Search Results (9)

The new mineral achyrophanite (K,Na)₃(Fe³⁺,Ti,Al,Mg)₅O₂(AsO₄)₅ was found in high-temperature sublimates of the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with aphthitalite-group sulfates, hematite, alluaudite-group arsenates (badalovite, calciojohillerite, johillerite, nickenichite, hatertite, and khrenovite), ozerovaite, pansnerite, arsenatrotitanite, yurmarinite, svabite, tilasite, katiarsite, yurgensonite, As-bearing sanidine, anhydrite, rutile, cassiterite, and pseudobrookite. Achyrophanite occurs as long-prismatic to acicular or, rarer, tabular crystals up to 0.02 × 0.2 × 1.5 mm, which form parallel, radiating, bush-like, or chaotic aggregates up to 3 mm across. It is transparent, straw-yellow to golden yellow, with strong vitreous luster. The mineral is brittle, with (001) perfect cleavage. D_calc is 3.814 g cm^–3. Achyrophanite is optically biaxial (+), α = 1.823(7), β = 1.840(7), γ = 1.895(7) (589 nm), 2V (meas.) = 60(10)°. Chemical composition (wt.%, electron microprobe) is: Na₂O 3.68, K₂O 9.32, CaO 0.38, MgO 1.37, MnO 0.08, CuO 0.82, ZnO 0.48, Al₂O₃ 2.09, Fe₂O₃ 20.42, SiO₂ 0.12, TiO₂ 7.35, P₂O₅ 0.14, V₂O₅ 0.33, As₂O₅ 51.88, SO₃ 1.04, and total 99.40. The empirical formula calculated based on 22 O apfu is Na_1.29K_2.15Ca_0.07Mg_0.34Mn_0.01Cu_0.11Zn_0.06Al_0.44Fe³⁺_2.77Ti_1.00Si_0.02P_0.02S_0.14V_0.04As_4.90O₂₂. Achyrophanite is orthorhombic, space group P222₁, a = 6.5824(2), b = 13.2488(4), c = 10.7613(3) Å, V = 938.48(5) ų and Z = 2. The strongest reflections of the PXRD pattern [d,Å(I)(hkl)] are 5.615(59)(101), 4.174(42)(022), 3.669(31)(130), 3.148(33)(103), 2.852(43)(141), 2.814(100)(042, 202), 2.689(29)(004), and 2.237(28)(152). The crystal structure of achyrophanite (solved from single-crystal XRD data, R = 4.47%) is unique. It is based on the octahedral-tetrahedral M-T-O pseudo-framework (M = Fe³⁺ with admixed Ti, Al, Mg, Na; T = As⁵⁺). Large-cation A sites (A = K, Na) are located in the channels of the pseudo-framework. The achyrophanite structure can be described as stuffed, with the defect heteropolyhedral pseudo-framework derivative of the orthorhombic Fe³⁺AsO₄ archetype. The mineral is named from the Greek άχυρον, straw, and φαίνομαι, to appear, in allusion to its typical straw-yellow color and long prismatic habit of crystals. Full article

Olivine-like NaFePO₄ glasses and nanocomposites are promising materials for cathodes in sodium batteries. Our previous studies focused on the preparation of NaFePO₄ glass, transforming it into a nanocomposite using high-pressure–high-temperature treatment, and comparing both materials’ structural, thermal, and DC electric conductivity. This work focuses on specific features of AC electric conductivity, containing messages on the dynamics of translational processes. Conductivity spectra measured at various temperatures are scaled by apparent DC conductivity and plotted against frequency scaled by DC conductivity and temperature in a so-called master curve representation. Both glass and nanocomposite conductivity spectra are used to test the (effective) exponent using Jonscher’s scaling law. In both materials, the values of exponent range from 0.3 to 0.9, with different relation to temperature. It corresponds to the electronic conduction mechanism change from low-temperature Mott’s variable range hopping (between Fe²⁺/Fe³⁺ centers) to phonon-assisted hopping, which was suggested by previous DC measurements. Following the pressure treatment, AC conductivity activation energies were reduced from $E_{AC}\approx 0.40 \mathrm{e}\mathrm{V}$ for glass to $E_{AC}\approx 0.18 \mathrm{e}\mathrm{V}$ for nanocomposite and are lower than their DC counterpart, following a typical empirical relation with the value of the exponent. While pressure treatment leads to a 2–3-orders-of-magnitude rise in the AC and apparent DC conductivity due to the reduced distance between the hopping centers, a nonmonotonic relation of AC power exponent and temperature is observed. It occurs due to the disturbance of polaron interactions with Na⁺ mobile ions. Full article

Recently, an interest in NASICON-type materials revived, as they are considered potential cathode materials in sodium–ion batteries used in large-scale energy storage. We applied a facile technique of thermal nanocrystallization of glassy analogs of these compounds to enhance their electrical parameters. Six nanomaterials of the Na₃M₂(PO₄)₂F₃ (M = V, Ti, Fe) system were studied. Samples with nominal compositions of Na₃V₂(PO₄)₂F₃, Na₃Ti₂(PO₄)₂F₃, Na₃Fe₂(PO₄)₂F₃, Na₃TiV(PO₄)₂F₃, Na₃FeV(PO₄)₂F₃ and Na₃FeTi(PO₄)₂F₃ have been synthesized as glasses using the melt-quenching method. X-ray diffraction measurements were conducted for as-synthesized samples and after heating at elevated temperatures to investigate the structure. Extensive impedance measurements allowed us to optimize the nanocrystallization process to enhance the electrical conductivity of cathode nanomaterials. Such a procedure resulted in samples with the conductivity at room temperature ranging from $1\times {10}^{-9}$ up to $8\times {10}^{-5}$ S/cm. We carried out in situ impedance spectroscopy measurements (in an ultra-high-frequency range up to 10 GHz) and compared them with thermal events observed in differential thermal analysis studies. Full article

A new nanocomposite material was prepared by high pressure processing of starting glass of nominal composition NaFePO${}_4$. Thermal, structural, electrical and dielectric properties of the prepared samples were studied by differential thermal analysis (DTA), X-ray diffraction (XRD) and broadband dielectric spectroscopy (BDS). It was demonstrated that high-pressure–high-temperature treatment (HPHT) led to an increase in the electrical conductivity of the initial glasses by two orders of magnitude. It was also shown that the observed effect was stronger than for the lithium analogue of this material studied by us earlier. The observed enhancement of conductivity was explained by Mott’s theory of electron hopping, which is more frequent in samples after pressure treatment. The final composite consisted of nanocrystalline NASICON (sodium (Na) Super Ionic CONductor) and alluaudite phases, which are electrochemically active in potential cathode materials for Na batteries. Average dimensions of crystallites estimated from XRD studies were between 40 and 90 nm, depending on the phase. Some new aspects of local dielectric relaxations in studied materials were also discussed. It was shown that a combination of high pressures and BDS method is a powerful method to study relaxation processes and molecular movements in solids. It was also pointed out that high-pressure cathode materials may exhibit higher volumetric capacities compared with commercially used cathodes with carbon additions. Full article

Alluaudite-type materials are systematically attracting more attention as prospective cathode materials for sodium-ion batteries. It has been demonstrated that optimized thermal nanocrystallization of glassy analogs of various cathode materials may lead to a significant increase in their electrical conductivity. In this paper, three alluaudite-like glasses (Na${}_2$Fe${}_3$(PO${}_4$)${}_3$—FFF, Na${}_2$VFe${}_2$(PO${}_4$)${}_3$—VFF, and Na${}_2$VFeMn(PO${}_4$)${}_3$—VFM) were synthesized and subjected to an optimized thermal nanocrystallization. This procedure resulted in nanostructured samples with increased electrical conductivity at room temperature: $5\times {10}^{-7}$ S/cm (FFF), $7\times {10}^{-5}$ S/cm (VFM), and $6\times {10}^{-4}$ S/cm (VFF). The nanocrystalline microstructure was also evidenced by ultra-high-frequency impedance spectroscopy (up to 10 GHz) and proposed electrical equivalent circuits. Prototype electrochemical cells were assembled and characterized with voltage cutoffs of 1.5 and 4.5 V. The electrochemical performance was, however, modest. The gravimetric capacity varied between the studied materials, but did not exceed 35 mAh/g. Capacity retention after ca. 100 cycles was satisfactory. Further optimization of the residual-glass-to-nanocrystallite volume ratio would be desirable. Full article

In this study, a new cobalt arsenate belonging to the alluaudite supergroup compounds with the general formula of Co₃(AsO₄)_0.5+x(HAsO₄)_2−x(H₂AsO₄)_0.5+x[(H,□)_0.5(H₂O,H₃O)_0.5]^2x+ (denoted as CoAsAllu) was synthesized under hydrothermal conditions. Its crystal structure was determined by a room-temperature single-crystal X-ray diffraction analysis: space group C2/c, a = 11.6978(8), b = 12.5713(7), c = 6.7705(5) Å, β = 113.255(5)°, V = 914.76(11) ų, Z = 2 for As₆H₈Co₆O₂₅. It represents a new member of alluaudite-like protonated arsenates and the first alluaudite-like phase showing both protonation of the tetrahedral site and presence of the H₂O molecules in the channels. In the asymmetric unit of CoAsAllu, one of the two Co, one of the two As and one of the seven O atoms lie at 4e special positions (site symmetry 2). The crystal structure consists of the infinite edge-shared CoO₆ octahedra chains, running parallel to the [10$\overline{1}$] direction. The curved chains are interconnected by [(As1O₄)_0.5(H₂As1O₄)_0.5]²⁻ and [HAs₂O₄]²⁻ tetrahedra forming a heteropolyhedral 3D open framework with two types of parallel channels. Both channels run along the c-axis and are located at the positions (1/2, 0, z) and (0, 0, z), respectively. The H2 and H4 hydrogen atoms of O2H2 and O4H4 hydroxyl groups are situated in channel 1, while the uncoordinated water molecule H₂O7 at half-occupied 4e special positions and hydrogen atoms of O6H6 hydroxyl group were found in channel 2. The results of the magnetic investigations confirm the quasi one-dimensional structure of divalent cobalt ions. They are antiferromagnetically coupled with the intrachain interaction parameter of J ≈ −8 cm⁻¹ and interchain parameter of J’ ≈ −2 cm⁻¹ that become effective below the Néel temperature of 3.4 K. Full article

Alluaudite-type materials are systematically attracting more attention as prospective cathode materials for sodium ion batteries. In this paper, we strove to optimize various synthesis parameters of three alluaudite compositions (Na${}_2$Fe${}_3$(PO${}_4$)${}_3$—FFF, Na${}_2$VFe${}_2$(PO${}_4$)${}_3$—VFF, and Na${}_2$VFeMn(PO${}_4$)${}_3$—VFM) to obtain nanostructured alluaudite-type glass-ceramics with high phase purity. We systematically investigated the role of the chemical reactions, temperature and time of melting, cooling rate, and reducing factors on the quality of the final products. A detailed synthesis protocol along with X-ray diffractometry, thermal analysis, scanning electron microscopy imaging, and electrical conductivity measurements (with impedance spectroscopy) are reported. As a result, a significant increase of the conductivity was observed in the nanomaterials. The highest value was reached for the VFF composition and was equal to $6\times {10}^{-4}$ S/cm at room temperature. Full article

High-voltage generation (over 4 V versus Li⁺/Li) of polyanion-positive electrode materials is usually achieved by Ni³⁺/Ni²⁺, Co³⁺/Co²⁺, or V⁴⁺/V³⁺ redox couples, all of which, however, encounter cost and toxicity issues. In this short review, our recent efforts to utilize alternative abundant and less toxic Fe³⁺/Fe²⁺ and Cr⁴⁺/Cr³⁺ redox couples are summarized. Most successful examples are alluaudite Na₂Fe₂(SO₄)₃ (3.8 V versus sodium and hence 4.1 V versus lithium) and β₁-Na₃Al₂(PO₄)₂F₃-type Na₃Cr₂(PO₄)₂F₃ (4.7 V versus sodium and hence 5.0 V versus lithium), where maximizing ΔG by edge-sharing Fe³⁺-Fe³⁺ Coulombic repulsion and the use of the 3d²/3d³ configuration of Cr⁴⁺/Cr³⁺ are essential for each case. Possible exploration of new high-voltage cathode materials is also discussed. Full article

A new sodium manganese-nickel phosphate of alluaudite supergroup with the general formula NaMnNi₂(H_2/3PO₄)₃ was synthesized by a hydrothermal method. The synthesis was carried out in the temperature range from 540 to 660 K and at the general pressure of 80 atm from the oxides mixture in the molar ratio MnCl₂: 2NiCl₂: 2Na₃PO₄: H₃BO₃: 10H₂O. The crystal structure was studied by a single-crystal X-ray diffraction analysis: space group C2/c (No. 15), a = 16.8913(4), b = 5.6406(1), c = 8.3591(3) Å, β = 93.919(3), V = 794.57(4) ų. The compound belongs to the alluaudite structure type based upon a mixed hetero-polyhedral framework formed by MX₆-octahedra and TX₄-tetrahedra. The characteristic feature of the title compound is the absence of cations or H₂O molecules in channel II, while the negative charge of the framework is balanced by the partial protonation of PO₄ tetrahedra. The presence of the transition metals at the A-type sites results in the changes of stoichiometry and the local topological features. Topological analysis of the hetero-polyhedral alluaudite-type frameworks and its derivatives (johillerite-, KCd₄(VO₄)₃-, and keyite-type) and quantitative characterization of their differences was performed by means of natural tilings. Full article