Pressure-driven relaxation processes in nanocomposite ionic glass LiFe0.75_{0.75}V0.10_{0.10}PO4_{4}

This paper presents results for systems formed in a solid glassy state after nanocrystallization process above the glass temperature. We analyze electric conductivity and relaxation processes after such treatment under high temperature (HT) and high pressure (HP-HT) as well. The latter leads to ca. 8% increase of density, two decades (100) increase of electric conductivity as well as qualitative changes in relaxation processes. The previtreous-type changes of the relaxation time on cooling is analyzed by the use of critical-like and the 'critical-activated' description. Presented results correspond well with obtained for this material and shown in ref. [8]. The evidence for pressure evolution of the glass and crystallization temperatures, indicating the unique possibility of maxima and crossovers is also reported

Observation of Metal–Insulator Transition (MIT) in Vanadium Oxides V₂O₃ and VO₂ in XRD, DSC and DC Experiments

Due to metal–insulator transitions occurring in those compounds, materials and devices based on vanadium (III) and (IV) oxides draw increasing scientific attention. In this paper, we observed the transitions in both oxides using contemporary laboratory equipment. Changes in the crystallographic structure were precisely investigated as a function of the temperature with a step of 2 °C. Thermal effects during transitions were observed using differential scanning calorimetry. The DC conductivity of the materials was measured quasi-continuously as a function of the temperature. All the experiments were consistent and showed considerable hysteresis of the metal–insulator transition in both vanadium oxides

Electrochemical performance of highly conductive nanocrystallized glassy alluaudite-type cathode materials for NIBs

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 (Na2Fe3(PO4)3—FFF, Na2VFe2(PO4)3—VFF, and Na2VFeMn(PO4)3—VFM) were synthesized and subjected to an optimized thermal nanocrystallization. This procedure resulted in nanostructured samples with increased electrical conductivity at room temperature: 5×10−7 S/cm (FFF), 7×10−5 S/cm (VFM), and 6×10−4 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

Electrochemical Performance of Highly Conductive Nanocrystallized Glassy Alluaudite-Type Cathode Materials for NIBs

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 (Na2Fe3(PO4)3—FFF, Na2VFe2(PO4)3—VFF, and Na2VFeMn(PO4)3—VFM) were synthesized and subjected to an optimized thermal nanocrystallization. This procedure resulted in nanostructured samples with increased electrical conductivity at room temperature: 5×10−7 S/cm (FFF), 7×10−5 S/cm (VFM), and 6×10−4 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

Novel High-Pressure Nanocomposites for Cathode Materials in Sodium Batteries

A new nanocomposite material was prepared by high pressure processing of starting glass of nominal composition NaFePO4. 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

Electrochemical Properties of Pristine and Vanadium Doped LiFePO₄ Nanocrystallized Glasses

In our recent papers, it was shown that the thermal nanocrystallization of glassy analogs of selected cathode materials led to a substantial increase in electrical conductivity. The advantage of this technique is the lack of carbon additive during synthesis. In this paper, the electrochemical performance of nanocrystalline LiFePO4 (LFP) and LiFe0.88V0.08PO4 (LFVP) cathode materials was studied and compared with commercially purchased high-performance LiFePO4 (C-LFP). The structure of the nanocrystalline materials was confirmed using X-ray diffractometry. The laboratory cells were tested at a wide variety of loads ranging from 0.1 to 3 C-rate. Their performance is discussed with reference to their microstructure and electrical conductivity. LFP exhibited a modest electrochemical performance, while the gravimetric capacity of LFVP reached ca. 100 mAh/g. This value is lower than the theoretical capacity, probably due to the residual glassy matrix in which the nanocrystallites are embedded, and thus does not play a significant role in the electrochemistry of the material. The relative capacity fade at high loads was, however, comparable to that of the commercially purchased high-performance LFP. Further optimization of the crystallites-to-matrix ratio could possibly result in further improvement of the electrochemical performance of nanocrystallized LFVP glasses