RESUMEN
The synthesis of langbeinite-type phosphates with small cations such as Li+ or Na+via a high-temperature solid-state reaction is a challenging task due to the predominant formation of a related NaSICON-type phase. This work reports on the synthesis route, crystal structure, thermal behavior, and Na-conductive properties of the langbeinite-type NaZr2(PO4)3 prepared by a mechanochemically activated ion-exchange reaction between hydrothermally prepared NH4Zr2(PO4)3 and NaNO3. The crystal structure of NaZr2(PO4)3 is refined based on X-ray diffraction data and validated by Fourier-transformed infrared spectroscopy. NaZr2(PO4)3 is found to be stable up to 730 °C, undergoing a transformation into the NaSICON phase with further heating. Notably, in the 25-500 °C range, the material shows negative thermal expansion. The Na+ conductivity within the range of 50-225 °C amounts to 1.7 × 10-8 S cm-1 at 50 °C and 1 × 10-6 S cm-1 at 225 °C with an activation energy of 0.44 eV, accompanied by a sufficiently low (â¼10-12 S cm-1) electronic conductivity. The bandgap of 4.44 eV and the electrochemical stability window covering the 1.39-4.18 V vs. Na/Na+ range are calculated using density functional theory. The obtained results open up opportunities for designing langbeinite-structured phosphates as potential solid electrolytes for Na-ion batteries.
RESUMEN
A novel vanadium hydroxide-phosphate, NH4 VPO4 OH, was synthesized hydrothermally in V2 O5 -NH4 H2 PO4 -citric acid system at 230 °C. It was characterized by XRD, TG-DSC, SEM-EDX, FTIR and NMR spectroscopy. NH4 VPO4 OH is isostructural with NH4 GaPO4 OH and features edge-sharing chains of VO6 octahedra. These chains running along [010] direction of the unit cell are connected by phosphate tetrahedra to form infinite layers parallel to the (100) plane. Ammonium cations are embedded between the heteropolyhedral layers. According to the thermodynamic and NMR measurements supported by the first-principles calculations, NH4 VPO4 OH presents a rare case of Haldane spin system with spin S=1 based on V3+ ions.
RESUMEN
Advanced ionic conductors are crucial for a large variety of contemporary technologies spanning solid state ion batteries, fuel cells, gas sensors, water desalination, etc. In this work, we report on a new member of KTiOPO4-structured materials, NaGaPO4F, with sodium-ion conductivity. NaGaPO4F has been obtained for the first time via a facile two-step synthesis consisting of a hydrothermal preparation of an ammonia-based precursor, NH4GaPO4F, followed by an ion exchange reaction with NaNO3. Its crystal structure was precisely refined using a combination of synchrotron X-ray powder diffraction and electron diffraction tomography. The material is thermally stable upon 450 °C showing no significant structural transformations or degradation but only a â¼1% cell volume expansion. Na-ion mobility in NaGaPO4F was investigated by a joint experimental and computational approach comprising solid-state nuclear magnetic resonance (NMR) and density functional theory (DFT). DFT and bond-valence site energy (BVSE) calculations reveal 3D diffusion of sodium in the [GaPO4F] framework with migration barriers amounting to 0.22 and 0.44 eV, respectively, while NMR yields 0.3-0.5 eV that, being coupled with a calculated bandgap of â¼4.25 eV, makes NaGaPO4F a promising fast Na-ion conductor.
RESUMEN
Metal-organic compounds (MOFs) are a class of substances composed of metal ions or clusters coordinated to organic ligands to form one-, two-, or three-dimensional structures. Due to their high porosity, excellent adsorption and catalytic activity, as well as the possibility of simultaneous implementation of various charge accumulation mechanisms, they can be used as electrode materials for metal-ion batteries. However, a significant disadvantage is that most MOFs have a low electrical conductivity, and the production of conductive MOFs is a costly, time-consuming and technically difficult process. In this work, we developed a method for synthesizing the Zn2(EDTA)(H2O) MOF composite and studied the possibility of using it as an anode material for sodium-ion batteries based on aqueous electrolytes. The structure and morphology of the compound was studied using XRD, IR, TGA and SEM. Using cyclic voltammetry, the electrochemical characteristics of the organometallic framework in alkaline electrolytes 1, 10 M NaOH, as well as in saturated aqueous electrolyte NaClO4, were evaluated. It has been established that the studied compound does not give a satisfactory electrochemical response in aqueous electrolytes (both in alkaline and neutral media) due to the strong degradation of the electrode material, which is associated with the high solubility of this MOF representative. Cyclic voltammetric studies showed the presence of two redox processes due to the release of metallic zinc from an electrolyte solution, where two forms of zinc exist in equilibrium (the ZnEDTA complex and the free zinc cation). Therefore, we concluded, it is not possible to use this material as an anode for water-based sodium-ion batteries in contrary to a published research study.
RESUMEN
All-solid-state Li-ion batteries (LIBs) with a solid electrolyte instead of a liquid one demonstrate significantly higher safety in contrast with the conventional liquid-based LIBs. An inorganic NASICON-type Li conductor Li1.3Al0.3Ti1.7(PO4)3 (LATP) is a promising solid electrolyte with an ionic conductivity of up to 10-3 S cm-1 at room temperature. However, LATP gradually degrades in contact with Li metal because of reduction of Ti4+ to Ti3+, resulting in a lower ionic conductivity at the electrolyte-electrode interface. Cation doping is a promising approach to stabilize the LATP structure and mitigate the Ti reduction. Here, we report our findings on the alternative polycationic doping strategy of the LiTi2(PO4)3 (LTP) structure, when a heterovalent cation is added along with Al. In particular, we studied the effect of tetravalent and divalent cation dopants (Zr, Hf, Ca, Mg, Sr) of LATP on the Li-ion conduction and Ti reduction during interaction with lithium metal. The samples were prepared by molten flux and solid-state reaction methods. The structure, morphology, and ion-transport properties of the samples were analyzed. The activation energy of Li-ion migration in all synthesized systems was calculated based on the electrochemical impedance spectroscopy (EIS) data retrieved for a temperature range of 25-100 °C. From the obtained results, the tetravalent doping (Zr4+ and Hf4+) appeared to be a more promissing route to improve the LATP electrolyte than the divalent doping (Mg2+, Ca2+, and Sr2+). The X-ray photoelectron spectroscopy analysis of the samples after their contact with lithium provided the data, which could shed light on the effect of the incorporated dopants onto the Ti reduction.
RESUMEN
Polyanion compounds offer a playground for designing prospective electrode active materials for sodium-ion storage due to their structural diversity and chemical variety. Here, by combining a NaVPO4F composition and KTiOPO4-type framework via a low-temperature (e.g., 190 °C) ion-exchange synthesis approach, we develop a high-capacity and high-voltage positive electrode active material. When tested in a coin cell configuration in combination with a Na metal negative electrode and a NaPF6-based non-aqueous electrolyte solution, this cathode active material enables a discharge capacity of 136 mAh g-1 at 14.3 mA g-1 with an average cell discharge voltage of about 4.0 V. Furthermore, a specific discharge capacity of 123 mAh g-1 at 5.7 A g-1 is also reported for the same cell configuration. Through ex situ and operando structural characterizations, we also demonstrate that the reversible Na-ion storage at the positive electrode occurs mostly via a solid-solution de/insertion mechanism.
RESUMEN
Lithium iron phosphate, LiFePO4, a widely used cathode material in commercial Li-ion batteries, unveils a complex defect structure, which is still being deciphered. Using a combined computational and experimental approach comprising density functional theory (DFT)+U and molecular dynamics calculations and X-ray and neutron diffraction, we provide a comprehensive characterization of various OH point defects in LiFePO4, including their formation, dynamics, and localization in the interstitial space and at Li, Fe, and P sites. It is demonstrated that one, two, and four (five) OH groups can effectively stabilize Li, Fe, and P vacancies, respectively. The presence of D (H) at both Li and P sites for hydrothermally synthesized deuterium-enriched LiFePO4 is confirmed by joint X-ray and neutron powder diffraction structure refinement at 5 K that also reveals a strong deficiency of P of 6%. The P occupancy decrease is explained by the formation of hydrogarnet-like P/4H and P/5H defects, which have the lowest formation energies among all considered OH defects. Molecular dynamics simulation shows a rich structural diversity of these defects, with OH groups pointing both inside and outside vacant P tetrahedra creating numerous energetically close conformers, which hinders their explicit localization with diffraction-based methods solely. The discovered conformers include structural water molecules, which are only by 0.04 eV/atom H higher in energy than separate OH defects.
RESUMEN
Prussian blue analogues (PBAs) are commonly believed to reversibly insert divalent ions, such as calcium and magnesium, rendering them as perspective cathode materials for aqueous magnesium-ion batteries. In this study, the occurrence of Mg2+ insertion into nanosized PBA materials is shown to be a misconception and conclusive evidence is provided for the unfeasibility of this process for both cation-rich and cation-poor nickel, iron, and copper hexacyanoferrates. Based on structural, electrochemical, IR spectroscopy, and quartz crystal microbalance data, the charge compensation of PBA redox can be attributed to protons rather than to divalent ions in aqueous Mg2+ solution. The reversible insertion of protons involves complex lattice water rearrangements, whereas the presence of Mg2+ ion and Mg salt anion stabilizes the proton (de)insertion reaction through local pH effects and anion adsorption at the PBA surface. The obtained results draw attention to the design of proton-based batteries operating in environmentally benign aqueous solutions with low acidity.
RESUMEN
In this paper we report the synthesis of the new layered perovskite oxide carbonate, Ba3Yb2O5CO3. This phase is formed when 3BaCO3 : 1Yb2O3 mixtures are heated in air at temperatures ≤1000 °C, while above this temperature the carbonate is lost and the simple oxide phase Ba3Yb4O9 is observed. The structure of Ba3Yb2O5CO3 was determined from neutron diffraction studies and consists of a tripled perovskite with double Yb-O layers separated by carbonate layers, the first example of a material with such a structure. Further studies showed that analogous Ba3Ln2O5CO3 phases could be formed for other rare earths (Ln = Y, Dy, Ho, Er, Tm and Lu). The results highlight the ability of the perovskite structure to accommodate carbonate groups, and emphasise the need to consider their potential presence particularly for perovskite systems prepared in lower temperature synthesis routes.