LiAlO2 is synthesized by a solid-state reaction. The obtained product has nanocryst. structure with the Li deficient regions near the surfaces. Combining X-ray diffraction (XRD) and thermogravimetry-differential scanning calorimetry (TG-DSC), the synthesis mechanism is revealed. The measured room-temp. ionic cond. of the α-LiAlO2 ceramic pellet is as low as 10- 21 S·cm- 1. This could be caused by the absence of conduction pathways, as calcd. from the bond-valence (BV) method. In addn., a first-principles calcn. is performed. The calcd. result suggests that although the α-LiAlO2 bulk has the extremely low ionic cond., its ionic cond. could be increased significantly when applied the bias voltage, which is due to the introduction of external lithium sources (lithium reservoirs of interstitials/vacancies) and external charge sources (electrons/holes). This may explain why α-LiAlO2 as the coating layer on cathode for Li-ion batteries does not block the transport of lithium ions.
    46. 46
      Leube, B. T.; Inglis, K. K.; Carrington, E. J.; Sharp, P. M.; Shin, J. F.; Neale, A. R.; Manning, T. D.; Pitcher, M. J.; Hardwick, L. J.; Dyer, M. S. Lithium Transport in Li4.4M0.4M′0.6S4 (M = Al3+, Ga3+, and M′ = Ge4+, Sn4+): Combined Crystallographic, Conductivity, Solid State NMR, and Computational Studies. Chem. Mater. 2018, 30, 7183– 7200,  DOI: 10.1021/acs.chemmater.8b03175
      46
      Lithium Transport in Li4.4M0.4M'0.6S4 (M =Al3+, Ga3+, and M' =Ge4+, Sn4+): Combined Crystallographic, Conductivity, Solid State NMR, and Computational Studies
      Leube, Bernhard T.; Inglis, Kenneth K.; Carrington, Elliot J.; Sharp, Paul M.; Shin, J. Felix; Neale, Alex R.; Manning, Troy D.; Pitcher, Michael J.; Hardwick, Laurence J.; Dyer, Matthew S.; Blanc, Frederic; Claridge, John B.; Rosseinsky, Matthew J.
      Chemistry of Materials (2018), 30 (20), 7183-7200CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      To understand the structural and compositional factors controlling Li transport in sulfides, we explored the Li5AlS4-Li4GeS4 phase field for new materials. Both parent compds. are defined structurally by a hcp. sulfide lattice, where distinct arrangements of tetrahedral metal sites give Li5AlS4 a layered structure and Li4GeS4 a 3-dimensional structure related to γ-Li3PO4. The combination of the 2 distinct structural motifs is expected to lead to new structural chem. We identified the new cryst. phase Li4.4Al0.4Ge0.6S4, and investigated the structure and Li+ ion dynamics of the family of structurally related materials Li4.4M0.4M'0.6S4 (M =Al3+, Ga3+ and M' =Ge4+, Sn4+). We used neutron diffraction to solve the full structures of the Al-homologues, which adopt a layered close-packed structure with a new arrangement of tetrahedral (M/M') sites and a novel combination of ordered and disordered lithium vacancies. AC impedance spectroscopy revealed lithium conductivities in the range of 3(2) × 10-6 to 4.3(3) × 10-5 S/cm at room temp. with activation energies between 0.43(1) and 0.38(1) eV. Electrochem. performance was tested in a plating and stripping expt. against Li metal electrodes and showed good stability of the Li4.4Al0.4Ge0.6S4 phase over 200 h. A combination of variable temp. 7Li solid state NMR spectroscopy and ab initio mol. dynamics calcns. on selected phases showed that 2-dimensional diffusion with a low energy barrier of 0.17 eV is responsible for long-range Li transport, with diffusion pathways mediated by the disordered vacancies while the ordered vacancies do not contribute to the cond. This new structural family of sulfide Li+ ion conductors offers insight into the role of disordered vacancies on Li+ ion cond. mechanisms in hexagonally close packed sulfides that can inform future materials design.
    47. 47
      Kresse, G.; Furthmüller, J. Efficient Iterative Schemes for Ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set. Phys. Rev. B 1996, 54, 11169– 11186,  DOI: 10.1103/PhysRevB.54.11169
      47
      Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
      Kresse, G.; Furthmueller, J.
      Physical Review B: Condensed Matter (1996), 54 (16), 11169-11186CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
      The authors present an efficient scheme for calcg. the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set. In the first part the application of Pulay's DIIS method (direct inversion in the iterative subspace) to the iterative diagonalization of large matrixes will be discussed. This approach is stable, reliable, and minimizes the no. of order Natoms3 operations. In the second part, we will discuss an efficient mixing scheme also based on Pulay's scheme. A special "metric" and a special "preconditioning" optimized for a plane-wave basis set will be introduced. Scaling of the method will be discussed in detail for non-self-consistent and self-consistent calcns. It will be shown that the no. of iterations required to obtain a specific precision is almost independent of the system size. Altogether an order Natoms2 scaling is found for systems contg. up to 1000 electrons. If we take into account that the no. of k points can be decreased linearly with the system size, the overall scaling can approach Natoms. They have implemented these algorithms within a powerful package called VASP (Vienna ab initio simulation package). The program and the techniques have been used successfully for a large no. of different systems (liq. and amorphous semiconductors, liq. simple and transition metals, metallic and semiconducting surfaces, phonons in simple metals, transition metals, and semiconductors) and turned out to be very reliable.
    48. 48
      Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 1996, 77, 3865– 3868,  DOI: 10.1103/PhysRevLett.77.3865
      48
      Generalized gradient approximation made simple
      Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
      Physical Review Letters (1996), 77 (18), 3865-3868CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
      Generalized gradient approxns. (GGA's) for the exchange-correlation energy improve upon the local spin d. (LSD) description of atoms, mols., and solids. We present a simple derivation of a simple GGA, in which all parameters (other than those in LSD) are fundamental consts. Only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked. Improvements over PW91 include an accurate description of the linear response of the uniform electron gas, correct behavior under uniform scaling, and a smoother potential.
    49. 49
      Kresse, G.; Joubert, D. From Ultrasoft Pseudopotentials to the Projector Augmented-Wave Method. Phys. Rev. B 1999, 59, 1758– 1775,  DOI: 10.1103/PhysRevB.59.1758
      49
      From ultrasoft pseudopotentials to the projector augmented-wave method
      Kresse, G.; Joubert, D.
      Physical Review B: Condensed Matter and Materials Physics (1999), 59 (3), 1758-1775CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
      The formal relationship between ultrasoft (US) Vanderbilt-type pseudopotentials and Blochl's projector augmented wave (PAW) method is derived. The total energy functional for US pseudopotentials can be obtained by linearization of two terms in a slightly modified PAW total energy functional. The Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional. A simple way to implement the PAW method in existing plane-wave codes supporting US pseudopotentials is pointed out. In addn., crit. tests are presented to compare the accuracy and efficiency of the PAW and the US pseudopotential method with relaxed-core all-electron methods. These tests include small mols. (H2, H2O, Li2, N2, F2, BF3, SiF4) and several bulk systems (diamond, Si, V, Li, Ca, CaF2, Fe, Co, Ni). Particular attention is paid to the bulk properties and magnetic energies of Fe, Co, and Ni.
    50. 50
      Ong, S. P.; Richards, W. D.; Jain, A.; Hautier, G.; Kocher, M.; Cholia, S.; Gunter, D.; Chevrier, V. L.; Persson, K. A.; Ceder, G. Python Materials Genomics (Pymatgen): A Robust, Open-Source Python Library for Materials Analysis. Comput. Mater. Sci. 2013, 68, 314– 319,  DOI: 10.1016/j.commatsci.2012.10.028
      50
      Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis
      Ong, Shyue Ping; Richards, William Davidson; Jain, Anubhav; Hautier, Geoffroy; Kocher, Michael; Cholia, Shreyas; Gunter, Dan; Chevrier, Vincent L.; Persson, Kristin A.; Ceder, Gerbrand
      Computational Materials Science (2013), 68 (), 314-319CODEN: CMMSEM; ISSN:0927-0256. (Elsevier B.V.)
      We present the Python Materials Genomics (pymatgen) library, a robust, open-source Python library for materials anal. A key enabler in high-throughput computational materials science efforts is a robust set of software tools to perform initial setup for the calcns. (e.g., generation of structures and necessary input files) and post-calcn. anal. to derive useful material properties from raw calcd. data. The pymatgen library aims to meet these needs by (1) defining core Python objects for materials data representation, (2) providing a well-tested set of structure and thermodn. analyses relevant to many applications, and (3) establishing an open platform for researchers to collaboratively develop sophisticated analyses of materials data obtained both from first principles calcns. and expts. The pymatgen library also provides convenient tools to obtain useful materials data via the Materials Project's REpresentational State Transfer (REST) Application Programming Interface (API). As an example, using pymatgen's interface to the Materials Project's RESTful API and phase diagram package, we demonstrate how the phase and electrochem. stability of a recently synthesized material, Li4SnS4, can be analyzed using a min. of computing resources. We find that Li4SnS4 is a stable phase in the Li-Sn-S phase diagram (consistent with the fact that it can be synthesized), but the narrow range of lithium chem. potentials for which it is predicted to be stable would suggest that it is not intrinsically stable against typical electrodes used in lithium-ion batteries.
    51. 51
      Clark, S. J.; Segall, M. D.; Pickard, C. J.; Hasnip, P. J.; Probert, M. I. J.; Refson, K.; Payne, M. C. First Principles Methods Using CASTEP. Z. Kristallogr. - Cryst. Mater. 2005, 220, 567– 570,  DOI: 10.1524/zkri.220.5.567.65075
      51
      First principles methods using CASTEP
      Clark, Stewart J.; Segall, Matthew D.; Pickard, Chris J.; Hasnip, Phil J.; Probert, Matt I. J.; Refson, Keith; Payne, Mike C.
      Zeitschrift fuer Kristallographie (2005), 220 (5-6), 567-570CODEN: ZEKRDZ; ISSN:0044-2968. (Oldenbourg Wissenschaftsverlag GmbH)
      The CASTEP code for first principles electronic structure calcns. is described. A brief, non-tech. overview is given and some of the features and capabilities highlighted. Some features which are unique to CASTEP are described and near-future development plans outlined.
    52. 52
      Pickard, C. J.; Mauri, F. All-Electron Magnetic Response with Pseudopotentials: NMR Chemical Shifts. Phys. Rev. B 2001, 63, 245101,  DOI: 10.1103/PhysRevB.63.245101
      52
      All-electron magnetic response with pseudopotentials: NMR chemical shifts
      Pickard, Chris J.; Mauri, Francesco
      Physical Review B: Condensed Matter and Materials Physics (2001), 63 (24), 245101/1-245101/13CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
      A theory for the ab initio calcn. of all-electron NMR chem. shifts in insulators using pseudopotentials is presented. It is formulated for both finite and infinitely periodic systems and is based on an extension to the projector augmented-wave approach of Blochl [P. E. Blochl, Phys. Rev. B 50, 17953 (1994)] and the method of Mauri et al. [F. Mauri, B. G. Pfrommer, and S. G. Louie, Phys. Rev. Lett. 77, 5300 (1996)]. The theory is successfully validated for mols. by comparison with a selection of quantum chem. results, and in periodic systems by comparison with plane-wave all-electron results for diamond.
    53. 53
      Yates, J. R.; Pickard, C. J.; Mauri, F. Calculation of NMR Chemical Shifts for Extended Systems Using Ultrasoft Pseudopotentials. Phys. Rev. B 2007, 76, 024401  DOI: 10.1103/PhysRevB.76.024401
      53
      Calculation of NMR chemical shifts for extended systems using ultrasoft pseudopotentials
      Yates, Jonathan R.; Pickard, Chris J.; Mauri, Francesco
      Physical Review B: Condensed Matter and Materials Physics (2007), 76 (2), 024401/1-024401/11CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)
      The authors present a scheme for the calcn. of magnetic response parameters in insulators using ultrasoft pseudopotentials. It uses the gauge-including projector augmented wave method [C. J. Pickard and F. Mauri, Phys. Rev. B 63, 245101(2001)] to obtain all-electron accuracy for both finite and infinitely periodic systems. In detail the calcn. of NMR chem. shieldings are considered. The approach is successfully validated 1st for mol. systems by comparing calcd. chem. shieldings for a range of mols. with quantum chem. results and then in the solid state by comparing 17O NMR parameters calcd. for silicates with expt.
    54. 54
      Finger, L. W.; Cox, D. E.; Jephcoat, A. P. A Correction for Powder Diffraction Peak Asymmetry Due to Axial Divergence. J. Appl. Crystallogr. 1994, 27, 892– 900,  DOI: 10.1107/S0021889894004218
      54
      A correction for powder diffraction peak asymmetry due to axial divergence
      Finger, L. W.; Cox, D. E.; Jephcoat, A. P.
      Journal of Applied Crystallography (1994), 27 (6), 892-900CODEN: JACGAR; ISSN:0021-8898. (Munksgaard)
      Anal. of a crystal structure using the Rietveld profile technique requires a suitable description of the shape of the peaks. In general, modern refinement codes include accurate formulations for most effects; however, the functions used for peak asymmetry are semi-empirical and take very little account of diffraction optics. The deficiencies in these methods are most obvious for high-resoln. instruments. This study describes the implementation of powder diffraction peak profile for mutations devised by van Laar and Yelon [J. Appl. Cryst. (1984) 17, 47-54]. This formalism, which describes the asymmetry due to axial divergence in terms of finite sample and detector sizes,does not require any free parameters and contains intrinsic corrections for the angular dependence of the peak shape. The method results in an accurate description of the obsd. profiles for a variety of geometries, including conventional x-ray diffractometers, synchrotron instruments with or without crystal analyzers and neutron diffractometers.
    55. 55
      Kara, M.; Kurki-Suonio, K. Symmetrized Multipole Analysis of Orientational Distributions. Acta Crystallogr., Sect. A: Cryst. Phys., Diffr., Theor. Gen. Crystallogr. 1981, 37, 201– 210,  DOI: 10.1107/S0567739481000491
      There is no corresponding record for this reference.
    56. 56
      Warren, B. E. X-Ray Diffraction; New edition edition.; Dover Publications Inc.: New York, 2003.
      There is no corresponding record for this reference.
    57. 57
      Medek, A.; Harwood, J. S.; Frydman, L. Multiple-Quantum Magic-Angle Spinning NMR: A New Method for the Study of Quadrupolar Nuclei in Solids. J. Am. Chem. Soc. 1995, 117, 12779– 12787,  DOI: 10.1021/ja00156a015
      57
      Multiple-Quantum Magic-Angle Spinning NMR: A New Method for the Study of Quadrupolar Nuclei in Solids
      Medek, Ales; Harwood, John S.; Frydman, Lucio
      Journal of the American Chemical Society (1995), 117 (51), 12779-87CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Whereas solid state isotropic spectra can be obtained from spin-1/2 by fast magic-angle spinning (MAS), this methodol. fails when applied on half-integer quadrupoles due to the presence of non-negligible second-order anisotropic effects. Very recently, however, we have shown that the combined use of MAS and bidimensional multiple-quantum (MQ) spectroscopy can refocus these anisotropies; the present paper discusses theor. and exptl. aspects of this novel MQMAS methodol. and illustrates its application on a series of sodium salts. It is shown that even under fixed magnetic field operation, a simple model-free inspection of the peaks in a bidimensional MQMAS NMR spectrum can sep. the contributions of isotropic chem. and isotropic quadrupolar shifts for different chem. sites. Moreover the anisotropic line shapes that can be resolved from these spectra are almost unaffected by excitation distortions and can thus be used to discern the values of a site's quadrupolar coupling const. and asymmetry parameter. The conditions that maximize the MQMAS signal-to-noise ratio for a spin-3/2 are then explored with the aid of a simple anal. model, which can also be used to explain the absence of distortions in the anisotropic line shapes. The MQMAS method thus optimized was applied to the high-resoln. 23Na NMR anal. of the multi-site ionic compds. Na2TeO3, Na2SO3, Na3P5O10, and Na2HPO4; extensions of the MQMAS NMR methodol. to the quant. anal. of inequivalent sites are also discussed and demonstrated.
    58. 58
      Amoureux, J.-P.; Fernandez, C.; Steuernagel, S. ZFiltering in MQMAS NMR. J. Magn. Reson., Ser. A 1996, 123, 116– 118,  DOI: 10.1006/jmra.1996.0221
      58
      Z filtering in MQMAS NMR
      Amoureux, Jean-Paul; Fernandez, Christian; Steuernageel, Stefan
      Journal of Magnetic Resonance, Series A (1996), 123 (1), 116-118CODEN: JMRAE2; ISSN:1064-1858. (Academic)
      A Z-filtering method is applied to MQMAS NMR which greatly improves the efficiency of the method. This approach was used to analyze the 27Al 3QMAS NMR spectrum of AlPO-14.
    59. 59
      Johnson, D. ZView: A Software Program for IES Analysis 3.5d. http://www.scribner.com/ (January 15th, 2019), Scribner Associates Inc.
      There is no corresponding record for this reference.
    60. 60
      Flahaut, J.; Kamsukom, J.; Ourmitchi, M.; Domange, L.; Guittard, M. Sur Une Nouvelle Série de Cinq Spinelles Soufrés, de Formule Générale AB5S8. Bull. Société Chim. Fr. 1961, 12, 2382– 2387
      There is no corresponding record for this reference.
    61. 61
      Jain, A.; Ong, S. P.; Hautier, G.; Chen, W.; Richards, W. D.; Dacek, S.; Cholia, S.; Gunter, D.; Skinner, D.; Ceder, G. Commentary: The Materials Project: A Materials Genome Approach to Accelerating Materials Innovation. APL Mater. 2013, 1, 011002
      61
      Commentary: The Materials Project: A materials genome approach to accelerating materials innovation
      Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy; Chen, Wei; Richards, William Davidson; Dacek, Stephen; Cholia, Shreyas; Gunter, Dan; Skinner, David; Ceder, Gerbrand; Persson, Kristin A.
      APL Materials (2013), 1 (1), 011002/1-011002/11CODEN: AMPADS; ISSN:2166-532X. (American Institute of Physics)
      Accelerating the discovery of advanced materials is essential for human welfare and sustainable, clean energy. In this paper, we introduce the Materials Project (www.materialsproject.org), a core program of the Materials Genome Initiative that uses high-throughput computing to uncover the properties of all known inorg. materials. This open dataset can be accessed through multiple channels for both interactive exploration and data mining. The Materials Project also seeks to create open-source platforms for developing robust, sophisticated materials analyses. Future efforts will enable users to perform rapid-prototyping'' of new materials in silico, and provide researchers with new avenues for cost-effective, data-driven materials design. (c) 2013 American Institute of Physics.
    62. 62
      Jaulmes, S.; Julien-Pouzol, M.; Dugué, J.; Laruelle, P.; Guittard, M. Structure d’un oxysulfure de gallium et de thallium. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 1986, 42, 1111– 1113,  DOI: 10.1107/S0108270186093228
      There is no corresponding record for this reference.
    63. 63
      Hellstrom, E. E.; Huggins, R. A. A Study of the Systems M2S·Al2S3, M = Li, Na, K; Preparation, Phase Study and Electric Conductivity. Mater. Res. Bull. 1979, 14, 881– 889,  DOI: 10.1016/0025-5408(79)90153-3
      63
      A study of the systems metal sulfide-aluminum sulfide, M = lithium, sodium, potassium; preparation, phase study and electrical conductivity
      Hellstrom, E. E.; Huggins, R. A.
      Materials Research Bulletin (1979), 14 (7), 881-9CODEN: MRBUAC; ISSN:0025-5408.
      A study of the systems M2S-Al2S3 (M = Li, Na, K) was undertaken to det. the phases present in these systems. New phases identified were LiAlS2, NaAlS2, Na2S.(10±1)Al2S3, KAlS2, and K2S.(10±1)Al2S3, none of which were analogous to the beta-alumina structure. Elec. cond. measurements were made on the K phases, and KAlS2 is an electronic conductor, while K2S.(10±1)Al2S3 is an ionic conductor (2 × 10-5 (S/m) at 573 K).
    64. 64
      Murayama, M. Synthesis of New Lithium Ionic Conductor Thio-LISICON—Lithium Silicon Sulfides System. J. Solid State Chem. 2002, 168, 140– 148,  DOI: 10.1006/jssc.2002.9701
      64
      Synthesis of New Lithium Ionic Conductor Thio-LISICON - Lithium Silicon Sulfides System
      Murayama, Masahiro; Kanno, Ryoji; Irie, Michihiko; Ito, Shinya; Hata, Takayuki; Sonoyama, Noriyuki; Kawamoto, Yoji
      Journal of Solid State Chemistry (2002), 168 (1), 140-148CODEN: JSSCBI; ISSN:0022-4596. (Elsevier Science)
      New Li-ion conductors, thio-LISICON (lithium superionic conductor), can be based on the ternary systems Li2S-SiS2-Al2S3 and Li2S-SiS2-P2S5. The structures of the new materials, Li4+xSi1-xAlxS4 and Li4-xSi1-xPxS4 were detd. by x-ray Rietveld anal. Their elec. and electrochem. properties were studied by electronic cond., a.c. cond., and cyclic voltammetry. The structure of the host material, Li4SiS4, is related to the γ-Li3PO4-type structure, and when Li+ interstitials or Li+ vacancies are created by partial substitution of Al3+ or P5+ for Si4+, the cond. increases significantly. The solid soln. member Li3.4Si0.4P0.6S4 had an ionic cond. of 6.4 × 10-4 S/cm at 27° and negligible electronic cond. The solid solns., Li4-xSi1-xPxS4, also had high electrochem. stability up to ∼5 V vs. Li at room temp. All-solid-state Li batteries were studied using the Li3.4Si0.4P0.6S4 electrolyte, a LiCoO2 cathode and an In anode.
    65. 65
      Lim, H.; Kim, S.-C.; Kim, J.; Kim, Y.-I.; Kim, S.-J. Structure of Li5AlS4 and Comparison with Other Lithium-Containing Metal Sulfides. J. Solid State Chem. 2018, 257, 19– 25,  DOI: 10.1016/j.jssc.2017.09.018
      65
      Structure of Li5AlS4 and comparison with other lithium-containing metal sulfides
      Lim, Hanjin; Kim, Sung-Chul; Kim, Jaegyeom; Kim, Young-Il; Kim, Seung-Joo
      Journal of Solid State Chemistry (2018), 257 (), 19-25CODEN: JSSCBI; ISSN:0022-4596. (Elsevier B.V.)
      Lithium aluminum sulfide (Li5AlS4) was synthesized by solid state reaction, and its crystal structure was characterized by ab initio structure detn. on the basis of powder neutron diffraction (ND) data. Li5AlS4 was found to have monoclinic unit cell (space group, P21/m) with the lattice parameters: a = 6.8583(4) Å, b = 7.8369(4) Å, c = 6.2488(4) Å, and β = 90.333(4)°. This structure is built from a hcp. (hcp) arrangement of sulfur atoms with a stacking sequence of ...ABAB. The hcp sulfide lattice consists of two different double-sulfide layers alternately stacked along the c-axis. Between the first pair of sulfur layers all the tetrahedral interstices (T+ and T- sites) are filled with lithium and aluminum atoms. All octahedral interstices between the second pair of sulfur layers are occupied by the remaining lithium atoms. The structure of Li5AlS4 is compared with those of various lithium-contg. metal sulfides like Li2FeS2, NaLiMS2 (M = Zn, Cd), Li4GeS4, LiM'S2 (M' = Al, Ga, In) and γ-Li3PS4. Each sulfide represents a specific distribution of lithium atoms in the lattice depending on how the octahedral and tetrahedral interstitial sites are filled. The low ionic cond. of Li5AlS4 (9.7 × 10-9 S cm-1 at 323 K) relative to other sulfides may be due to the highly-ordered distribution of the lithium atoms in the layered structure and the lack of adjacent void spaces that can be used for lithium ion hopping.
    66. 66
      Yu, X.; Boyer, M. J.; Hwang, G. S.; Manthiram, A. Room-Temperature Aluminum-Sulfur Batteries with a Lithium-Ion-Mediated Ionic Liquid Electrolyte. Chem 2018, 4, 586– 598,  DOI: 10.1016/j.chempr.2017.12.029
      66
      Room-Temperature Aluminum-Sulfur Batteries with a Lithium-Ion-Mediated Ionic Liquid Electrolyte
      Yu, Xingwen; Boyer, Mathew J.; Hwang, Gyeong S.; Manthiram, Arumugam
      Chem (2018), 4 (3), 586-598CODEN: CHEMVE; ISSN:2451-9294. (Cell Press)
      Aluminum-sulfur (Al-S) chem. is attractive for the development of future-generation electrochem. energy storage technologies. However, to date, only limited reversible Al-S chem. has been demonstrated. This paper demonstrates a highly reversible room-temp. Al-S battery with a lithium-ion (Li+-ion)-mediated ionic liq. electrolyte. Mechanistic studies with electrochem. and spectroscopic methodologies revealed that the enhancement in reversibility by Li+-ion mediation is attributed to the chem. reactivation of aluminum polysulfides and/or sulfide by Li+ during electrochem. cycling. The results obtained with XPS and d. functional theory calcns. suggest the presence of a Li3AlS3-like product with a mixt. of Li2S- and Al2S3-like phases in the discharged sulfur cathode. With Li+-ion mediation, the cycle life of room-temp. Al-S batteries is greatly improved. The cell delivers an initial capacity of ∼1,000 mA hr g-1 and maintains a capacity of up to 600 mA hr g-1 after 50 cycles.
    67. 67
      Toby, B. H.; Von Dreele, R. B. GSAS-II: The Genesis of a Modern Open-Source All Purpose Crystallography Software Package. J. Appl. Crystallogr. 2013, 46, 544– 549,  DOI: 10.1107/S0021889813003531
      67
      GSAS-II: the genesis of a modern open-source all purpose crystallography software package
      Toby, Brian H.; Von Dreele, Robert B.
      Journal of Applied Crystallography (2013), 46 (2), 544-549CODEN: JACGAR; ISSN:0021-8898. (International Union of Crystallography)
      The newly developed GSAS-II software is a general purpose package for data redn., structure soln. and structure refinement that can be used with both single-crystal and powder diffraction data from both neutron and x-ray sources, including lab. and synchrotron sources, collected on both two- and 1-dimensional detectors. It is intended that GSAS-II will eventually replace both the GSAS and the EXPGUI packages, as well as many other utilities. GSAS-II is open source and is written largely in object-oriented Python but offers speeds comparable to compiled code because of its reliance on the Python NumPy and SciPy packages for computation. It runs on all common computer platforms and offers highly integrated graphics, both for a user interface and for interpretation of parameters. The package can be applied to all stages of crystallog. anal. for const.-wavelength x-ray and neutron data. Plans for considerable addnl. development are discussed.
    68. 68
      Petříček, V.; Dušek, M.; Palatinus, L. Crystallographic Computing System JANA2006: General Features. Z. Kristallogr. - Cryst. Mater. 2014, 229, 345– 352,  DOI: 10.1515/zkri-2014-1737
      68
      Crystallographic Computing System JANA2006: General features
      Petricek, Vaclav; Dusek, Michal; Palatinus, Lukas
      Zeitschrift fuer Kristallographie - Crystalline Materials (2014), 229 (5), 345-352CODEN: ZKCMAJ; ISSN:2194-4946. (Oldenbourg Wissenschaftsverlag GmbH)
      JANA2006 is a freely available program for structure detn. of std., modulated and magnetic samples based on X-ray or neutron single crystal/ powder diffraction or on electron diffraction. The system has been developed for 30 years from specialized tool for refinement of modulated structures to a universal program covering std. as well as advanced crystallog. The aim of this article is to describe the basic features of JANA2006 and explain its scope and philosophy. It will also serve as a basis for future publications detailing tools and methods of JANA.
    69. 69
      Palatinus, L.; Chapuis, G. SUPERFLIP – a Computer Program for the Solution of Crystal Structures by Charge Flipping in Arbitrary Dimensions. J. Appl. Crystallogr. 2007, 40, 786– 790,  DOI: 10.1107/S0021889807029238
      69
      SUPERFLIP. A computer program for the solution of crystal structures by charge flipping in arbitrary dimensions
      Palatinus, Lukas; Chapuis, Gervais
      Journal of Applied Crystallography (2007), 40 (4), 786-790CODEN: JACGAR; ISSN:0021-8898. (International Union of Crystallography)
      SUPERFLIP is a computer program that can solve crystal structures from diffraction data using the recently developed charge-flipping algorithm. It can solve periodic structures, incommensurately modulated structures and quasicrystals from x-ray and neutron diffraction data. Structure soln. from powder diffraction data is supported by combining the charge-flipping algorithm with a histogram-matching procedure. SUPERFLIP is written in Fortran90 and is distributed as a source code and as precompiled binaries. It was successfully compiled and tested on a variety of operating systems.
    70. 70
      FullProf Suite - Crystallographic Tool for Rietveld, Profile Matching & Integrated Intensity Refinements of X-Ray and/or Neutron Data. https://www.ill.eu/sites/fullprof/ (October 19th, 2019)
      There is no corresponding record for this reference.
    71. 71
      Xu, Z.; Stebbins, J. F. 6Li Nuclear Magnetic Resonance Chemical Shifts, Coordination Number and Relaxation in Crystalline and Glassy Silicates. Solid State Nucl. Magn. Reson. 1995, 5, 103– 112,  DOI: 10.1016/0926-2040(95)00026-M
      71
      6Li nuclear magnetic resonance chemical shifts, coordination number, and relaxation in crystalline and glassy silicates
      Xu, Z.; Stebbins, Jonathan F.
      Solid State Nuclear Magnetic Resonance (1995), 5 (1), 103-12CODEN: SSNRE4; ISSN:0926-2040. (Elsevier)
      Unlike 7Li magic-angle spinning NMR (MAS NMR) spectra, 6Li MAS NMR spectra of silicates are dominated by chem. shift effects, often have a very high resoln., and hence can provide significant structural information. In this study, the authors demonstrate a good correlation between 6Li isotropic chem. shifts and oxygen coordination no., and use this result to describe the range of coordination environments for Li in silicate glasses. They also show that the second-order quadrupolar shift for 7Li can often be derived from 7Li and 6Li MAS spectra acquired at a single magnetic field. For a series of natural lepidolite samples with significant but varying contents of Mn and Fe, spin-lattice relaxation data show a power-law behavior and a three-dimensional distribution of paramagnetic centers, but homonuclear dipolar couplings can be important. The 6Li spectrum for lithium orthosilicate (which has three-, four-, five-, and six-coordinated Li) is consistent with that predicted by the X-ray structure.
    72. 72
      Eisenmann, B.; Hofmann, A. Crystal Structure of Hexasodium Di-μ-Thio-Bis(Dithioindate), Na6In2S6. Z. Kristallogr. - Cryst. Mater. 1991, 197, 151– 152,  DOI: 10.1524/zkri.1991.197.1-2.151
      72
      Crystal structure of hexasodium di-μ-thio-bis(dithioindate), Na6In2S6
      Eisenmann, B.; Hofmann, A.
      Zeitschrift fuer Kristallographie (1991), 197 (1-2), 151-2CODEN: ZEKRDZ; ISSN:0044-2968.
      The title compd. is monoclinic, space group C2/c, with a 15.945(6), b 13.456(6), c 7.358(4) Å, and β 117.41(6)°; Z = 4; R = 0.044. At. coordinates are given. The anionic partial structure is characterized by dimers In2S66- of 2 edge-sharing InS4 tetrahedra.
    73. 73
      Klepp, K.; Böttcher, P.; Bronger, W. Preparation and Crystal Structure of Na2Mn2S3. J. Solid State Chem. 1983, 47, 301– 306,  DOI: 10.1016/0022-4596(83)90022-1
      73
      Preparation and crystal structure of sodium thiomanganate (Na2Mn2S3)
      Klepp, K.; Boettcher, P.; Bronger, W.
      Journal of Solid State Chemistry (1983), 47 (3), 301-6CODEN: JSSCBI; ISSN:0022-4596.
      Na2Mn2S3 was prepd. by reacting Mn powder with an excess of anhyd. Na2CO3 and elemental S at 870 K. Extn. of the solidified melt with water and alc. yielded well-developed, bright red crystals. Na2Mn2S3 crystallizes with a new monoclinic structure type, space group C2/c, Z = 8, with a 14.942(2), b = 13.276(2), c 6.851(2) Å, and β 116.50(1)°. The crystal structure was detd. from single crystal diffractometer data and refined to a conventional R value of 0.026 for 1613 obsd. reflections. The at. arrangement shows S-Mn-S slabs which are sepd. from each other by corrugated layers of Na atoms. A prominent feature of the crystal structure is the formation of short, 4-membered zigzag chains built up by MnS4 tetrahedra sharing edges. These chains are further connected by the remaining apexes to form an infinite sheet. Short Mn-Mn distances (3.02 and 3.05 Å, resp.) are found within the 4-membered chains. Susceptibility measurements show antiferromagnetic interactions between the Mn atoms.
    74. 74
      Kim, J.; Hughbanks, T. Synthesis and Structures of New Layered Ternary Manganese Selenides: AMnSe2 (A=Li, Na, K, Rb, Cs) and Na2Mn2Se3. J. Solid State Chem. 1999, 146, 217– 225,  DOI: 10.1006/jssc.1999.8339
      74
      Synthesis and Structures of New Layered Ternary Manganese Selenides: AMnSe2 (A = Li, Na, K, Rb, Cs) and Na2Mn2Se3
      Kim, Joonyeong; Hughbanks, Timothy
      Journal of Solid State Chemistry (1999), 146 (1), 217-225CODEN: JSSCBI; ISSN:0022-4596. (Academic Press)
      The synthesis and crystal structures of new ternary Mn selenides, AMnSe2 (A = Li, Na, K, Rb, Cs) and Na2Mn2Se3, are reported. These compds. were synthesized by solid state reaction and cation exchange techniques. Crystal data are: LiMnSe2: a 4.1905(3), c 6.619(2) Å, and space group P3m1, (No. 156, Z = 1); NaMnSe2: a 4.2330(7), c 6.942(3) Å, and space group P3m1, (No. 156, Z = 1); RbMnSe2: a 4.2660(4), c 14.033(2) Å, and I4m2 (No. 119, Z = 2); Na2Mn2Se3: a 15.689(2), b 13.888(2), c 7.220(1) Å, β 115.65(2)°, and C2/c (No. 15, Z = 8). The fundamental building blocks of the title compds. are MnSe4 tetrahedra. AMnSe2 (A = Li, Na) are layered compds. in which MnSe4 tetrahedra share three corners in the formation of polar 2∞[MnSe3/3Se]- layers. AMnSe2 (A = K, Rb, Cs) exhibit 2∞[MnSe4/2]- layers which are built up by four-corner-shared MnSe4 tetrahedra. Na2Mn2Se3 shows four-membered zigzag chains formed by edge-shared MnSe4 tetrahedra. These chains are fused by the remaining apexes to form a two-dimensional layer, 2∞[MnSe2/3Se1/3Se1/2]-. Magnetic susceptibility data for these compds. were fit with a modified Curie-Weiss expression. (c) 1999 Academic Press.
    75. 75
      Luthy, J. A.; Goodman, P. L.; Martin, B. R. Synthesis of Li(x)Na(2–x)Mn2S3 and LiNaMnS2 through Redox-Induced Ion Exchange Reactions. J. Solid State Chem. 2009, 182, 580– 585,  DOI: 10.1016/j.jssc.2008.11.025
      75
      Synthesis of Li(x)Na(2-x)Mn2S3 and LiNaMnS2 through redox-induced ion exchange reactions
      Luthy, Joshua A.; Goodman, Phillip L.; Martin, Benjamin R.
      Journal of Solid State Chemistry (2009), 182 (3), 580-585CODEN: JSSCBI; ISSN:0022-4596. (Elsevier B.V.)
      Na2Mn2S3 was oxidatively deintercalated using I in MeCN to yield Na1.3Mn2S3, with lattice consts. nearly identical to that of the reactant. Li was then reductively intercalated into the oxidized product to yield Li0.7Na1.3Mn2S3. When heated, this metastable compd. decompd. to form a new cryst. compd., LiNaMnS2, along with MnS and residual Na2Mn2S3. Single crystal x-ray diffraction structural anal. of LiNaMnS2 revealed that this compd. crystallizes in P‾3m1 with a 4.0479(6), c 6.7759(14) Å, V = 96.15(3) Å3 (Z = 1, wR2 = 0.0367) in the NaLiCdS2 structure-type.
    76. 76
      Eisenmann, B.; Hofmann, A. Crystal Structure of Hexasodium Di-μ-Thio-Bis(Dithioaluminate) – HT, Na6Al2S6. Z. Kristallogr. - Cryst. Mater. 1991, 197, 161– 162,  DOI: 10.1524/zkri.1991.197.1-2.161
      76
      Crystal structure of hexasodium di-μ-thio-bis(dithioaluminate) - HT, Na6Al2S6
      Eisenmann, B.; Hofmann, A.
      Zeitschrift fuer Kristallographie (1991), 197 (1-2), 161-2CODEN: ZEKRDZ; ISSN:0044-2968.
      The title compd. is monoclinic, space group P21/c, with a 13.706(5), b 12.071(5), c 7.608(3) Å, and β 98.60(6)°; Z = 4; R = 0.078. At. coordinates are given. This high temp. (H.T.) modification, stable above 775 K, is characterized by dimeric anions Al2S66- of 2 edge-sharing AlS4 tetrahedra.
    77. 77
      Müller, P.; Bronger, W. Na3FeS3, Ein Thioferrat Mit Isolierten [Fe2S6]− Anionen /Na3FeS3, a Thioferrate with Isolated [Fe2S6]− Anions. Z. Naturforsch., B: J. Chem. Sci. 2014, 34, 1264– 1266,  DOI: 10.1515/znb-1979-0920
      There is no corresponding record for this reference.
    78. 78
      Blandeau, L.; Ouvrard, G.; Calage, Y.; Brec, R.; Rouxel, J. Transition-Metal Dichalcogenides from Disintercalation Processes. Crystal Structure Determination and Mossbauer Study of Li2FeS2 and Its Disintercalates LixFeS2(0.2≤x≤ 2). J. Phys. C Solid State Phys. 1987, 20, 4271– 4281,  DOI: 10.1088/0022-3719/20/27/007
      78
      Transition-metal dichalcogenides from disintercalation processes: crystal structure determination and Moessbauer study of lithium iron sulfide (Li2FeS2) and its disintercalates LixFeS2 (0.2 ≤ x ≤ 2)
      Blandeau, L.; Ouvrard, G.; Calage, Y.; Brec, R.; Rouxel, J.
      Journal of Physics C: Solid State Physics (1987), 20 (27), 4271-81CODEN: JPSOAW; ISSN:0022-3719.
      In agreement with its hexagonal subcell parameters (a 3.908(2) and c 6.279(4) Å) and c/a ratio of 1.601, the Li2FeS2 structure is constructed from a hexagonal close packing of S2- anions with tetrahedral Fe ions. Different filling of the 2 (FeS4) sites is responsible for the 2a × 2b × c supercell. Li ions are scattered on tetrahedral and octahedral sites, some of the latter remaining empty because of intercationic Coulombic repulsions. Moessbauer study of LixFeS2 disintercalates (0.2 ≤ x ≤2) shows the occurrence of oxidn. of Fe(II) into Fe(III) and a sudden change from tetrahedral to octahedral coordination in accord with the break in the equil. discharge curve at Li1.5FeS2 of a LixFeS2/Li electrochem. cell. The occurrence of a new FeS2(Fe3+S2-(S2)1/22-), as characterized by previous IR analyses, is confirmed by its Moessbauer characteristics showing 2 distinct Fe(III) sites different from that of FeS2 of the pyrite or marcassite type. The oxidoredn. process of the disintercalations and intercalations involving Fe and S as redox centers is better understood as well as their actions on the cationic structural alterations.
    79. 79
      Alahmari, F.; Davaasuren, B.; Emwas, A.-H.; Rothenberger, A. Thioaluminogermanate M(AlS2)(GeS2)4 (M = Na, Ag, Cu): Synthesis, Crystal Structures, Characterization, Ion Exchange and Solid-State 27Al and 23Na NMR Spectroscopy. Inorg. Chem. 2017, 57, 3713– 3719,  DOI: 10.1021/acs.inorgchem.7b02980
      There is no corresponding record for this reference.
    80. 80
      Eisenmann, B.; Hofmann, A. Crystal Structure of Hexasodium Di-μ-Thio-Bis(Dithiogallate) – I, Na6Ga2S6. Z. Kristallogr. - Cryst. Mater. 1991, 197, 143– 144,  DOI: 10.1524/zkri.1991.197.1-2.143
      80
      Crystal structure of hexasodium di-μ-thio-bis(dithiogallate) Na6Ga2S6-I
      Eisenmann, B.; Hofmann, A.
      Zeitschrift fuer Kristallographie (1991), 197 (1-2), 143-4CODEN: ZEKRDZ; ISSN:0044-2968.
      The title compd. is monoclinic, space group P21/n, with a 7.207(4), b 6.931(4), c 12.740(5) Å, and β 90.67(6)°; Z = 2; R = 0.093. At. coordinates are given. Na6Ga2S6 crystallizes in the Na6Fe2S6 type. The anionic partial structure is characterized by units of 2 edge-sharing GaS4 tetrahedra.
    81. 81
      Shannon, R. D. Revised Effective Ionic Radii and Systematic Studies of Interatomic Distances in Halides and Chalcogenides. Acta Crystallogr., Sect. A: Cryst. Phys., Diffr., Theor. Gen. Crystallogr. 1976, 32, 751– 767,  DOI: 10.1107/S0567739476001551
      There is no corresponding record for this reference.
    82. 82
      Müller, P.; Bronger, W. Darstellung Und Kristallstruktur von Na3FeSe3 / Preparation and Crystal Structure of Na3FeSe3. Z. Naturforsch., B: J. Chem. Sci. 1981, 36, 646– 648,  DOI: 10.1515/znb-1981-0518
      There is no corresponding record for this reference.
    83. 83
      Eisenmann, B.; Hofmann, A. Crystal Structure of Hexasodium Di-μ-Selenido-Bis(Diselenidoaluminate), Na6Al2Se6. Z. Kristallogr. - Cryst. Mater. 1991, 197, 141– 142,  DOI: 10.1524/zkri.1991.197.1-2.141
      83
      Crystal structure of hexasodium di-μ-selenido-bis(diselenidoaluminate), Na6Al2Se6
      Eisenmann, B.; Hofmann, A.
      Zeitschrift fuer Kristallographie (1991), 197 (1-2), 141-2CODEN: ZEKRDZ; ISSN:0044-2968.
      The title compd. is monoclinic, space group P21/n, with a 7.499(4), b 7.203(4), c 13.196(5) Å, and β 90.37(6)°; Z = 2; R = 0.076. At. coordinates are given. Na6Al2Se6 crystallizes in the Na6Fe2S6 type. The anionic partial structure is characterized by units of 2 edge-sharing AlSe4 tetrahedra.
    84. 84
      Eisenmann, B.; Hofmann, A. Crystal Structure of Hexasodium Di-μ-Selenido Bis(Diselenidogallate), Na6Ga2Se6. Z. Kristallogr. - Cryst. Mater. 1991, 197, 149– 150,  DOI: 10.1524/zkri.1991.197.1-2.149
      84
      Crystal structure of hexasodium di-μ-selenido-bis(diselenidogallate), Na6Ga2Se6
      Eisenmann, B.; Hofmann, A.
      Zeitschrift fuer Kristallographie (1991), 197 (1-2), 149-50CODEN: ZEKRDZ; ISSN:0044-2968.
      The title compd. is monoclinic, space group P21/n, with a 7.506(4), b 7.239(4), c 13.208(5) Å, and β 90.59(6)°; Z = 2; R = 0.089. At. coordinates are given. The anionic partial structure is characterized by units of 2 edge-sharing GaSe4 tetrahedra.
    85. 85
      Singh, D. N. Basic Concepts of Inorganic Chemistry; 2nd edition.; Pearson India: New Delhi, 2012.
      There is no corresponding record for this reference.
    86. 86
      Welz, D.; Bennington, S. M.; Müller, P. Inverted Biquadratic Exchange of Heisenberg Antiferromagnetic Dimers in Na3FeS3. Phys. B 1995, 213-214, 339– 341,  DOI: 10.1016/0921-4526(95)00149-4
      86
      Inverted biquadratic exchange of Heisenberg antiferromagnetic dimers in Na3FeS3
      Welz, D.; Bennington, S. M.; Mueller, P.
      Physica B: Condensed Matter (Amsterdam) (1995), 213&214 (1-4), 339-41CODEN: PHYBE3; ISSN:0921-4526. (Elsevier)
      Excitation energies of Fe3+ antiferromagnetic dimers in Na3FeS3 were measured at room temp., 250°, and 500° by time-of-flight neutron scattering to a precision of 0.1 to 0.3%. Thermal fluctuations decrease the exchange interaction and cause line broadening. Deviations from a Heisenberg level spacing reveal a biquadratic exchange term that cannot be attributed to magneto-elastic coupling.
    87. 87
      Kusainova, A. M.; Berdonosov, P. S.; Akselrud, L. G.; Kholodkovskaya, L. N.; Dolgikh, V. A.; Popovkin, B. A. New Layered Compounds with the General Composition (MO)(CuSe) , Where M=Ci,Nd,Gd,Dy, and BiCuOS: Synthesis and Crystal Structure. J. Solid State Chem. 1994, 112, 189– 191,  DOI: 10.1006/jssc.1994.1285
      87
      New layered compounds with the general composition (MO)(CuSe), where M = Bi, Nd, Gd, Dy, and BiOCuS: syntheses and crystal structure
      Kusainova, A. M.; Berdonosov, P. S.; Akselrud, L. G.; Kholodkovskaya, L. N.; Dolgikh, V. A.; Popovkin, B. A.
      Journal of Solid State Chemistry (1994), 112 (1), 189-91CODEN: JSSCBI; ISSN:0022-4596.
      The syntheses of four new copper oxyselenides (MO)(CuSe) (M = Bi, Nd, Gd, Dy) and one copper oxysulfide, BiOCuS, are reported. The tetragonal unit cell dimensions of all compds. are given. A new bismuth-copper oxyselenide, BiOCuSe, was structurally characterized from powder x-ray diffraction data and solved by the Rietveld profile method with final R1 = 0.069. The BiCuSeO crystal structure is formed by alternating [Bi2O2] and [Cu2Se2] layers.
    88. 88
      Kageyama, H.; Hayashi, K.; Maeda, K.; Attfield, J. P.; Hiroi, Z.; Rondinelli, J. M.; Poeppelmeier, K. R. Expanding Frontiers in Materials Chemistry and Physics with Multiple Anions. Nat. Commun. 2018, 9, 772,  DOI: 10.1038/s41467-018-02838-4
      88
      Expanding frontiers in materials chemistry and physics with multiple anions
      Kageyama Hiroshi; Hayashi Katsuro; Maeda Kazuhiko; Attfield J Paul; Hiroi Zenji; Rondinelli James M; Poeppelmeier Kenneth R
      Nature communications (2018), 9 (1), 772 ISSN:.
      During the last century, inorganic oxide compounds laid foundations for materials synthesis, characterization, and technology translation by adding new functions into devices previously dominated by main-group element semiconductor compounds. Today, compounds with multiple anions beyond the single-oxide ion, such as oxyhalides and oxyhydrides, offer a new materials platform from which superior functionality may arise. Here we review the recent progress, status, and future prospects and challenges facing the development and deployment of mixed-anion compounds, focusing mainly on oxide-derived materials. We devote attention to the crucial roles that multiple anions play during synthesis, characterization, and in the physical properties of these materials. We discuss the opportunities enabled by recent advances in synthetic approaches for design of both local and overall structure, state-of-the-art characterization techniques to distinguish unique structural and chemical states, and chemical/physical properties emerging from the synergy of multiple anions for catalysis, energy conversion, and electronic materials.
    89. 89
      Irvine, J. T. S.; Sinclair, D. C.; West, A. R. Electroceramics: Characterization by Impedance Spectroscopy. Adv. Mater. 1990, 2, 132– 138,  DOI: 10.1002/adma.19900020304
      89
      Electroceramics: characterization by impedance spectroscopy
      Irvine, John T. S.; Sinclair, Derek C.; West, Anthony R.
      Advanced Materials (Weinheim, Germany) (1990), 2 (3), 132-8CODEN: ADVMEW; ISSN:0935-9648.
      A review with 13 refs. Various examples are chosen which illustrate the power and usefulness of impedance spectroscopy for characterizing a wide variety of electroceramic materials and phenomena.

  • Supporting Information

    Supporting Information

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.9b03230.

    • Experimental synthesis procedure for the preparation of LiAlO2 and the attempted Li3AlO3, X-ray diffraction patterns of the samples prepared in the Li–Al–O–S phase fields, comparison of the Le Bail fits of the SXRD data with and without the use of the spherical harmonics, details of the elemental analysis of Li3AlS3, structural information of Li3AlS3 determined by diffraction data refinement (refinement details, atomic positions, Fourier difference map of the Li2 and Li3 positions, bond distances and angles), NMR shift calculations, and additional NMR experimental results, analysis of the impedance data (PDF)

    • Crystallographic data (CIF)


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