A new metastable phase, featuring a lithium-stabilized mixed-valence cobalt(II,III) hydroxide phosphate framework, Co11.0(1)Li1.0(2)[(OH)5O][(PO3OH)(PO4)5], corresponding to the simplified composition Co1.84(2)Li0.16(3)(OH)PO4, is prepared by hydrothermal synthesis. Because the pH-dependent formation of other phases such as Co3(OH)2(PO3OH)2 and olivine-type LiCoPO4 competes in the process, a pH value of 5.0 is crucial for obtaining a single-phase material. The crystals with dimensions of 15 μm × 30 μm exhibit a unique elongated triangular pyramid morphology with a lamellar fine structure. Powder X-ray diffraction experiments reveal that the phase is isostructural with the natural phosphate minerals holtedahlite and satterlyite, and crystallizes in the trigonal space group P31m (a = 11.2533(4) Å, c = 4.9940(2) Å, V = 547.70(3) Å3, Z = 1). The three-dimensional network structure is characterized by partially Li-substituted, octahedral [M2O8(OH)] (M = Co, Li) dimer units which form double chains that run along the [001] direction and are connected by [PO4] and [PO3(OH)] tetrahedra. Because no Li-free P31m-type Co2(OH)PO4 phase could be prepared, it can be assumed that the Li ions are crucial for the stabilization of the framework. Co L-edge X-ray absorption spectroscopy demonstrates that the cobalt ions adopt the oxidation states +2 and +3 and hence provides further evidence for the incorporation of Li in the charge-balanced framework. The presence of three independent hydroxyl groups is further confirmed by infrared spectroscopy. Magnetization measurements imply a paramagnetic to antiferromagnetic transition at around T = 25 K as well as a second transition at around 9–12 K with a ferromagnetic component below this temperature. The metastable character of the phase is demonstrated by thermogravimetric analysis and differential scanning calorimetry, which above 558 °C reveal a two-step decomposition to CoO, Co3(PO4)2, and olivine-type LiCoPO4 with release of water and oxygen.

Semiconducting silver tellurides gained reasonable interest in the past years due to its thermoelectric, magneto-caloric, and nonlinear optic properties. Nanostructuring has been frequently used to address quantum-confinement effects of minerals and synthetic compounds in the Ag–Te system. Here, we report on the structural, thermal, and thermoelectric properties of stuetzite-like Ag1.54Te (or Ag4.63Te3) and Ag1.9Te. By a quasi-topotactic reaction upon tellurium evaporation Ag1.54Te can be transferred to Ag1.9Te after heat treatment. Crystal structures, thermal and thermoelectric properties of stuetzite-like Ag1.54Te (or Ag4.63Te3) and Ag1.9Te were determined by ex situ and in situ experiments. This method represents an elegant chemical way to Ag1.9Te, which was so far only accessible electrochemically via electrochemical removal of silver from the mineral hessite (Ag2Te). The mixed conductors show reasonable high total electric conductivities, very low thermal conductivities, and large Seebeck coefficients, which result in a significant high thermoelectric figure of 0.57 at 680 K.

Two-dimensional (2D) nanoflakes have emerged as a class of materials that may impact electronic technologies in the near future. A challenging but rewarding work is to experimentally identify 2D materials and explore their properties. Here, we report the synthesis of a layered material, P20.56(1)Sb0.44(1), with a systematic study on characterizations and device applications. This material demonstrates a direct band gap of around 1.67 eV. Using a laser-cutting method, the thin flakes of this material can be separated into multiple segments. We have also fabricated field effect transistors based on few-layer P20.56(1)Sb0.44(1) flakes with a thickness down to a few nanometers. Interestingly, these field effect transistors show strong photoresponse within the wavelength range of visible light. At room temperature, we have achieved good mobility values (up to 58.96 cm2/V·s), a reasonably high on/off current ratio (∼103), and intrinsic responsivity up to 10 μA/W. Our results demonstrate the potential of P20.56(1)Sb0.44(1) thin flakes as a two-dimensional material for applications in visible light detectors.Keywords: antimony-substituted violet phosphorus; field effect transistor; layered material; mobility; photoresponse;

Poly(ethylene oxide) (PEO)-based polymer fibers, containing different amounts of the conductive salt LiBF4 and the plasticizer succinonitrile, were prepared by an electrospinning process. This process resulted in fiber membranes of several square centimeters area and an overall thickness of ∼100 μm. All membranes are characterized by scanning electron microscopy, differential scanning calorimetry, X-ray diffraction, impedance spectroscopy, cyclic voltammetry (CV), and solid-state NMR spectroscopy, to evaluate the influence of the preparation process and the composition on the conductivity of the materials. Impedance spectroscopy was used to measure the conductivities and activation barriers for the different membranes. The highest conductivity of 2 × 10–4 S/cm at room temperature and 9 × 10–4 S/cm at 328 K is reached for a PEO/SN/LiBF4 (36:8:1) membrane, featuring an activation energy of 31 kJ/mol. Li mobilities, as deduced from the evaluation of the temperature dependence of the 7Li NMR line width and the overall electrochemical performance, are found to be distinctively superior to nonspun samples, synthesized via conventional solution casting. The same trend was found for the conductivities. NMR spectroscopy clearly substantiated that the mobility of the PEO segments drastically increases with the addition of succinonitrile pushing the conductivity to reasonable high values. In CV experiments the reversible Li transport through the dry membrane was evaluated and proved. This study shows that electrospinning provides a direct synthesis of solvent-free solid-state electrolyte membranes, ready to use in electrochemical applications.

While the majority of research activities on LiCoPO4 is focussed on the thermodynamically stable olivine-type Pnma polymorph, the metastable Pna21 and Cmcm modifications have recently attracted considerable attention due to their interesting material properties. In this study, we present the first Li-deficient structural derivative of the Cmcm modification with the nominal composition Li0.5−δCoPO4. As opposed to the substoichiometric olivine (Pnma) phases LixCoPO4 (x = 0; 2/3), which are exclusively accessible by electrochemical or chemical Li extraction techniques, this is also the first time that a direct soft-chemical synthesis route towards a LixCoPO4-type material is accomplished. X-ray and neutron diffraction studies indicate that Cmcm-type Li0.5−δCoPO4 shows vacancies on both the Li and Co sites, whereas X-ray absorption spectra demonstrate that the structure features heterovalent Co ions (+2/+3) to compensate for the Li deficit. Magnetic measurements reveal a long-range antiferromagnetic order below 10.5 K. A thorough investigation of the thermal stability using thermogravimetric analysis, differential scanning calorimetry, and temperature-dependent in situ X-ray powder diffraction demonstrates that Li0.5−δCoPO4 is metastable and exhibits a complex, multi-step thermal decomposition mechanism. In the first step at 394 °C, it decomposes to α-Co2P2O7 (P21/c) and LiCoPO4 (Cmcm) upon O2 release. The LiCoPO4 (Cmcm) intermediate is then irreversibly transformed to olivine-type LiCoPO4 (Pnma) at 686 °C. The material properties of Li0.5−δCoPO4 are further compared to the fully lithiated, isostructural LiCoPO4 (Cmcm) phase, for which an improved structure solution as well as Co L2,3-edge X-ray absorption spectra are reported for the first time.

NaCd4P3 and NaCd4As3 were synthesized via short-way transport using the corresponding elements and CdI2 as mineralizer. At room temperature, the two β-polymorphs adopt the RbCd4As3 structure type which has been recently reported for alkali metal (A)–d10 transition metal (T)–pnictides (Pn). The title compounds crystallize rhombohedrally in space group R3̅m at room temperature and show reversible phase transitions to incommensurately modulated α-polymorphs at lower temperatures. The low-temperature phases are monoclinic and can be described in space group Cm(α0γ)s with q vectors of q = (−0.04,0,0.34) for α-NaCd4P3 and q1 = (−0.02,0,0.34) for α-NaCd4As3. Thermal properties, Raman spectroscopy, and electronic structures have been determined. Both compounds are Zintl phases with band gaps of 1.05 eV for β-NaCd4P3 and ∼0.4 eV for β-NaCd4As3.

Solids with high ion mobility are of broad interest for energy storage applications. New systems featuring low-activated ion mobility are important to improve the performance in such systems. Herein we report on a model system dealing with such improved properties. Li0.2CdP2 was synthesized from the elements, lithium as structure stabilizer and CdI2 as reaction promoters in sealed silica ampoules at 823 K. It crystallizes tetragonal, in space group I4122 (α-CdAs2 structure type), with lattice parameters a = 7.6691(8) Å, c = 4.4467(4) Å and V = 261.53(4) Å3. After 24 h of storage in air lithium ions can be removed in a spontaneous delithiation reaction resulting in Li(OH)·H2O formation on the surface of the crystals. Formed α′-CdP2 adopts the α-CdAs2 structure type. Both compounds consist of isolated cadmium atoms and helical 1∞[P−]-chains generating empty channels suitable to accommodate Li ions. The heavy atom structure was determined by X-ray diffraction methods while a full model including lithium was derived from a combined solid state NMR and quantum chemical calculation approach. An low activation barrier range in the order of 0.1 to 0.2 eV was determined by NMR spectroscopy pointing towards an extraordinary high Li mobility in Li0.2CdP2. Of course a Cd-based solid will have certain disadvantages like toxicity and mass for storage applications but substitution of Cd by suitable lighter elements can solve this issue.

AgP15 was synthesized from the elements via a short-way transport reaction following the mineralizer concept. The needle-shaped crystals were characterized by single-crystal and powder X-ray diffraction. It crystallizes triclinically in space group P1̅ with cell parameters of a = 6.937(1) Å, b = 9.000(1) Å, c = 11.103(2) Å, α = 99.95(1)°, β = 99.61(1)°, and γ = 105.980(9)°. AgP15 exhibits a tubular phosphorus substructure related but neither isotypic nor isostructural to the alkaline phosphides MP15 (M = Li–Rb). The thermal properties, electronic structure, and experimental band gap of this new semiconductor have been determined. Finally, Raman spectra of AgP15 and selected alkaline-metal polyphosphides MP15 have been measured and interpreted. AgP15 represents the first transition-metal representative of this class of materials.

Antimony containing compounds have drawn interest as anode materials in Li batteries due to their high Li packing density and the resulting volumetric charge density. Reasonable specific capacities outperforming graphite by a factor of 2 have been reported for antimonides and polyantimonides. Together with good cycling stabilities, rate capabilities and a high potential level against Li metal, both classes of materials are discussed as potential candidates to substitute carbonaceous hosts. Unfortunately, severe volume expansion during the reaction with lithium takes place which has to be taken into account during optimization of the systems. This feature demands size tailoring and electrode optimization to push the electrochemical performance and the lifetime of half cells and full batteries in applicable dimensions. While antimonides are more or less intermetallic compounds, performing a conversion reaction to electrochemical active (in most cases Sb) and non-active species, polyantimonides can offer a greater flexibility due to their anisotropic structural features. Polyantimonides, containing simple dumbbells up to layered arrangements of covalently bonded antimony, can provide voids or interstitials for insertion and intercalation of lithium. The chance to preserve such favourable structural features during this process is in principle higher than for antimonides where conversion reactions to other species take place.Herein we report on structural features and electrochemical performance of antimony containing active materials for anodes in lithium batteries. Our focus lies on recent developments in polyantimonides chemistry but we will also address the scientific progress with antimonides.

[Cd3Cu]CuP10, a polyphosphide containing adamantine-analogue [P10] unit undergoes a solid-state polymerization to form [P6] rings and tubular [P26] polymer units at elevated temperatures. This reaction represents the rare case of a polyphosphide polymerization in the solid state. The formation of such a polymeric unit starting from a molecular precursor is the first evidence of the general possibility to perform a bottom-up route to the well-known tubular polyphosphide units of elemental phosphorus in a solid material. Temperature-dependent X-ray powder diffraction experiments substantiate the solid phase transformation of [Cd3Cu]CuP10 starting at 550 °C to the polymerized form via an additional intermediate step. A single crystal structure determination of the quenched product at room temperature was performed to evaluate the structural properties and the resulting polyphosphide units. The full polymerization and decomposition mechanism has been analyzed by thermogravimetric experiments and subsequent X-ray powder phase analyses. The present [P26] polymer unit represents a former unseen one-dimensional cut-out of the two-dimensional polyphosphide substructure of Ag3P11 and can be directly related to the tubular polyphosphide substructures of violet or fibrous phosphorus.

The ternary Laves phase Cd4Cu7As is the first intermetallic compound in the system Cu–Cd–As and a representative of a new substitution variant for Laves phases. It crystallizes orthorhombically in the space group Pnnm (No. 58) with lattice parameters a = 9.8833(7) Å; b = 7.1251(3) Å; c = 5.0895(4) Å. All sites are fully occupied within the standard deviations. The structure can be described as typical Laves phase, where Cu and As are forming vertex-linked tetrahedra and Cd adopts the structure motive of a distorted diamond network. Cd4Cu7As was prepared from stoichiometric mixtures of the elements in a solid state reaction at 1000 °C. Magnetic measurements are showing a Pauli paramagnetic behavior. During our systematical investigations within the ternary phase triangle Cd–Cu–As the cubic C15-type Laves phase Cd4Cu6.9(1)As1.1(1) was structurally characterized. It crystallizes cubic in the space group Fd3m̅ with lattice parameter a = 7.0779(8) Å. Typically for quasi-binary Laves phases Cu and As are both occupying the 16c site. Chemical bonding, charge transfer and atomic properties of Cd4Cu7As were analyzed by band structure, ELF, and AIM calculations. On the basis of the general formula for Laves phases AB2, Cd is slightly positively charged forming the A substructure, whereas Cu and As represent the negatively charged B substructure in both cases. The crystal structure distortion is thus related to local effects caused by Arsenic that exhibits a larger atomic volume (18 Å3 compared to 13 Å3 for Cu) and higher ionicity in bonding.

Recently silver(I)-(poly)chalcogenides have received special interest in energy conversion materials because of their thermoelectric and resistivity switching properties. In order to understand these features, a new topological principle has been developed, which is an useful tool to plan new synthesis strategies and to vary functional properties. It has been shown that anion substitution is powerful tool to tune the physical properties in terms of a thermoelectric performance optimization. Herein we report on the recently introduced substance class of silver(I)-(poly)chalcogenidehalides and the well-established class of silver(I)-chalcogenidehalides. We focus our report on the electrochemical behaviour of all known silver-(poly)telluridehalides Ag10Te4Br3, Ag23Te12Br, Ag20Te10BrI,Ag5Te2Cl and selected substituted phases.Highlights► Silver(I)-polychalcogenide halides are effective phonon scatterer due to attractive interactions. ► Low dimensional units are responsible for the tuning of the electronic structure. ► Thermopower and thermoelectric performance can be manipulated by such interactions.

A selection of mixed conducting silver chalcogenide halides of the general formula Ag5Q2X with Q=sulfur, selenium and tellurium and X=chlorine and bromine has been investigated due to their thermoelectric properties. Recently, the ternary counterpart Ag5Te2Cl showed a defined d10–d10 interaction in the disordered cation substructure at elevated temperatures where Ag5Te2Cl is present in its high temperature α-phase. A significant drop of the thermal diffusivity has been observed during the β−α phase transition reducing the values from 0.12 close to 0.08 mm2 s−1. At the same transition the thermopower reacts on the increasing silver mobility and jumps towards less negative values.Thermal conductivities, thermopower and thermal diffusivity of selected compounds with various grades of anion substitution in Ag5Q2X were determined around the silver-order/disorder β−α phase transition. A formation of attractive interactions could be observed for selenium substituted phases while no effect was detected for bromide and sulfide samples. Depending on the grade and type of substitution the thermopower changes significantly at and after the β−α phase transition. Thermal conductivities are low reaching values around 0.2–0.3 W m−1 K−1 at 299 K. Partial anion exchange can substantially tune the thermoelectric properties in Ag5Q2X phases.Graphical abstractA structure section of the α-Ag5Te2Cl structure type and the thermopower evolution of Ag5Te2Cl0.4Br0.6 undergoing a silver ion order/disorder phase transition.Figure optionsDownload full-size imageDownload as PowerPoint slideResearch highlights► We report on thermoelectric properties of silver(I) chalcogenide halides. ► We examine thermopower, thermal diffusivity and thermal behavior. ► Silver mobility, phase transitions and order/disorder phenomena are discussed. ► Partial anion exchange can tune thermoelectric properties significantly.

Antimony containing compounds have drawn interest as anode materials in Li batteries due to their high Li packing density and the resulting volumetric charge density. Reasonable specific capacities outperforming graphite by a factor of 2 have been reported for antimonides and polyantimonides. Together with good cycling stabilities, rate capabilities and a high potential level against Li metal, both classes of materials are discussed as potential candidates to substitute carbonaceous hosts. Unfortunately, severe volume expansion during the reaction with lithium takes place which has to be taken into account during optimization of the systems. This feature demands size tailoring and electrode optimization to push the electrochemical performance and the lifetime of half cells and full batteries in applicable dimensions. While antimonides are more or less intermetallic compounds, performing a conversion reaction to electrochemical active (in most cases Sb) and non-active species, polyantimonides can offer a greater flexibility due to their anisotropic structural features. Polyantimonides, containing simple dumbbells up to layered arrangements of covalently bonded antimony, can provide voids or interstitials for insertion and intercalation of lithium. The chance to preserve such favourable structural features during this process is in principle higher than for antimonides where conversion reactions to other species take place.Herein we report on structural features and electrochemical performance of antimony containing active materials for anodes in lithium batteries. Our focus lies on recent developments in polyantimonides chemistry but we will also address the scientific progress with antimonides.

•Preparation of uniform 15–20 nm nanospheres of metastable Pna21-LiCoPO4 polymorph.•Structure redetermination shows cation-mixing (Co blocking Li sites).•In situ investigation of phase transformation to olivine Pnma-LiCoPO4 at 527 °C.•Pna21-LiCoPO4 reemerges as a stable high-temperature phase above 800 °C.•X-ray absorption spectroscopy confirms local tetrahedral symmetry (Td Co2+).The majority of research activities on LiCoPO4 are focused on the phospho-olivine (space group Pnma), which is a promising high-voltage cathode material for Li-ion batteries. In contrast, comparably little is known about its metastable Pna21 modification. Herein, we present a comprehensive study on the structure–property relationships of 15–20 nm Pna21-LiCoPO4 nanospheres prepared by a simple microwave-assisted solvothermal process. Unlike previous reports, the results indicate that the compound is non-stoichiometric and shows cation-mixing with Co ions on the Li sites, which provides an explanation for the poor electrochemical performance. Co L2,3-edge X-ray absorption spectroscopic data confirm the local tetrahedral symmetry of Co2+. Comprehensive studies on the thermal stability using thermogravimetric analysis, differential scanning calorimetry, and in situ powder X-ray diffraction show an exothermic phase transition to olivine Pnma-LiCoPO4 at 527 °C. The influence of the atmosphere and the particle size on the thermal stability is also investigated.Blue nano-sized Pna21-LiCoPO4, featuring tetrahedrally-coordinated Co2+, was synthesized in a rapid one-step microwave-assisted solvothermal process. The phase relation between this metastable and the stable polymorph was analyzed and electrochemical properties are discussed.

•Preparation of LiCoPO4 platelets by simple microwave-assisted solvothermal process.•Influence of solvent on morphology and electrochemical performance is investigated.•Co-solvent plays a key role in tuning the size, shape and orientation of crystals.•LiCoPO4 from triethylene glycol co-solvent shows best electrochemical performance.•Discharge capacity of 141 mAh g−1 and energy density of 677 Wh kg−1 are reached.High-performance particles of the high-voltage cathode material LiCoPO4 for Li-ion batteries are synthesized by a simple and rapid one-step microwave-assisted solvothermal route at moderate temperatures (250 °C). Using a variety of water/alcohol 1:1 (v:v) solvent mixtures, including ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), tetraethylene glycol (TTEG), polyethylene glycol 400 (PEG), and benzyl alcohol (BA), the focus of the study is set on optimizing the electrochemical performance of the material by controlling the particle size and morphology. Scanning electron microscopy studies reveal a strong influence of the co-solvent on the particle size and morphology, resulting in the formation of variations between square, rhombic and hexagonal platelets. According to selected area electron diffraction experiments, the smallest crystal dimension is in the [010] direction for all materials, which is along the lithium diffusion pathways of the olivine crystal structure. The anisotropic crystal orientations with enhanced Li-ion diffusion properties result in high initial discharge capacities and gravimetric energy densities (up to 141 mAh g−1 at 0.1 C and 677 Wh kg−1 for LiCoPO4 obtained from TEG), excellent rate capabilities, and cycle life for 20 cycles.

•Large black phosphorus crystals were grown by a short way transport reaction.•In situ neutron diffraction affirms the formation of black P directly from gas phase.•Large crystals can be used as starting material for phosphorene synthesis.Single crystals of orthorhombic black phosphorus can be grown by a short way transport reaction from red phosphorus and Sn/SnI4 as mineralization additive. Sizes of several millimeters can be realized with high crystal quality and purity, making a large area preparation of single or multilayer phosphorene possible. An in situ neutron diffraction study was performed addressing the formation of black phosphorus. Black phosphorus is formed directly via gas phase without the occurrence of any other intermediate phase. Crystal growth was initiated after cooling the starting materials down from elevated temperatures at 500 °C.

Solids with high ion mobility are of broad interest for energy storage applications. New systems featuring low-activated ion mobility are important to improve the performance in such systems. Herein we report on a model system dealing with such improved properties. Li0.2CdP2 was synthesized from the elements, lithium as structure stabilizer and CdI2 as reaction promoters in sealed silica ampoules at 823 K. It crystallizes tetragonal, in space group I4122 (α-CdAs2 structure type), with lattice parameters a = 7.6691(8) Å, c = 4.4467(4) Å and V = 261.53(4) Å3. After 24 h of storage in air lithium ions can be removed in a spontaneous delithiation reaction resulting in Li(OH)·H2O formation on the surface of the crystals. Formed α′-CdP2 adopts the α-CdAs2 structure type. Both compounds consist of isolated cadmium atoms and helical 1∞[P−]-chains generating empty channels suitable to accommodate Li ions. The heavy atom structure was determined by X-ray diffraction methods while a full model including lithium was derived from a combined solid state NMR and quantum chemical calculation approach. An low activation barrier range in the order of 0.1 to 0.2 eV was determined by NMR spectroscopy pointing towards an extraordinary high Li mobility in Li0.2CdP2. Of course a Cd-based solid will have certain disadvantages like toxicity and mass for storage applications but substitution of Cd by suitable lighter elements can solve this issue.